The results of a combined chemico-osmotic/diffusion experiment conducted on a geosynthetic clay liner (GCL) containing Na-bentonite illustrate the destructive role of diffusion on the ability of the GCL to act as a semipermeable membrane. The experiment is conducted by maintaining a concentration difference of 5 mM CaCl2 across the GCL specimen while preventing the flow of solution through the specimen. A time-dependent membrane efficiency is derived from measured pressure differences induced across the specimen in response to the applied concentration difference. The diffusive mass fluxes of the solutes (Cl− and Ca2+) through the specimen are also measured simultaneously. An initial increase in induced pressure difference across the specimen to a peak value of 19.3 kPa is observed, followed by a gradual decrease to zero. The decrease in induced pressure difference is consistent with compression of diffuse double layers between clay particles and particle clusters due to diffusion of Ca2+, resulting in a concomitant increase in pore sizes and decrease in the observed membrane behavior. The time required for effective destruction of the initially observed semipermeable membrane behavior correlates well with the time required to achieve steady-state Ca2+ diffusion. The results have important implications for the ability of clays to sustain membrane behavior.

In the Nuussuaq Basin, West Greenland, a thick succession of Tertiary dolerites has penetrated Upper Cretaceous mudstone. The mixed-layer minerals of mudstone core samples have been analyzed by X-ray diffraction, solid-state 29Si and 27A1 magic-angle spinning nuclear magnetic resonance, Mössbauer and infrared spectroscopies, thermal analysis, chemical analysis, stable isotopes (18O/16O), and K/Ar dating. The mixed-layer minerals include for each sample two mixed-layer phases consisting of pyrophyllite, margarite, paragonite, tobelite, illite, smectite and vermiculite layers. The main, 80 m thick intrusion resulted in the formation of pyrophyllite, margarite, paragonite and tobelite layers. However, the tobelite layers are absent in samples <21 m from this intrusion. Furthermore, chlorite was formed and kaolinite destroyed in samples adjacent to minor intrusions and at distances <60 m from the large intrusion. For the first time, the detailed, complex mixed-layer structures formed during contact metamorphism of kaolinitic, oil-forming mudstones have been investigated accurately. The formation of tobelite layers reveals that oil formation has taken place during contact metamorphism. Furthermore, K/Ar dating of mixed-layer minerals from shale indicates that the intrusives are of early Eocene age. The 80 m thick intrusive is responsible for the main mixed-layer transformations, whereas two thin (3 m and 0.5 m thick) intrusions contribute little. Thus, the detailed mixed-layer investigation has contributed significantly to the understanding of the regional geology and the contact metamorphic processes.

Mineralogical and geochemical variations among the Carboniferous and Cretaceous sedimentary kaolin deposits from Sinai provided an opportunity to examine the effect of the source area on compositions of the deposits. The Carboniferous kaolin deposits are mineralogically and geochemically heterogeneous. The Khaboba and Hasbar deposits consist of kaolinite, quartz, anatase, illite, chlorite, zircon, and leucoxene. The shale-normalized rare earth element (REE) patterns of the Khaboba deposit showed a slight LREE over HREE enrichment ((La/Yb)SN = 1.19–1.51) with a MREE depletion (Gd/Gd*SN = 0.51–0.75), while the Hasbar kaolin had a MREE enrichment. The Abu Natash kaolin deposit consisted of kaolinite, anatase, and a little quartz with larger TiO2, Cr, and V and smaller Zr and Nb contents compared to other Carboniferous deposits. The shale-normalized REE patterns of the Abu Natash deposit exhibited a positive Eu anomaly (Eu/Eu*SN = 1.28–1.40) and a MREE enrichment (Gd/Gd*SN = 1.41–2.05). The Cretaceous deposits were relatively homogeneous in terms of mineralogical composition and geochemistry and are composed of kaolinite, quartz, anatase, rutile, zircon, and leucoxene. The Cretaceous kaolin deposits showed mostly flat shale-normalized REE patterns with a variable LREE depletion.

