Kaolinite is often used as a base for the synthesis of new organo-mineral nanomaterials designed for applications in industry and in environmental protection. To make the mineral structure more likely to interact with organic molecules, a kaolinite-methanol complex (KM) can be used. In the present study, different experimental procedures were tested to investigate the formation of the KM. The kaolinitedimethyl sulfoxide intercalation compound (KDS), either wet or dried, was used as a pre-intercalate. The samples obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, CHNS elemental analysis, 13C CP-magic angle spinning nuclear magnetic resonance (MAS NMR), and 27Al and 29Si MAS NMR techniques. The method of density functional theory with dispersion corrections (DFT-D2) was used to explain the structure and to simulate the vibrational spectra of KM. Theoretical results were compared with experimental data. The most effective formation of the KM (d001 = 11.1 Å — wet; d001 = 8.7 Å — dried) was observed when the dried KDS precursor was used. In such conditions the degree of intercalation reached ~98% after 24 h of reaction time. As indicated by the CHNS elemental analysis, ~1/6 of the inner-surface OH groups were grafted by OCH3 groups. The esterification reaction was less efficient at higher temperatures or when wet KDS was used. In the latter case, the excess of very polar dimethyl sulfoxide molecules prevented intercalation of methanol and further grafting. Detailed analysis of the results of theoretical simulations revealed that the reaction of the KDS with methanol led to the formation of kaolinite with both grafted methoxy groups and intercalated methanol, and water molecules in the interlayer space. The spectra calculated revealed the contribution of individual vibrational modes into the complex bands, i.e. the energy of C-H vibrations was in the order: νasCHmet > νasCHmtx > νsCHmet > νsCHmtx.

To acquire a better understanding of the influence exerted by the presence of Cd2+ during the process of transforming ferrihydrite to goethite, the morphological and structural changes of several samples obtained by the addition of Cd2+ to a suspension of nascent goethite were explored, and their chemical reactivity in acid media assessed. The samples (series Gi) were obtained by adding, at different times during the synthesis process, Cd2+ ions to ferrihydrite (Fe5HO8.4H2O) formed in alkaline media. The suspensions were aged for 5 days at 70°C, and the amorphous materials were extracted using a HCl solution (series GHCl-i). The X-ray diffraction (XRD) patterns showed that a goethite-like phase was formed, and chemical analyses indicated that the Cd content, xCd, increased with the earlier addition of the Cd2+ ions to the Fe oxyhydroxide suspension. Lattice parameters and cell volume, obtained by the Rietveld simulation of XRD data, indicated an enlargement of the cell parameters of goethite in line with the Cd-for-Fe substitution. In order to determine the influence of oxalate ions on the non-extracted solids, a second set of samples was also prepared that was kept in contact with an ammonium oxalate solution for 4 h (series Gox-i). The dissolution behavior of two series of Cd goethites and of a third series, obtained from coprecipitation of Fe3+ and Cd2+ ions in alkaline media, was observed. Kinetics measurements in 4 M HCl showed that the initial dissolution rate of samples Gox-i decreased with aging time, while the opposite effect was observed for series GHCl-i. Dissolution–time curves were well described by the Kabai equation, and activation energies were calculated using the Arrhenius equation. The results indicate that the presence of Cd during the crystallization process of goethite leads to the formation of a Cd goethite with modified morphology, structural parameters, and chemical reactivity.

The design of the repository for high-level nuclear waste (HLW) in France consists of a multiple-barrier system including steel canisters in a clay host rock. The system will undergo temperature variations in time and space, the heat source being the HLW within the canisters. The effect of a thermal gradient in space on the Fe-claystone interaction was investigated here by applying a thermal gradient (150–300°C and 80–150°C) to a mix of claystone, Fe, and an aqueous chloride solution over periods of 3 and 6 months. Following the reaction, the starting clay minerals (mostly illite and mixed-layer illite-smectite) evolved toward chlorite, Fe-serpentine, Fe-saponite, mixed-layer chlorite-smectite, or mixed-layer serpentine-smectite as a function of temperature. Iron corrosion made the medium basic and reductive. Magnesium enrichment of clay minerals was observed in the hottest part of the experiment due to Mg migration under the thermal gradient. Reaction progress was enhanced at the lowest temperatures, compared to batch experiments.

