The present work deals with the synthesis of Na-A zeolite using 10 Å halloysite (collected near Grosseto, Italy) as the starting material, instead of the more expensive chemicals currently used in industry (Na aluminates and Na silicates). The process of synthesizing Na-A zeolite from 10 Å halloysite is rather simple as the reaction of halloysite with alkali occurs very readily and is achieved without prior thermal activation at high temperature. The optimal conditions of crystallization of Na-A zeolite from 10 Å halloysite are reached at 80°C. At lower temperatures, transformation of halloysite into an amorphous material requires more time, and the field within which Na-A zeolite exists overlaps that of 7 Å halloysite, G and HS zeolites. The products of synthesis at 80°C were characterized by X-ray diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry and infrared spectroscopy. We also propose a model to study the reaction kinetics of zeolite (Na-A and HS) nucleation and growth by real-time X-ray powder diffraction data.

Montmorillonite dissolution under highly alkaline conditions (pH = 13.3; I = 0.3 M) was investigated by bulk dissolution methods and in situ atomic force microscopy (AFM). In bulk dissolution experiments, initial SiO2 concentrations were high, and a steady state was reached after 136 h. The dissolution rates derived from the edge surface area (ESA) at the steady-state condition at 30, 50 and 70°C were 3.39 x 10−12, 1.75 × 10−11 and 5.81 × 10−11 mol/m2 s, respectively. The AFM observations were conducted under three conditions: (Run I) short-term in situ batch dissolution at RT; (Run II) long-term in situ flow-through dissolution at RT; and (Run III) long-term batch dissolution at 50°C. The observed reductions in montmorillonite particle volume for Runs I and II were due primarily to edge-surface dissolution. The ESA-based dissolution rate for Run I (10−9 mol/m2 s) was three orders of magnitude faster than that for Run II (10−12 mol/m2 s). The rate obtained for Run II corresponded to the rate at the steady-state conditions in the bulk dissolution experiments. A small number of etch pits developed in Run III slightly increased the ESA of montmorillonite since most of the montmorillonite particles were separated into monolayers lacking three-dimensional periodicity. The ESA-based dissolution rate for Run III was 2.26 × 10−11 mol/m2 s. Dissolution rates based on long-term AFM observations could be directly compared with steady-state rates obtained from bulk dissolution experiments. The AFM observations indicated that dissolution occurred at edge surfaces; therefore, the ESA should be used to calculate the dissolution rate for montmorillonite under alkaline conditions. Dissolution rates of individual particles with different morphologies estimated by AFM were similar to rates estimated from bulk dissolution experiments.

This study was undertaken to investigate the changes in flocculation properties of Fe-rich smectite (nontronite, NAu-1) suspensions, including settling velocity, aggregate size and floc architecture associated with microbial Fe(III)-reduction in the smectite structure. The dissimilatory Fe-reducing bacterium Shewanella oneidensis MR-1 was incubated with lactate as the electron donor and structural Fe(III) as the sole electron acceptor for 3, 12, 24 and 48 h in an anaerobic chamber. Two controls were prepared; the first was identical to the experimental treatments except that heat-killed cells were used (non-reduced control), and the second control was the same as the first except that the incubation was carried out in an aerobic environment. The extent of Fe(III) reduction for the 48 h incubation was observed to reach up to 18%. Neither the non-reduced control nor the aerobically inoculated sample showed Fe(III) reduction. Compared with the non-reduced control, there was a 2.7 μm increase in mean aggregate size and a 30-fold increase in average settling velocity in the bioreduced smectite suspensions as measured using a Micromeritics Sedigraph®. The aerobically inoculated smectite showed a similar aggregate-size distribution to that of the non-reduced control. Significant changes in physical properties of smectite suspensions induced by microbial Fe(III) reduction were measured directly using transmission electron microscopy. The floc architecture of bioreduced smectite revealed less open structures compared to those of a non-reduced control. The aspect ratio (thickness/length) of individual smectite particle increased from 0.11 for the non-reduced control to 0.18 on average for the bioreduced smectite suspensions. The effects of pH on the clay flocculation were minimal in this study because the value of pH remained nearly constant at pH = 7.0–7.3 before and after the experiments. We therefore suggest that the increase in net negative charge caused by microbial Fe(III) reduction significantly promoted clay flocculation by increasing the electrochemical attraction in the smectite suspensions.