The presence of illite and chlorite, the absence of rutile, large Zr and Nb contents, and the REE patterns suggested a component of weathered low-grade metasediments as a source for the Carboniferous deposits in the Khaboba and Hasbar areas, while the large Ti, Cr, and V, and small quartz contents indicated mafic source rocks for the Abu Natash deposit. The abundance of high-Cr rutile and the absence of illite and chlorite, and large Zr, Ti, Cr, and V contents suggested a mixture of medium- to high-grade metamafic and granitic rocks as source rocks for the Cretaceous kaolin deposits. The occurrence of alkaline rocks in the source of the deposits studied was identified by high-Nb contents and the presence of bastnaesite. The mineralogical and geochemical heterogeneity and lesser maturity of the Carboniferous deposits suggested local sources for each deposit and their deposition in basins close to the sources. The mineralogical and geochemical homogeneity and maturity of the Cretaceous deposits, on the other hand, indicated common sources for all deposits and their deposition in relatively remote basins.

Natural and synthetic micas have been used widely as substrates to study biological systems; but, as in the case of negatively charged DNA, anionic charge repulsion may render micas a less than ideal templating surface for many biological systems. The purpose of this study was to investigate the potential for the chlorite clinoclore, which contains a positively charged interlayer octahedral sheet, to serve as a substrate for DNA adsorption. The relationships between clinochlore cleavage characteristics, in terms of nano-morphology, and surface potential are investigated, as are its average crystal chemistry and topology. That the structural features of clinochlore can be used successfully to condense, order, and self assemble complex biomolecules, such as DNA is also proven.

A natural IIb-4 clinochlore [$C\overline{1}$\$\end{document} symmetry, unit-cell parameters a = 0.53301(4); b = 0.92511(6); c = 1.4348(1) (nm); α = 90.420(3); β = 97.509(3); γ = 89.996(4) (°)] with chemical composition $\left({\text{Mg}}_{1.701}{\text{Fe}}_{0.245}^{2+}{\text{Ti}}_{0.004}{\text{Al}}_{0.998}{\text{Cr}}_{0.052}^{3+}\right){\text{Mg}}_3\left({\text{Si}}_{2.939}{\text{Al}}_{1.015}{\text{Fe}}_{0.046}^{3+}\right){\text{O}}_{10}\left({\text{OH}}_{7.913}{\text{F}}_{0.087}\right)$\$\end{document} was selected. The octahedral sites of the silicate layer (<M(1)−O> = 0.2080 nm and <M(2)−O> = 0.2081 nm) are equal and occupied by Mg, whereas the octahedral sites in the interlayer M(3) and M(4) (<M(3)−O> = 0.2088 nm and <M(4) − O> = 0.1939 nm) show different sizes and are mostly completely occupied by divalent (Mg2+ and Fe2+) and trivalent (Al3+) cations, respectively.

The clinochlore cleaved surface is present in two forms: (1) the stripe type (0.40 nm in height, up to several micrometers long and ranging from some nanometers to a few microns in lateral size); and (2) the triangular type (0.40 nm in height). Both features may result either from interlayer sheets whose cleavage weak directions are related to the different M(3) and M(4) site occupancy, or from weak interlayer bonding along specific directions to the 2:1 layer underneath. The cleaved surface, particularly at the cleaved edges, presents high DNA affinity, which is directly related to an average positive surface and ledge potential.

