This study was undertaken to investigate mechanisms of mineral transformations associated with microbial reduction of structural Fe(III) in smectite. Shewanella oneidensis strain MR-1 cells were inoculated with lactate as the electron donor and Fe(III) in smectite as the electron acceptor. The extent of Fe(III) reduction was observed to reach up to 26%. Reduction proceeded via association of live bacterial cells with smectite. At the end of incubation, a large fraction of starting smectite was transformed to euhedral flakes of biogenic smectite with different morphology, structure, and composition. Lattice-fringe images obtained from environmental cell transmission electron microscope displayed a decrease of layer spacing from 1.5±0.1 nm for the unreduced smectite to 1.1±0.1 nm for the reduced smectite. The biogenic smectite contained more abundant interlayer cations, apparently as a result of charge compensation for the reduced oxidation state of Fe in the octahedral site. To capture the dynamics of smectite reduction, a separate experiment was designed. The experiment consisted of several systems, where various combinations of carbon source (lactate) and different concentrations of AQDS, an electron shuttle, were used. Selected area electron diffraction patterns of smectite showed progressive change from single-crystal patterns for the control experiment (oxidized, unaltered smectite), to diffuse ring patterns for the no-carbon experiment (oxidized, but altered smectite), to well-ordered single crystal pattern for the experiment amended with 1 mM AQDS (well crystalline, biogenic smectite). Large crystals of vivianite and finegrained silica of biogenic origin were also detected in the bioreduced sample. These data collectively demonstrate that microbial reduction of Fe(III) in smectite was achieved via dissolution of smectite and formation of biogenic minerals. The microbially mediated mineral dissolution-precipitation mechanism has important implications for mineral reactions in natural environments, where the reaction rates may be substantially enhanced by the presence of bacteria.

The present work is part of a study focused on the use of organo-zeolite conditioner to remediate soil polluted by toxic elements. The Neapolitan yellow tuff (NYT) was utilized as a component of an organo-mineral sorbent/exchanger soil conditioner with pellet manure (NYT/PM) to reduce the mobility of Cd and Pb and recover plant performance in heavily polluted soils from illegal dumps near Santa Maria La Fossa (Lower Volturno river basin, Campania Region, southern Italy). Pot experiments were performed by adding the NYT/PM mixture (1:1, w/w) to polluted soil at the rates of 0%, 25%, 50% or 75% (w/w). Wheat (Triticum aestivum) was used as the test plant. The addition of organo-zeolite NYT/PM mixture significantly reduced the DTPA (diethylene-triamine-pentaaceti c acid)-extractable Cd and Pb from 1.01 and 97.5 mg kg−1 in the polluted soil, to 0.14 and 11.6 mg kg−1, respectively, in the soil amended with 75% NYT/PM. The best plant response was observed in amended soil systems treated with 25% NYT/PM, whereas larger additions induced plant toxicities due to increased soil salinity.

Evidence for the formation of maghemite from goethite due to a bushfire on acid sulfate soil at East Trinity, Australia, is presented. Oxidation of pyrite-bearing acid sulfate soils led to precipitation of goethite-impregnated leaf litter. During a major bushfire, goethite with a crystal size calculated from broadening of the 110 reflection of ∼9 nm was converted to microcrystalline maghemite (size 12 nm, 220 reflection) and hematite (17 nm, 104 reflection) in a matrix of partly combusted plant litter. Replication of this natural formation of maghemite from goethite was achieved in the laboratory by burning goethite-impregnated leaf litter.