Using first-principles molecular-dynamics simulations, probable inner-sphere complexes of Fe2+ adsorbed on the edge surfaces of clay minerals were investigated. Ferrous ions are important reductants in natural processes and their properties can be altered significantly by complexation on edge surfaces of clay minerals. However, the microscopic picture of adsorption sites and structures of Fe2+ is difficult to reveal with modern experimental techniques and, therefore, remains unclear. From the results of first-principles molecular-dynamics simulations, evidence has been provided that complexes on ≡Si—O sites were the most stable forms, which should be responsible for the experimentally observed pH-dependent uptake. Such complexation was found to be strong enough to distort the local coordination structures of Si—O tetrahedra in the substrate. Analyses showed that Fe2+—Owater coordination structures were dominated by the solvent with surface groups participating in the complexes via H bonding. The present study provided a microscopic basis for understanding the chemical processes involving surface-complexed Fe2+ ions.

The island-arc volcanics situated in the eastern part of the Căpîlnaş-Techereu nappe (South Apuseni Mountains, Romania) were studied to evaluate the temperature, fluid properties, and mineral chemistry during low-temperature metamorphism. Detailed observations of metamorphic mineral assemblages were conducted using powder X-ray diffraction and electron microprobe. The metamorphism involved albitization of plagioclase feldspar and the formation of mafic phyllosilicates, zeolites, and other hydrous Ca-Al-silicate minerals. Mafic phyllosilicates consisted of transitional dioctahedral-trioctahedral smectites, mixed-layer chlorite-smectite (C/S, 6–96% chlorite), and discrete chlorite. The zeolites were analcime, stilbite ± stellerite, heulandite, laumontite, epistilbite, and mordenite. Also present, as secondary minerals filling amygdales and veins, are prehnite, pumpellyite, and secondary amphibole. Two mineral assemblages were identified which provide important information about metamorphic conditions (temperature, reaction progress, and fluid properties): (1) heulandite + analcime + quartz; and (2) laumontite + albite + quartz + prehnite + pumpellyite ± amphibole. The types of and relations between minerals in the first assemblage suggest the occurrence of low-temperature hydrothermal metamorphism in the zeolite facies at ~125°C, whereas the second assemblage was metamorphosed at 200°C. The composition and variability of the mineral assemblages in the study area suggest that, due to slow reaction rates, the low-temperature transformations and mineral assemblages were influenced not only by temperature but also by local rock composition, fluid-rock ratio, and fluid chemistry.

Particle–particle interactions in natural clays can be evaluated by their rheological behavior, but the results are often affected by the physicochemical properties of the clays. The behaviors of two fundamentally different types of clays (low-activity and high-activity) differ with respect to salinity and a time factor (duration of shearing at a given shear rate): illite-rich Jonquiere clay (low-activity clay, Canada) and montmorillonite-rich Wyoming bentonite (high-activity clay, USA). The purpose of the present study was to investigate these different behaviors. Most natural clays exhibit shear-thinning and thixotropic behavior with respect to salinity and the volumetric concentration of the solids. Natural clays also exhibit time-dependent non-Newtonian behavior. In terms of index value and shear strength, lowactivity and high-activity clays are known to exhibit contrasting responses to salinity. The geotechnical and rheological characteristics as a function of salinity and the shearing time for the given materials are compared here. The clay minerals were compared to estimate the inherent shear strengths, such as remolded shear strength (which is similar to the yield strength). Low-activity clay exhibits thixotropic behavior in a time-dependent manner. High-activity clay is also thixotropic for a short period of shearing, although rare cases of rheopectic behavior have been measured for long periods of shearing at high shear rates. The change from thixotropic to rheopectic behavior by bentonite clay has little effect at low shearing speeds, but appears to have a significant effect at higher speeds.