Phenol and its derivatives are regarded as ‘priority pollutants’ and p-nitrophenol (p-NP), in particular, is of great interest due to its toxicity and frequent presence in waste waters and fresh waters. Straightforward, inexpensive methods to identify p-NP in water, however, is lacking. In the present study, an electrochemical technique using clay-modified electrodes to measure p-NP was investigated as a potentially promising method to fill that gap. A glassy carbon electrode (GCE) was modified with a thin layer of Na-enriched bentonite and a series of benzyltrimethylammonium (BTMA+)-bentonites (BTMA+-B) in order to confirm these materials as p-NP electrosensitive. A series of organobentonites was synthesized using different BTMA+/bentonite ratios. The materials obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, and a low-temperature nitrogen adsorptiondesorption method. A monolayer arrangement of BTMA+ within the interlamellar region of beidellite-rich smectite was confirmed. Deterioration of the textural properties was observed with increase of BTMA+ loading. The electro-oxidation of p-NP in an acidic medium on BTMA+-B-modified GCE was investigated. The cyclic voltammetry method with a three-electrode cell was used. The reference electrode was Ag/AgCl in 3 M KCl and a Pt foil was the counter electrode. For each electrochemical measurement, a different BTMA+ loading in BTMA+-B was used as the material for GCE coating and applied as the working electrode. The electrochemical activity of BTMA+-B-based electrodes increased with BTMA+ loading. The results confirmed that the organophylic character of the BTMA+-B-modified surface was the main influence on the electrochemical activity of the BTMA+-B-based GCE; the influence of textural properties was almost negligible. The increased electrode activity toward p-NP was achieved by the adsorption of p-NP on the electrode surface, the process that commonly precedes the electro-oxidation. The present study showed that synthesized materials could potentially be used in an electrochemical test for the presence of p-NP in water solutions.

Nitroaromatic compounds (NACs) are components of munitions commonly found as soil contaminants at military training sites and elsewhere. These compounds pose possible threats to human health and ecological systems. Recent studies indicate that these compounds are strongly retained by smectite clays. The adsorption mechanisms are not fully reconciled, but it is known that the type of exchangeable cation strongly affects NAC affinity for smectites. This study examined the sorption of 1,3-dinitrobenzene, 2,4-dinitrotoluene and naphthalene from water by a smectite clay (SWy-2) saturated with ammonium, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA). In all cases, we observed greater sorption of 2,4-dinitrotoluene compared with 1,3-dinitrobenzene. The sorption isotherms for 2,4-dinitrotoluene and 1,3-dinitrobenzene displayed a concave-downward curve for NH4-SWy-2 and TMA-SWy-2, whereas the isotherms for sorption of HDTMA-SWy-2 and TMPA-SWy-2 were essentially linear. The magnitude of sorption followed the order: NH4-SWy-2 > TMA-SWy-2 > TMPA-SWy-2 > HDTMA-SWy-2 for both compounds. The greater affinity of NACs for NH4- and TMA-SWy-2 is due in part to complex formation between the exchangeable cation and −NO2 groups. These clays also provide near optimal interlayer distances that approximate the molecular thickness of NACs hence promoting the simultaneous interaction of the planar aromatic rings with opposing siloxane surfaces and solute dehydration. Both processes are energetically favorable. In HDTMA-SWy-2, sorption of all solutes is via a partition-dominated process. Solute competition (diminished uptake of one solute in the presence of a second) was observed for TMA-SWy-2 but not HDTMA-SWy-2. This is consistent with an adsorptive mechanism for TMA-SWy-2 and a partitioning mechanism for HDTMA-SWy-2. This study demonstrates that the dominant molecular mechanism of NAC sorption by smectite changes fundamentally from complexation between −NO2 groups and the exchangeable cation (viz. NH4 and TMA) to partitioning for a systematic series of ammonium and quaternary ammonium cations in which the locus of positive charge (the central N atom) is progressively shielded by organic moieties of increasing size.

Mineralization of microbial biomass is a common phenomenon in geothermal habitats, but knowledge of the structure of the minerals formed in these environments is limited. A combination of spectroscopic, microscopic, and stable isotopic methods, as well as the chemical analysis of spring water, were employed in the present study to characterize calcium carbonate minerals deposited in filamentous cyanobacterial mats in different locations of La Duke hot spring, a circumneutral thermal feature near the north entrance of Yellowstone National Park, Montana, USA. Calcite was the primary crystalline mineral phase associated with biofilm-containing deposits closest to the source of the spring and the suspended microbial biomass in a pool further from the source. The carbonate minerals at all sites occurred as aggregated granules, ~2 μm in diameter, in close association with the microbial biomass. Only in the deposits closest to the source were the granules organized as laminated structures interspersed with microbial biomass. The calcium carbonate grains contained two distinct regions: a dense monolithic calcite core and a porous dendritic periphery containing organic matter (OM). Electron energy loss spectroscopy (EELS) indicated that the voids were infilled with OM and carbonates. The EELS technique was employed to distinguish the source of carbon in the organic matter and carbonate mixture. The studies of carbon isotope compositions of the calcium carbonates and the saturation indices for calcite in the spring waters suggest that processes (abiotic vs. biotic) controlling the carbonate formation may vary among the sampling sites.