The Serinhisar-Acıpayam basin of western Anatolia hosts a Neogene alkaline lake which formed in some graben and semi-graben depression zones as a result of N–S tension. The basin is filled with fluvial and lacustrine sediments dominated by clayey materials. The filling of the basin with fine sediments and associated water level changes caused the development of swampy and/or semi-swampy, alkaline-lake environments where sepiolite, palygorskite, saponite and dolomitic sepiolite or palygorskite precipitated periodically in the basin. Sepiolite is predominant in the Kuyucak section and is intercalated with saponite-dominated levels, whereas saponite accompanied palygorskite at Kocapınar where basaltic volcanism occurred. The contacts between sepiolite-palygorskite and saponite levels are more or less sharp, reflecting rapid changes in the physicochemical conditions of the depositional environment. Micromorphological images reveal that both sepiolite and palygorskite grew as interwoven fibers or fiber bundles and masses where dolomite was absent, indicating direct precipitation from solution, whereas fibrous networks grew authigenically on and out of dolomite in dolomitic sepiolite and dolomitic palygorskite. Saponite is either green or reddish brown due to its organic material-rich content and derivation from products of basaltic volcanism. Synsedimentary basaltic volcanism was the main source of Fe and Al, whereas Si and Mg were derived from surrounding ultrabasic and detrital units and partly from the volcanism. It can be concluded that sepiolite, palygorskite and saponite formed either by direct precipitation from alkaline lake water or authigenically from interstitial pore-water between dolomite rhombs as controlled by concentration of Si, Mg, Al and Fe, rather than by mutual transformation.

The resistance to acidic and sulfate attack of Portland-pozzolan cement containing 35 wt.% of zeolite was compared with that of unamended Portland cement. Mortar specimens kept in 0.5% and 1.0% HCl solution, 5% Na2SO4 solution, and in reference water for 365 and 720 days were tested using a set of physical-mechanical and chemical techniques. The ability of mortars containing zeolitic cements with 15 to 50 wt.% of zeolite to protect steel against corrosion was verified by a potentiodynamic method. Mortar with zeolitic cement performs better when exposed to 1% HCl solution due to the presence of a finer pore matrix, a hydrate phase poorer in CaO-containing hydration products with lower leachability, and the high resistance of zeolite material itself to acidic attack, compared with Portland cement and siliceous sand. The improved sulfate resistance of the mortar with zeolitic cement is caused by the decreased C3A in the cement blend in comparison with that in Portland cement, a reduction in SO3 binding into the cement paste and decreased amount of CaO-containing hydration products capable of reacting with a sulfate solution forming voluminous reaction products, and consequent crack propagation, large expansion and structural disintegration. Passivation of steel in mortars with blends of Portland cement to zeolite percentage ratios of 85/15, 75/25 and 65/35 by weight is comparable to that of Portland cement mortar. This is particularly important because the mortar with zeolitic cement exhibits late strengths similar to that of Portland cement mortar. This confirms that zeolitic cement can replace Portland cement in many applications with the advantage of higher resistance to acidic and sulfate attack.

It has been suggested that interstratified illite-smectite (I-S) minerals are composed of aggregates of fundamental particles. Many attempts have been made to measure the thickness of such fundamental particles, but each of the methods used suffers from its own limitations and uncertainties. Small-angle X-ray scattering (SAXS) can be used to measure the thickness of particles that scatter X-rays coherently. We used SAXS to study suspensions of Na-rectorite and other illites with varying proportions of smectite. The scattering intensity (I) was recorded as a function of the scattering vector, q = (4 π/λ) sin(θ/2), where λ is the X-ray wavelength and θ is the scattering angle. The experimental data were treated with a direct Fourier transform to obtain the pair distance distribution function (PDDF) that was then used to determine the thickness of illite particles. The Guinier and Porod extrapolations were used to obtain the scattering intensity beyond the experimental q, and the effects of such extrapolations on the PDDF were examined. The thickness of independent rectorite particles (used as a reference mineral) is 18.3 Å. The SAXS results are compared with those obtained by X-ray diffraction peak broadening methods. It was found that the power-law exponent (α) obtained by fitting the data in the region of q = 0.1–0.6 nm−1 to the power law (I = I0q−α) is a linear function of illite particle thickness. Therefore, illite particle thickness could be predicted by the linear relationship as long as the thickness is within the limit where α <4.0.

Titanium was introduced into the clay structure by cation exchange with polymeric Ti cations which were formed by partial hydrolysis of Ti alkoxide in HCl. X-ray diffraction, N2 adsorption-desorption, chemical analysis, thermogravimetric analysis, differential thermal analysis, temperature-programmed desorption of ammonia and temperature-programmed reduction were used to characterize the resulting Ti-pillared clays (Ti-PILCs). Titanium methoxide allows the synthesis of a solid with a large basal spacing (26 Å), a large surface area (360 m2/g), a significant amount of micropore surface area (90%), and notable acidity. Moreover, Ti-PILCs obtained from methoxide were found to be thermally stable up to 500°C. A correlation between the increase in acidity and the increases in both microporosity and Ti content was observed. The surface area, the micropore volume, the acidity and the d001 peak intensity all increased upon increasing the amount of Ti added to the preparation (up to ∼15 mmoles of Ti/g clay). The use of an aqueous suspension of 0.13 wt.% of clay yielded the best structural and textural properties in terms of subsequent use of the clay as a catalyst.