The clay mineralogy of the Zhada sediments was investigated, using X-ray diffraction and scanning electron microscopy, to obtain a better understanding of climatic change and uplift of the Himalayas in the Zhada region of Tibet. The sediments of Zhada basin in the late Miocene to Pliocene consist of lacustrine and fluvial deposits >800 m thick and can be subdivided into five clay assemblage zones based on their clay-mineral composition. The upward zonation is as follows: (1) smectite-kaolinite; (2) illite-chlorite; (3) chlorite-illite-kaolinite; (4) illite-chlorite; and (5) smectite, illite, and kaolinite. The ratio of chlorite + illite to kaolinite + smectite (Ch+I/K+S) and the Kübler index indicate a warm and humid climate from 9.5 to 8.4 Ma, a cold and dry climate from 8.4 to 7.2 Ma, a warm and seasonal arid climate from 7.2 to 4.5 Ma, a cool and humid climate from 4.5 to 3.6 Ma, and a warm and seasonally humid climate from 3.6 to 3.0 Ma. Intense fluctuations in the Kübler index and in the quantities of evaporite minerals dolomite, aragonite, and gypsum, during the period 7.2–4.5 Ma suggest strong climatic fluctuations between humid and seasonally humid conditions in the Zhada basin. Rapid uplift around the Zhada basin occurred at 8.4 and 3.6 Ma, with sharp subsidence at 7.2 and 4.5 Ma. Evolution of the climate at Zhada showed a different model from that of global climate change, and tectonics-led climate change was the major contributor to climate evolution in the area.

The increasing exploration and exploitation of hydrocarbon resources hosted by oil and gas shales demands the correct measurement of certain properties of sedimentary rocks rich in organic matter (OM). Two essential properties of OM-rich shales, the total specific surface area (TSSA) and cation exchange capacity (CEC), are primarily controlled by the rock’s clay mineral content (i.e. the type and quantity). This paper presents the limitations of two commonly used methods of measuring bulk-rock TSSA and CEC, ethylene glycol monoethyl ether (EGME) retention and visible light spectrometry of Co(III)-hexamine, in OM-rich rocks. The limitations were investigated using a suite of OM-rich shales and mudstones that vary in origin, age, clay mineral content, and thermal maturity.

Ethylene glycol monoethyl ether reacted strongly with and was retained by natural OM, producing excess TSSA if calculated using commonly applied adsorption coefficients. Although the intensity of the reaction seems to depend on thermal maturity, OM in all the samples analyzed reacted with EGME to an extent that made TSSA values unreliable; therefore, EGME is not recommended for TSSA measurements on samples containing >3% OM.

Some evidence indicated that drying at ⩾200°C may influence bulk-rock CEC values by altering OM in early mature rocks. In light of this evidence, drying at 110°C is recommended as a more suitable pretreatment for CEC measurements in OM-rich shales. When using visible light spectrometry for CEC determination, leachable sample components contributed to the absorbance of the measured wavelength (470 nm), decreasing the calculated bulk rock CEC value. A test of sample-derived excess absorbance with zero-absorbance solutions (i.e. NaCl) and the introduction of corrections to the CEC calculation are recommended.

A diapiric intrusion of clays in the Carlentini Formation (Tortonian) was discovered in a quarry at S. Demetrio High (Hyblean Plateau, Sicily, Italy). Seven clay samples were analyzed by different analytical methods, including X-ray powder diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy, to determine the composition and mechanism of formation (sedimentary vs. hydrothermal) of these clays. Ferric saponite, carbonates (calcite and traces of ankerite), quartz, pyrite, and zeolites (phillipsite and harmotome) were detected using XRD and FTIR. This mineral assemblage, dominated by Fe-rich saponite, and the abundance of light rare-earth elements (LREE), Eu, fluid-mobile elements (FME > 10 × primordial mantle: Li, Be, B, As, Sb, Pb, U, Ba, Sr, Cs), and other incompatible elements (Zr = 169 ppm, Nb = 46 ppm, Th = 11 ppm, on average) imply that S. Demetrio clays precipitated from a mixture of hot Si-rich hydrothermal fluids (350–400°C) and cold seawater. The evidence is in accord with the affinity of clays for hydrothermally modified mafic and ultramafic rocks, forming the Hyblean lower crust, based on multi-element comparisons, and on the occurrence of trace amounts of chrysotile 2Mc1 and sepiolite. The association of long-chain aliphatic-aromatic hydrocarbons (intensity ratios I2927/I2957 > 0.5) with hydrothermal clays, the lack of fossils, and the similarity of the IR absorption bands with those of organic compounds detected previously in some metasomatized Hyblean gabbroic xenoliths suggest a possible abiogenic origin of hydrocarbons via a Fischer-Tropsch-type reaction. The S. Demetrio clay diapir was emplaced at shallow crustal levels in the Late Miocene as a consequence of the interaction, at a greater depth, of an uprising basalt magma and the products of an early, serpentinite-hosted hydrothermal system.