In the present study, the gradual layer-charge reduction of two Li-saturated smectites, SAz-1 from Arizona, USA, and FEO-G from Troodos, Cyprus, with octahedral charge of 0.54 electrons per half unit cell (e/huc) and 0.39 e/huc, respectively, was monitored by X-ray diffraction of K-saturated, ethylene glycol-solvated samples, by thermogravimetry-differential thermogravimetry, and by mid- and near-Fourier transform infrared spectroscopy after heating at 80–300ºC. With increasing heating temperature, the layer charge and cation exchange capacity (CEC) of both smectites decreased gradually due to Li fixation. At temperatures >200ºC, ~25% residual CEC was observed, suggesting incomplete Li fixation due to kinetic constraints. Dehydration of the original Li-smectites occurred in two steps, one peaking at ~100ºC and another at 175–180ºC. The latter decreased upon progressive Li fixation and vanished from smectites treated above ~125ºC. Dehydroxylation occurred at 635–640ºC in both smectites and was not affected by Li fixation. The second derivative analysis of the infrared spectra showed that Li fixation was manifested in both smectites by the growth of two new sharp OH-stretching fundamentals at ~3640 and 3670 cm−1 and their overtones at ~7115 and 7170 cm−1. The new bands constitute pairs of fixed energy and relative intensity which grow simultaneously at the expense of the broad OH-stretching and overtone features of the original smectites. Based on this result, Li fixation is suggested to be accompanied by the simultaneous formation of two distinct trioctahedral-like structural OH species, which is compatible with Li+ occupying trans-octahedral vacancies in both smectites.

Iron oxides, typical constituents of many soils, represent a natural immobilization mechanism for toxic elements. Most iron oxides are formed during the transformation of poorly crystalline ferrihydrite to more crystalline iron phases. The present study examined the impact of well known contaminants, such as P(V), As(V), and Sb(V), on the ferrihydrite transformation and investigated the transformation products with a set of bulk and nano-resolution methods. Irrespective of the pH, P(V) and As(V) favor the formation of hematite (α-Fe2O3) over goethite (α-FeOOH) and retard these transformations at high concentrations. Sb(V), on the other hand, favors the formation of goethite, feroxyhyte (d’-FeOOH), and tripuhyite (FeSbO4) depending on pH and Sb(V) concentration. The elemental composition of the transformation products analyzed by inductively coupled plasma optical emission spectroscopy show high loadings of Sb(V) with molar Sb:Fe ratios of 0.12, whereas the molar P:Fe and As:Fe ratios do not exceed 0.03 and 0.06, respectively. The structural similarity of feroxyhyte and hematite was resolved by detailed electron diffraction studies, and feroxyhyte was positively identified in a number of the samples examined. These results indicate that, compared to P(V) and As(V), Sb(V) can be incorporated into the structure of certain iron oxides through Fe(III)-Sb(V) substitution, coupled with other substitutions. However, the outcome of the ferrihydrite transformation (hematite, goethite, feroxyhyte, or tripuhyite) depends on the Sb(V) concentration, pH, and temperature.

Adsorption isotherms and differential heats of adsorption of water vapor by muscovite were measured at 303 K. The heats of adsorption are stepwise and each step corresponds to the stoichiometric formation of adsorption complexes of H2O molecules with K+ ions, (H2O)n/K+, (n = 1–6), which are located on the basal and lateral (edge) faces. At saturation, the ditrigonal cavities of the basal faces are fully occupied by hexameric clusters. It is suggested that half of the K+ ions on the basal faces come from neighboring layers by migration under the influence of the adsorbed H2O at the initial stage of adsorption. Similar migration of K+ to the edges was also hypothesized, suggesting that only every second site can be occupied by a cluster. At the final stage of adsorption, H2O molecules are believed to form H-bonded bridges between the hexameric water/cation clusters on the basal faces, whereas on the edge faces no such effect is believed to occur. The mean molar integral adsorption entropy of water is ∼−7 J/mol K less than the molar entropy of the bulk liquid. The mobility of H2O on muscovite is slightly less than in bulk water. Migration of K+ cations under the influence of adsorbed H2O both on the basal and lateral faces of muscovite is reversible.