The structural and physical effects of partially substituting Cd for Fe in goethite have been investigated. The solubility of Cd2+ in goethite is ∼10 mol.%, i.e. Fe0.905Cd0.095OOH. The structures of the substituted goethites have been refined, using the Rietveld method, from synchrotron X-ray powder diffraction data. There is a progressive increase in the size of the unit-cell parameters and unit-cell volume, upon the incorporation of much larger Cd2+ ion (0.95 Å) compared with Fe3+ (0.645 Å) in the goethite structure, together with a reduction in crystallinity. Transmission electron microscopy measurements confirm the crystallite size decreases as the Cd2+ content increases in goethite structure.

The organoclay quasicrystals formed by exchange reactions of fluoromagnesian smectite (FMS) and two kinds of cationic surfactants were investigated by X-ray diffraction (XRD) of both aqueous suspensions and dried powders. ζ potential measurements were also carried out. The two cationic surfactants employed in this study, dodecyltriphenylphosphonium bromide (C12PBr) and dodecyltrimethylammonium bromide (C12NBr), have the same alkyl chain length but different head group structures. In aqueous suspensions of C12N/FMS, regular stacking with a basal spacing of 2.28 nm was observed within the range 0.4 to 1.0 of the cation exchange capacity (CEC) of the C12N/FMS ratios. The basal spacing was constant in this range. The most intense diffraction for the C12N/FMS suspension was observed at 0.6 CEC, and a further increase in the C12N/FMS ratio resulted in a decline of the diffraction intensity and a slight increase in the peak width. On the other hand, in C12P/FMS suspensions with the surfactant/FMS ratios <0.6 CEC, only weak, broad XRD peaks were observed. With higher C12P/FMS ratios (0.8 and 1.0 CEC), strong diffraction peaks appeared with a basal spacing of 3.20 nm. The difference in the observed basal spacings of C12N/FMS and C12P/FMS tactoids was ∼0.9 nm, which did not agree with the difference in the estimated height of the two surfactants (∼0.1 nm). These differences of the tactoid structures between C12N/FMS and C12P/FMS suspensions could be explained in terms of the difference in the adsorption manner of the surfactants on the silicate surface and in the size of the surfactant head groups.

Analyses of the layer structure of Na-montmorillonite have been performed using 27Al MAS and 27Al MQMAS NMR techniques. Results of 27Al MAS NMR measurements at higher magnetic field strength (16.4 T) suggest that the 4-coordinated Al site in Na-montmorillonite has two different structures. This was confirmed by the fact that two peaks corresponding to 4-coordinated Al are observed in the 27Al MQMAS NMR at high magnetic field strength. The ratio of two 4-coordinated Al sites was found to be affected by water in the interlayer space because the area ratio of cross peaks corresponding to two 4-coordinated Al sites changes with the water content.