The objective of the present study was to investigate changes in the structural, textural, and surface properties of tubular halloysite under heating, which are significant in the applications of halloysite as functional materials but have received scant attention in comparison with kaolinite. Samples of a purified halloysite were heated at various temperatures up to 1400°C, and then characterized by X-ray diffraction, electron microscopy, Fourier-transform infrared spectroscopy, thermal analysis, and nitrogen adsorption. The thermal decomposition of halloysite involved three major steps. During dehydroxylation at 500–900°C, the silica and alumina originally in the tetrahedral and octahedral sheets, respectively, were increasingly separated, resulting in a loss of long-range order. Nanosized (5–40 nm) γ-Al2O3 was formed in the second step at 1000–1100°C. The third step was the formation of a mullite-like phase from 1200 to 1400°C and cristobalite at 1400°C. The rough tubular morphology and the mesoporosity of halloysite remained largely intact as long as the heating temperature was <900°C. Calcination at 1000°C led to distortion of the tubular nanoparticles. Calcination at higher temperatures caused further distortion and then destruction of the tubular structure. The formation of hydroxyl groups on the outer surfaces of the tubes during the disconnection and disordering of the original tetrahedral and octahedral sheets was revealed for the first time. These hydroxyl groups were active for grafting modification by an organosilane (γ-aminopropyltriethoxysilane), pointing to some very promising potential uses of halloysite for ceramic materials or as fillers for novel clay-polymer nanocomposites.

In order to obtain nanopatterned surfaces, natural allophane particles originating from Japanese soils were immobilized as single particles on Si wafer substrates.When derived from aqueous suspensions, only a few nanoparticles were deposited and detected on the surface due to the weak adsorption of allophanes on the substrate. The amount of immobilized allophane was increased significantly, however, by using an organic solvent in combination with a micelle-based technique to suspend the allophane particles. The micelles were formed from a tailored, aliphatic diblock copolymer that was dissolved in toluene and contained several allophane particles. A cleaned silica chip was used as a substrate on which a monolayer of micelles was immobilized equidistant from each other by dip coating. To remove the polymer from the substrate and to produce free, single allophane nanoparticles, ultraviolet (UV) irradiation was used. After UV treatment, single allophane particles formed ring-shaped deposition patterns with a high surface density. Transmission electron microscopy (TEM) was used to verify the presence of single allophane nanoparticles in the Japanese samples which came from natural sources. The single allophane particles as well as the allophane-containing di-block copolymer micelles, both immobilized on Si substrates and TEM sample grids, were imaged by atomic force microscopy and TEM. In this way, the diameters of the single allophane particles, as well as the distances between the immobilized micelles and the particles and their topography on the substrates, were determined.

Nitrate is linked to chronic human illness and to a variety of environmental problems, and continues to be a contaminant of concern in soils and natural waters. Improved methods for nitrate abatement, thus, are still needed. The purpose of this study was to assess the potential for redox-modified, iron-bearing clay minerals to act as nitrate decontamination agents in natural environments. The model clay mineral tested was ferruginous smectite (sample SWa-1) exchanged with either sodium (Na+) or polydiallyldimethylammonium chloride (poly-DADMAC). Structural iron (Fe) in SWa-1 was in either the oxidized or reduced state. Little nitrate uptake was observed in the Na+-SWa-1, which was attributed to coulombic repulsion between the basal surfaces of the smectite and the nitrate anion. The addition of the DADMAC to the SWa-1 reversed the electrostatic charge manifested at the smectite surface from negative to positive, as measured by the zeta (ζ) potential. The positively charged poly-DADMAC-SWa-1 yielded high nitrate uptake due to coulombic attraction in both the oxidized and reduced states of the Fe in the SWa-1. The presence of reduced structural Fe(II) in the positively charged poly-DADMAC-SWa-1 enabled a chemical reduction reaction with the nitrate to produce nitrite. The amounts of nitrite found in solution, however, failed to account for all of the Fe(II) oxidized, so other N reduction products may also have formed or perhaps nitrite was also present in the adsorbed phase. The effects of other complexities, such as polymer configuration at the surface, also need further investigation. The results do clearly establish abiotic nitrate reduction to nitrite and possibly other reduction products. The combination of bacterial activity in soils and sediments, which is known to reduce structural Fe in smectites, and the abundance of organic cations in soil organic matter creates an environment where reversed-charge smectite could exist in nature. This represents a potentially effective system for mitigating harmful effects of nitrate in soils, sediments, groundwater, and surface water.