Previous studies of dispersant—aqueous kaolin dispersions have indicated clearly that the concentration of the dispersant determines the type of rheological behavior. Those studies focused on the use of dispersant concentrations below the limit of saturation, ignoring what might have happened at concentrations above that limit, and the practical uses to which such information might be put. The present study examined the influence of sodium hexametaphosphate dispersant on the viscous and viscoelastic properties of aqueous kaolin dispersions when its concentration was greater than the saturation limit. A concentric-cylinders geometry sensor system (with a narrow gap between the cylinders) was used to test the rheological behavior of Na hexametaphosphate-aqueous kaolin dispersions. Aqueous kaolin dispersions were viscoplastic, thixotropic, and viscoelastic fluids. The analysis of frequency sweep tests in the linear viscoelastic limit and steady-flow curves led to the conclusion that an increase in the dispersant concentration above the limit of saturation gave way to ‘solid-like’ dispersions.

Montmorillonite (Mnt)-based solid acids have a wide range of applications in catalysis and adsorption of pollutants. For such solid acids, the acidic characteristic often plays a significant role in these applications. The objective of the current study was to examine the effects of H3PO4-activation and supporting WO3 on the textural structure and surface acidic properties of Mnt. The Mnt-based solid acid materials were prepared by H3PO4 treatment and an impregnation method with a solution of ammonium metatungstate (AMT) and were examined as catalysts in the dehydration of glycerol to acrolein. The catalysts were characterized by nitrogen adsorption-desorption, powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultraviolet-visible (DR UV-Vis) spectroscopy, temperature programmed desorption of NH3 (NH3-TPD), diffuse reflectance Fourier-transform infrared (DR FTIR) spectroscopy of adsorbed pyridine, and thermogravimetric (TG) analyses. The phosphoric acid treatment of Mnt created Brönsted and Lewis acid sites and led to increases in specific surface areas, porosity, and acidity. WO3 species influenced total acidity, acid strength, the numbers of Brönsted and Lewis acid sites, and catalytic performances. A high turnover frequency (TOF) value (31.2 h−1) based on a maximal 60.7% yield of acrolein was reached. The correlation of acrolein yield with acidic properties indicated that the cooperative role of Brönsted and Lewis acid sites was beneficial to the formation of acrolein and a little coke deposition (<3.3 wt.%). This work provides a new idea for the design of solid acid catalysts with cooperative Brönsted and Lewis acidity for the dehydration of glycerol.

Geophagy is the intentional consumption of earth. Although widely documented among vulnerable populations, including children and pregnant women, the causes and consequences of geophagy remain poorly understood. Relevant literature was, therefore, reviewed to describe geophagy across species, geographies, life stages, and disease states. After a brief consideration of hypothesized etiologies, the potential harmful and beneficial consequences of geophagy are described, considering current evidence for each. Data available to date suggest that the greatest potential risks of geophagy include toxicity or heavy metal poisoning, and diseases resulting from consumed clays binding nutrients and beneficial pharmaceuticals in the gut. Evidence also suggests that geophagy may be beneficial by protecting against harmful pathogens and toxins through two distinct physiological pathways. Future research should explore causal relationships between geophagy and iron deficiency, as well as investigate the biological and psychosocial conditions that govern geophagy.

Compositional data for 464 clay minerals (2:1 type) were analyzed by statistical techniques. The objective was to understand the similarities and differences between the groups and subgroups and to evaluate statistically clay mineral classification in terms of chemical parameters. The statistical properties of the distributions of total layer charge (TLC), K, VIAl, VIMg, octahedral charge (OC) and tetrahedral charge (TC) were initially evaluated. Critical-difference (P = 1%) comparisons of individual characteristics show that all the clay micas (illite, glauconite and celadonite) differ significantly from all the smectites (montmorillonite, beidellite, nontronite and saponite) only in their TLC and K levels; they cannot be distinguished by their VIAl, VIMg, TC or OC values which reveal no significant differences between several minerals.