The crystal structure of biotite-1 M from Bancroft, Ontario, with the formula: $\left({\text{K}}_{1.96}{\text{Na}}_{0.13}{\text{Ca}}_{0.01}\right)\left({\text{Mg}}_{3.15}{\text{Fe}}_{2.59}^{2+}{\text{Ti}}_{0.17}{\text{Mn}}_{0.09}\right)\left({\text{Si}}_{5.98}{\text{Al}}_{1.92}{\text{Ti}}_{0.10}\right){\text{O}}_{20}\left[{\left(\text{OH}\right)}_{1.47}{\text{F}}_{1.98}\right]$, was determined by Rietveld refinement using high-resolution neutron powder diffraction at in situ temperatures ranging from 20 to 900°C. The room-temperature structure of the samples heated to between 400 and 900°C using an electric furnace in air was also refined. The crystal structures were refined to an RP of 2.98 — 5.06% and Rwp of 3.84–6.77%. For the in situ heating experiments in a vacuum, the unit-cell dimensions increased linearly to 600°C. The linear expansion coefficient for the c axis was 1.65 × 10−5°C−1, while those for the a and b dimensions were 4.44 × 10−6°C−1 and 5.21 × 10−6°C−1, respectively. Accordingly, the increase in the unit-cell volume up to 600 C occurred mainly along the c axis, resulting from the expansion in the K coordination sphere along that direction. Results for all K−O bonds were analyzed in terms of the lattice component and an inner component of the structural strain. The ditrigonal distortion decreased (3.76 at 20°C to 1.95 at 600°C) with temperature, because the shorter bonds expanded and the longer bonds contracted. The increase in the interlayer separation and the decrease in the interlayer octahedral flattening angle confirmed that the c-dominated expansion occurred in the interlayer region. In the case of the ex situ-heated samples, the cell dimensions decreased sharply at temperatures over 400 C. The octahedral sheet thickness and mean <M−O> distance decreased linearly due to oxidation of octahedral Fe. However, the interlayer separation and mean <K−O> distance decreased at temperatures over 400°C. At 400°C, dehydroxylation began to increase and interlayer regions became more constricted. The overall cell parameters decreased rapidly with increasing temperatures due to dehydroxylation. The large inner strain components in the K−O bonds also resulted in an increase in the considerable ditrigonal distortion (3.57° at 400°C to 6.15° at 900°C).

The intercalation of a saponite with the Al polycation [Al13(OH)24(H2O)24]15+ is described. This polycation is obtained by reaction of alumina with Al chloride. The intercalation is achieved by reaction of very concentrated solutions of this polycation with the clay in powder form. Solids with a basal spacing of 18.9 Å were obtained in this way, stable up to 700°C (17.0 Å). The Langmuir surface area of the intercalated solid was 366 m2/g, and that value decreases to 119, 138 and 125 m2/g for the solids pillared at 500, 600 and 700°C, respectively.

De-tert-butylation of 2-tert-butylphenol was carried out over thermally-treated and acid-treated Jordanian bentonite clay samples. This reaction was found to follow first-order kinetics for all clay samples with different pretreatment procedures. The apparent rate constant, k, was also determined, and found to depend on the pretreatment. Thermal pretreatment at temperatures up to 250°C has an enhancing effect on surface acid sites. The total surface acidity (Ho <4.8) and the concentration of strong acid sites peaked at 250°C. Also, as a result, the maximum catalyst activity was obtained with samples treated at this temperature. Acid pretreatment with 0.10 M HCl, 1.0 M H2SO4 or 1.0 M H3PO4, followed by thermal treatment at 250°C produced the best enhancement effect on the surface acidity and catalytic activity.

The thermal behavior of two clinoptilolites from an epiclastic and a pyroclastic deposit of central-northern Sardinia and of their exchanged forms (Li, Na, K, Cs, Mg, Ca, Sr and ammonium) were investigated by differential thermal analysis and thermogravimetry up to 1000°C. Their thermal stability was studied by evaluating the residual crystallinity (expressed as rehydration capacity) after 2 h thermal treatments at 450, 600 and 900°C. The water loss at 1000°C was linearly related to the radius (r) and the charge (z) of the exchangeable cations by the equations r2/z or r3/z, which are proportional to the inverse of the charge density over the surface or to the charge density over the volume of the cations.

The cation composition plays a crucial role in determining the thermal behavior of clinoptilolite. The presence of cations such as Cs or K, which have low surface or volume charge densities, was found to increase the thermal resistance. In particular, the crystallinity of Cs- and K-exchanged forms of both clinoptilolites was not affected by thermal treatment at 450°C and was only slightly reduced by thermal treatment at 600°C.

Predicting the thermal behavior of natural and cation-exchanged forms of these clinoptilolites can provide useful information for possible applications in catalysis, in the case of high thermal stability, or for thermal transformation into ceramics or lightweight aggregates.