Hydrothermal syntheses of the magadiite, a layered silicate structure, were conducted in the presence of a heteroatom source (SnCl4.5H2O) with the intention of investigating its influence on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms in the abovementioned structure. For comparison, unmodified magadiite, Al-containing magadiite, and impregnated magadiite were synthesized. The magadiite structure was identified for samples with Sn/Si ratios up to 0.015. Synthetic methods applied to Sn-modified materials were found to be unsuitable for the introduction of Al. The characterization methods used were X-ray diffraction, temperature-programmed reduction, and 29Si magic angle spinning nuclear magnetic resonance and these revealed the substitution of Si by Sn in the silica layers. No additional acid centers on the surfaces of the modified samples were detected, suggesting the presence of the desired four-coordinate Sn in the silica layers.

The conformational behavior of polymers in clay-polymer nanocomposites (CPN) is not fully understood because of the many factors involved. The purpose of the present study was to investigate the conformational behavior of a polymer at the micro- and meso-scales in order to predict the behavior of tunable CPN. The study used a pH-responsive polymer, polyacrylamide, which has time-dependent hydrolysis response properties, to examine micro-scale conformational behavior of the polymer adsorbed on representative clay-mineral surfaces, SiO2 and Al2O3. A nanocomposite and a microcomposite were used to link meso-scale CPN behavior to micro-scale polymer conformation. The conformational behavior was characterized using in situ, real-time spectroscopic ellipsometry. The contracted coil conformation of polyacrylamide was observed at pH = 3, while extended conformation was observed at pH = 11.5 on both SiO2 and Al2O3 surfaces. At pH = 11.5, the polymer conformation changed from expanded coil to extended conformation over time. The polymer conformation changed more rapidly with the Al2O3 surface due to mineral dissolution at pH = 3 and 11.5. Swelling tests were conducted as functions of pH and time to link the micro-scale phenomena to meso-scale CPN behavior. The results indicated that the swelling potential of CPN corresponded to the conformation of adsorbed polyacrylamide, which varied with pH and time. The swelling potential of CPN was maximized at pH = 11.5 and decreased with decreasing pH, corresponding to the observed micro-scale conformational behavior.

To determine the relationships between the symmetry of the overall pyrophyllite and talc structure and the symmetry of individual layers, the geometry and symmetry of each 2:1 layer of pyrophyllite and talc were analyzed. For each, the previously published, refined unit cell may be rotated clockwise by ~60° for comparison to a layer unit cell. In pyrophyllite, the layer unit cell is ideal and shown to be orthogonal with C2/m symmetry. The agreement between the refined atomic coordinates and those calculated for the layer with C2/m symmetry confirms that the symmetry of the pyrophyllite layer is C2/m. The obliquity of the pyrophyllite refined cell results from the layer stacking and the choice of unit cell, but the interlayer stacking sequence does not disturb the layer symmetry. In contrast, talc has an oblique layer cell, without a mirror plane. For the most part, the distortion of the talc 2:1 layer is probably caused by an elongation of unshared O-O lateral edges around M1 that creates a slight corrugation of the octahedral sheet surface. Perhaps of lesser importance, the distortion of the talc layer cell may result from Coulombic interactions between cations of adjacent layers, and these cation-to-cation distances are sufficiently large (~6–7.5 Å) that the weak van der Waals forces that stabilize the stacking are not overcome. Because pyrophyllite has a vacant octahedral site, similar interactions are not present, and this results in a more idealized layer symmetry.