Linear discriminant analysis using equal prior was therefore performed to analyze the combined effect of all the chemical parameters. Using six parameters [TLC, K, VIAl, VIMg, TC and OC], eight minerals groups could be derived, corresponding to the three clay micas, four smectites (mentioned above) and vermiculite. The fit between predicted and experimental values was 88.1%. Discriminant analysis using two parameters (TLC and K) resulted in classification into three broad groups corresponding to the clay micas, smectites and vermiculites (87.7% fit). Further analysis using the remaining four parameters resulted in subgroup-level classification with an 85–95% fit between predicted and experimental results. The three analyses yielded D2 Mahalanobis distances, which quantify chemical similarities and differences between the broad groups, within members of a subgroup and also between the subgroups. Classification functions derived here can be used as an aid for classification of 2:1 minerals.

The alignment of phyllosilicates in clays has received a lot of attention because it is a major cause of seismic anisotropy in the Earth’s crust. Thus far, all attention has been on shales where the orientation pattern has been attributed to compaction and observed to increase with burial depth and diagenetic processes. Here, for the first time, the same methods that were developed to quantify shale preferred orientation were applied to clays forming in surface environments, a seasonal streambed in Death Valley, California; a mudpool from mud volcanoes in Imperial Valley, California, close to the Salton Sea; and a glacial lake from Val Albigna in the Swiss Alps. Preferred orientation was analyzed quantitatively with high-energy synchrotron X-ray diffraction. All three samples showed strong alignment of phyllosilicates with (001) pole figure maxima 2–4 multiples of a random distribution, comparable to shales, and indicating that significant preferred orientation can be produced at surface conditions. The original alignment during sedimentation may be an important factor for the final microstructure in many shales.

Late Miocene clayey sediments were deposited in lake-margin and shallow-lake environments of the southeastern Central Anatolian Volcanic Province (CAVP). Yellow to red mudstone, alternating with thin beds of conglomerate and sandstone in the Mustafapaşa Formation, is overlain by altered white Cemilköy ignimbrite. Grain size fines upward in each sequence (conglomerate, sandstone, and mudstone). The occurrence of reddish coloration upward, ripple marks, desiccation cracks, plant rootlets and remnants, and the development of initial-stage paleosols in association with smectite reveal that the area underwent alternating periods of siliciclastic and volcaniclastic sediment supply (wet) and drying. Micromorphologically, the development of spongy smectite in mudstone of the Mustafapaşa Formation and vermiform kaolinite in the Cemilköy ignimbrite on resorbed detrital feldspar and devitrified glass reveals in situ precipitation driven by dissolution and precipitation mechanisms. In addition, alteration of these sediments may have resulted in the depletion of soluble alkaline elements, such as Ca, Na, and K, from the ignimbrite downward into the Mustafapaşa Formation. Alternatively, the leaching of these elements — due to the hydrologically open system of the lake environment — may have resulted in the enhancement of Al+Fe/Si-favored precipitation of kaolinite in an acidic environmental condition, namely, of the altered Cemilköy ignimbrite at the top of the profile of the Mustafapaşa Formation, and of smectite in an alkaline setting within lower-level sediments where carbonate minerals were lacking. The coexistence of smectite with accessory illite indicates that illitization occurred via release of K and Al during excess desorption of feldspar. Large Ni and Co values in mudstone samples, and Fe oxidized and partly chloritized pyroxene and hornblende, indicate that the basin was also affected by ophiolite-related supply.