Single-crystal X-ray diffraction experiments were carried out on roscoelite crystals from Reppia, Val Graveglia, Italy. Roscoelite [structural formula: XII(Ba0.006K0.994)IV(Si3.150Al0.850) VI(Al0.040Fe0.150Mg0.100Mn0.062V1.696Ti0.003)O10(OH)2] shows a near-perfect three-dimensional stacking order with cell parameters a = 5.292(1), b = 9.131(2), c = 10.206(3) Å, β = 100.98(2)° and space group C2/m, which indicate a 1M polytype. The crystal structure was refined on the basis of Fo2 for 846 unique reflections to R1 = 3.29% calculated using 746 unique observed reflections [|Fo| ⩾ 4σ(Fo)]. The mean tetrahedral cation–oxygen atom distance, <T−O> = 1.641 Å, is close to the mean <T−O> value obtained for dioctahedral true micas from the literature, whereas the octahedral sheet is characterized by a larger cis-octahedral cation–oxygen atom bond distance <M2−O> = 2.020 Å which, together with the mean electron count, is consistent with V occupancy. The presence of V within the octahedral sheet produces the smallest tetrahedral rotation (α = 2.3°), the lowest flattening of the basal oxygen surface (Δz = 0.118 Å) and the narrowest interlayer separation (3.030 Å) in dioctahedral micas.

Dioctahedral and trioctahedral smectites of very low Fe contents were exchanged with Ca (0.8 N CaCl2) and then with Cd (0.004–0.2 N CdCl2), resulting in the approximate Ca/Cd interlayer compositions 100/0, 75/25, 50/50 and 0/100. The samples were analyzed using 113Cd and 1H MAS NMR spectroscopy, at different hydration states, and by FTIR using films oriented at 90 and 45° to the infrared beam. When adsorbed from low-concentration CdCl2 solutions, as in this study, Cd is in the smectite interlayer as Cd2+, surrounded by water molecules. In smectite specimens with no tetrahedral charge, Cd occupies one single site in the center of the interlayer along the c axis but in smectite with tetrahedral charge, the basal oxygen atoms with excess negative charge interact with some of the Cd atoms more strongly, generating a second site in which Cd is displaced from the center of the interlayer and closer to those oxygen atoms. The 1H NMR study showed protons from hydration water and smectite hydroxyls and showed that both have more than one component. The FTIR and 1H NMR experiments indicate that Cd interacts with hydroxyl groups through one of the solvating water molecules in the first coordination sphere. Cadmium retains water molecules bridging Cd and OH groups even at low hydration states. Comparison with previous studies shows that, when adsorbed from high-concentration CdCl2 solutions, Cd species other than Cd2+ are present in sufficient quantities to enter the interlayer and create a different Cd-water complex, seemingly displacing Cd2+ from the center of the interlayer.

The adsorption behavior of quaternary ammonium cationic surfactants with different hydrocarbon chain lengths, i.e. HDTMA (hexadecyltrimethylammonium), TDTMA (tetradecyltrimethylammonium) and DDTMA (dodecyltrimethylammonium), onto clinoptilolite has been investigated. The adsorption isotherms of these surfactants are correlated with the ζ potential curves of clinoptilolite. Accordingly, the applicability of the hemimicelle hypothesis to the adsorption of cationic surfactants at the clinoptilolite/water interface considering in the electrical double layer (EDL) of clinoptilolite is discussed. Even though the adsorption occurs in the EDL of clinoptilolite, the adsorption of HDTMA, TDTMA and DDTMA onto clinoptilolite is not conveniently described by the hemimicelle hypothesis. The absence of all expected marked increase in the ζ potential curves at the hemimicelle concentration is ascribed to the large external cation exchange capacity of clinoptilolite. The hydrocarbon chain length of surfactant molecules is found to have a significant effect on the ion exchange as well as hydrophobic interaction mechanisms. The effectiveness of both ion exchange and hydrophobic interactions increases with increasing chain length, and so the greatest surfactant adsorption onto clinoptilolite was obtained by HDTMA.