Phyllosilicates consisting of layers with an orthogonal cell and mirror plane (pyrophyllite, kaolinite, sudoite) were shown to have similar stacking faults. In these structures, the 2:1 or 1:1 layers have uniform orientation, and stacking faults occur owing to interstratifications of two alternative interlayer displacements in the same crystal that are related by a mirror plane in the projection on the (001) plane. In talc, stacking faults are associated with layer rotations by ±120°, whereas the lateral displacement between the adjacent tetrahedral sheets across the interlayer region is relatively ordered.

Microwave irradiation as a means for heating bentonites during acid activation has been investigated in the past but it has never been optimized for industrial applications. The purpose of this study was to apply a factorial 23 experimental design to a Serbian bentonite in order to determine the influence of microwave heating on the acid-activation process. The effect of acid activation under microwave irradiation on the textural and structural properties of bentonite was studied as a model reaction. A mathematical, second-order response surface model (RSM) was developed with a central composite design that incorporated the relationships among various process parameters (time, acid concentration, and microwave heating power) and the selected process response of specific surface area of the bentonite. The ranges of values for the process parameters chosen were: time, 5–21 min; acid concentration, 2–7 M; and microwave heating power, 63–172 W. The effect of individual variables and their interaction effects on the textural and structural properties of the bentonite were determined. Statistical analysis showed that the duration of microwave irradiation was less significant than the other two factors. The model showed that increasing the time and acid concentration improved the textural properties of bentonites, resulting in increased specific surface area. This model is useful for setting an optimum value of the activation parameters for achieving the maximum specific surface area. An optimum specific surface area of 142 m2g−1 was achieved with an acid concentration of 5.2 M, activation time of 7.4 min, and microwave power of 117 W.

Garnierites represent significant Ni ore minerals in the many Ni-laterite deposits worldwide. The occurrence of a variety of garnierite minerals with variable Ni content poses questions about the conditions of their formation. From an aqueous-solution equilibrium thermodynamic point of view, the present study examines the conditions that favor the precipitation of a particular garnierite phase and the mechanism of Ni-enrichment, and gives an explanation to the temporal and spatial succession of different garnierite minerals in Ni-laterite deposits. The chemical and structural characterization of garnierite minerals from many nickel laterite deposits around the world show that this group of minerals is formed essentially by an intimate intermixing of three Mg-Ni phyllosilicate solid solutions: serpentine-népouite, kerolite-pimelite, and sepiolite-falcondoite, without or with very small amounts of Al in their composition. The present study deals with garnierites which are essentially Al-free. The published experimental dissolution constants for Mg end-members of the above solid solutions and the calculated constants for pure Ni end-members were used to calculate Lippmann diagrams for the three solid solutions, on the assumption that they are ideal. With the help of these diagrams, congruent dissolution of Ni-poor primary minerals, followed by equilibrium precipitation of Ni-rich secondary phyllosilicates, is proposed as an efficient mechanism for Ni supergene enrichment in the laterite profile. The stability fields of the solid solutions were constructed using [log aSiO2(aq), log ((aMg2+ aNi2+)/(aH+)2)] (predominance) diagrams. These, combined with Lippmann diagrams, give an almost complete chemical characterization of the solution and the precipitating phase(s) in equilibrium. The temporal and spatial succession of hydrous Mg- Ni phyllosilicates encountered in Ni-laterite deposits is explained by the small mobility of silica and the increase in its activity.

Kaolin ores are usually contaminated by some Fe-bearing minerals, the strong colors of which degrade the quality of the final product. A spectroscopic technique is sought to quantify the content of hematite and goethite, the main contaminant minerals in the kaolin from Capim River in Brazil, was the focus of this study. The total Fe content obtained through X-ray fluorescence showed a poor correlation with the brightness of kaolin, due to the inability to differentiate between the Fe contained in the (oxyhydr)oxides and the Fe present in the crystalline structure of kaolinite, especially when the Fe-bearing minerals occur in small quantities. Here, a new generic technique to quantify Fe (oxyhydr)oxides in kaolin, based on the Kubelka-Munk theory, is presented. A new interpretation of the theory was made that enables its use without the need to measure thin layers of material. The results with synthetic goethite and hematite were very positive (R2pred ≈ 0.99) and experiments with contaminants from the mine are already underway.

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.