Chemically modified bentonites are being developed with the aim of preserving low hydraulic conductivity in the presence of potentially aggressive permeants in pollutant-containment applications. ‘Multiswellable’ bentonite (MSB) has been obtained by treating standard sodium bentonite with propylene carbonate. Research on the engineering properties of MSB has focused mainly on permeability and chemical compatibility. Solute diffusion and membrane behavior in MSB have not yet been investigated. A combined chemico-osmotic/diffusion test was performed on a MSB specimen using a 5 mM CaCl2 solution. Permeability with distilled water and with the 5 mM CaCl2 solution was measured prior to and after the chemico-osmotic/diffusion tests. The material exhibited time-dependent membrane behavior with a peak osmotic efficiency value (ω) of 0.172 that gradually shifted to zero upon breakthrough of calcium ions. Effective diffusion coefficients of calcium and chloride ions were in the range commonly described for untreated bentonite at similar porosities. After the chemico-osmotic/diffusion stage and permeation with 5 mM CaCl2, the hydraulic conductivity of MSB increased from 1.1 × 10−11 m/s to 7.0 × 10−11 m/s. The MSB was apparently converted into a calcium-exchanged bentonite at the end of the test. Prehydration and subsequent permeation might have contributed to elution of the organic additive from the clay. Further investigation is recommended to clarify the effect of prehydration on the hydraulic performance of MSB in the presence of potentially aggressive permeants.

The combination of zero-valent iron (ZVI) and a clay-type amendment is often observed to have a synergistic effect on the rate of reduction reactions. In the present study, electrochemical techniques were used to determine the mechanism of interaction between the iron (Fe) and smectite clay minerals. Iron electrodes coated with an evaporated smectite suspension (clay-modified iron electrodes, CMIEs) were prepared using five different smectites: SAz-1, SWa-1, STx-1, SWy-1, and SHCa-1. All the smectites were exchanged with Na+ and one sample of SWy-1 was also exchanged with Mg2+. Potentiodynamic polarization scans and cyclic voltammograms were taken using the CMIEs and uncoated but passivated Fe electrodes. These electrochemical experiments, along with measurements of the amount of Fe2+ and Fe3+ sorbed in the smectite coating, suggested that the smectite removed the passive layer of the underlying Fe electrode during the evaporation process. Cyclic voltammograms taken after the CMIEs were biased at the active-passive transition potential for varying amounts of time suggested that the smectite limited growth of a passive layer, preventing passivation. These results are attributed to the Brønsted acidity of the smectite as well as to its ability to sorb Fe cations. Oxides that did form on the surface of the Fe in the presence of the smectite when it was biased anodically were reduced at a different electrochemical potential from those that form on the surface of an uncoated Fe electrode under otherwise similar conditions; this difference suggested that the smectite reacted with the Fe2+ formed from the oxidation of the underlying Fe. No significant correlation could be found between the ability of the smectite to remove the Fe passive film and the smectite type. The results have implications for the mixing of sediments and Fe particles in permeable reactive barriers, underground storage of radioactive waste in steel canisters, and the use of smectite supports in preventing aggregation of nano-sized zero-valent iron.

Clays of a soil sequence with five profiles in the Val Genova (northern Italy) along an elevation gradient with climate ranging from moderate to Alpine were investigated with XRD using several diagnostic treatments. Smectites developed in the surface horizons of podzolic soils either from chlorite through the removal of hydroxy interlayers or from mica, which weathers in a first step to regularly or irregularly interstratified clay minerals. Citrate treatment allowed the detection of low-charge expandable minerals in the Bhs or Bs horizons. Therefore, the reduction of the charge of 2:1 clay minerals occurred before the removal of hydroxy polymers by fulvic acids and low-weight organic acids. Due to the more intense podzolization process near the tree line, the d060 region showed a temporal evolution of trioctahedral to dioctahedral mineral structures in the well developed Podzols. The pedogenic smectites of the E or Bhs horizons generally included one or several populations with various charges. In most cases, smectite was a heterogeneous mixture of montmorillonite and interstratified beidellite-montmorillonite. A pure beidellite phase could not be detected. The soils near the tree line, where weathering processes were most intense, had two main components: one with a charge >0.75, representing vermiculite-like minerals, and the other with a charge near 0.25, representing smectite. The charges of the beidellitic component and montmorillonite were almost equal. The higher the weathering state of the investigated soils, the lower was the layer charge of smectites.