The grafting, by chemical adsorption, of molecular 1.10-phenanthroline (OP) onto some Brazilian bentonite (montmorillonites) was studied to improve their adsorptive capacities to remove Cu ions from synthetic wastewater. The quantity of OP adsorbed was 112 mg g−1 of bentonite at pH 8.5 and no significant desorption was detectable in acidic or basic solutions. X-ray diffraction (XRD) spectra show that a complex type-β is formed in which the OP molecules lay inclined in the clay interlayer. After the intercalation of OP, the adsorptive capacities of the natural bentonites increased by a factor of ten. Thus, adsorption of Cu ions, at optimal pH of 8.0±0.5, showed saturation values, which, calculated by the Langmuir model, yielded 110 mg of Cu ions g−1 of bentonite (3.5 meq g−1). The mechanisms of Cu uptake are ion-exchange adsorption onto untreated bentonite and ion exchange plus Cu2+ phenanthroline complexation (chemisorption) on the modified pillared clay. The desorption of Cu ions from OP clay revealed high uptake irreversibility and physical stability (of the adsorbent) either in strongly acidic or basic solutions. Thus, after acid treatment ∼90% of the adsorbed Cu ions continued to be bound onto the OP-modified bentonite surface.

The size of quaternary ${\text{NH}}_4^{+}$ cations defines their packing configurations in the interlayers and the basal spacings of organoclays, and hence strongly influences the sorptive properties of organoclays. A series of organoclays (TAA-SACs) was prepared from a smectite (SAC) fully exchanged with symmetrical tetraalkylammonium (TAA) cations of progressively increasing sizes with the carbon number of single alkyl group from 1 to 6. X-ray diffraction analysis indicated the packing configurations of monolayer, monolayer-to-bilayer transition, bilayer, and bilayer-to-trilayer transition in the interlayers of SAC. Calculations of the interionic distances between TAA ions support such packing configurations. Sorption of benzene by TAA-SACs displayed a high-low-high uptake trend and progressively weaker sorptive interactions as the size of TAA ions increased. Both the siloxane surfaces and TAA ions contributed to the overall sorption, with their relative contributions dependent on the TAA interionic distances and the basal spacings of TAA-SACs. High benzene sorption by small TAA-SAC (tetramethylammonium(TMA)-SAC) was attributed to the strong interactions between the siloxane surfaces and benzene molecules. With large TAAs, high sorption was due to the effective solute partitioning. Compared to benzene sorption, TCE sorption by small TAA-SACs (TMA-SAC and tetraethylammonium(TEA)-SAC) was less effective and displayed an abnormal trend, due largely to the lack of the siloxane surface-TCE interactions and to the stronger hydration of TMA as compared to TEA ions. The results provide strong evidence to support the use of either small or large quaternary ${\text{NH}}_4^{+}$ cations in preparation of organoclays as effective sorbents for removing organic contaminants from water.

Hematite (α-Fe2O3) possesses distinct spectral properties which facilitate its identification in mineral mixtures. This paper reports the relationships between the visible diffuse reflectance (DR) spectrum and the color and crystal properties of a group of 81 natural and synthetic hematites. The visible DR spectra for powdered hematite samples diluted to 4 wt.% with BaSO4 white standard were recorded and used to calculate the corresponding Munsell colors. The second derivative of the Kubelka-Munk function of the DR was used to estimate the position and intensity of the main absorption bands, which occurred at ∼435, ∼485 and ∼545 nm. The Munsell hue ranged from 9.5P to 5.3YR and was negatively correlated with the position of the ∼545 nm band, so it became yellower as the band shifted to shorter wavelengths (higher energies). The Munsell value, which ranged from 4.9 to 8.6, and chroma, which ranged from 1.4 to 8.3, were negatively and positively correlated, respectively, with the intensity of the ∼545 nm band, the position of which exhibited a weak negative correlation with the degree of Al substitution (x). The position and intensity of this band also exhibited a weak negative correlation with the specific surface area (SSA); both, however, were uncorrelated with domain shape as measured by the ratio between the X-ray mean coherence lengths (MCLs) in the [110] and [104] directions. The properties of the ∼435 and ∼485 nm bands were unrelated to x, SSA or MCL110/MCL104. The negative relationship between the position of the ∼545 nm band and x does not support the assignment of this band to the 2(6A1) → 2(4T1g(4G)) electron pair transition (EPT), which relates to the to Fe3+−Fe3+ magnetic coupling between face-sharing octahedra. The ∼485 nm band might reflect a ‘goethitic’ structural component in Fe-defective hematites as it appears at the same wavelength as the hypothetical EPT related to Fe3+−Fe3+ magnetic coupling between edge-sharing octahedra in goethite (α-FeOOH).