The interaction of the water-soluble 5,10,15,20-tetrakis(l -methyl-4-pyridyl)-21H,23H-porphine (TMPyP) with different 2:1 phyllosilicates was examined by Raman and UV-visible spectroscopies. The clay samples were saturated with the tetracationic porphyrin and isolated from the aqueous suspension. A red shift of the Soret band was observed for all the clay-TMPyP systems in the order vermiculite < Laponite < mica-smectite (Syn-1) < montmorillonite (SWy-2). Furthermore, three components were observed for the Soret band (at ~425, 455 and 488 nm). Raman spectra of the isolated solids excited at 457.9 nm, 488.0 nm and 514.5 nm suggest the occurrence of porphyrin protonation, nonplanar distortion and rotation of the meso substituent. Based on the vibrational data, an acidity scale was proposed for the clays: vermiculite < Laponite < SWy-2 < Syn-1. The relative contribution of the protonated spectra is larger at 457.9 nm than at 488.0 nm, suggesting that the peak at 455 nm corresponds to the protonated species. In Laponite, the relative intensity of the meso substituent band at ~1635 cm-1 indicates that the dihedral angle formed between the porphyrin and the methyl-pyridyl rings decreased in the non-protonated porphyrin as a consequence of intercalation. Raman data are thus consistent with the presence of at least two porphyrin species in resonance at 457.9 nm: the protonated and a more planar non-protonated porphyrin. At 488.0 nm the number of enhanced modes increases suggesting a decrease in the porphyrin symmetry. This allows assignment of the absorption band centered at 488 nm to a non-planar porphyrin conformation.

The Gourougou volcanic massif (northeastern Morocco) is actively prospected for bentonite deposits. Five bentonites originating from different environments were selected for the present study: hydrothermal alteration of obsidian perlite glass inside the volcanoes themselves (Providencia and Tribia deposits); alteration of pyroclastic flows in a marine shallow water to lagoonal lacustrine environment (Ibourhardayn deposit); ash falls in marine or lacustrine systems (Moulay Rachid and Melg el Ouidan (formerly Camp Berteau) deposits). All of these bentonites were probably formed from volcanic glass originating from a rhyolitic magma at different stages of differentiation as shown by slight variations of REE and incompatible element abundances. The crystal-chemical characteristics of the smectite vary according to alteration conditions: beidellite predominates in hydrothermal systems, whereas montmorillonite predominates in lagoonal and lacustrine environments, and mixed-layer beidellite-montmorillonite in the sea-water-altered pyroclastic flows. All these dioctahedral smectites exhibit a heterogeneous distribution of charge as shown by the presence of partially expandable (1 EG) or non- expandable (0 EG) layers in the K-saturation state. The proportion of the collapsed or partially expandable layers is not related to the average layer charge or to the cation exchange capacity. This militates for an overall heterogeneous charge distribution. Compared to other natural or experimental alteration systems of similar rhyolitic glass, the formation of beidellite or montmorillonite appears to be controlled by the amounts of Mg in the system.

Dark Fe oxides and sulfides are major discoloring impurities in mined commercial white kaolin clay. In order to evaluate the potential influence of Fe-cycle bacteria on Fe cycling during post-depositional clay-weathering alteration, Fe(III)-reducing and/or Fe(II)-oxidizing microorganisms were examined in open-pit, subsurface mine samples from kaolin lenses and smectite formations collected from sites in central Georgia. Samples of varying age were examined, including late Eocene smectite overburden, hard kaolin of Middle Eocene age, soft gray kaolin from the late Paleocene, and soft tan kaolin of late Cretaceous age. These clays contained 0.06–5.33% organic carbon, which included various potential organic electron donors for bacterial metabolism: formate (1.1–30.6 mmol/kg), acetate (0–40.5 mmol/kg), lactate (0–12.1 mmol/kg), pyruvate (0.4–78 mmol/kg), oxalate (0–141.7 mmol/kg), and citrate (0–1.4 mmol/kg). All clay samples studied had small concentrations of ‘bio-available’ Fe(III) (0.5 M HCl-extractable Fe, 0.5–2.8 mmol/kg) compared to total Fe (HF-extractable, 25–171.9 mmol/kg). The highest Fe(III)/[Fe(II)+Fe(III)] ratio and the lowest organic carbon content were in kaolin samples in which Fe(III) reduction was determined to be the dominant terminal electron accepting process by hydrogen analysis. All clay samples showed greater numbers of Fe(II)-oxidizing bacteria (22–22,000 cells/g) than Fe(III)-reducing bacteria (3–410 cells/g) as determined by MPN analysis. The Fe(III)-reducing activity in clays could be stimulated with the addition of 1 mM of the Fe(III) chelator, nitrilotriacetic acid. The addition of nitrate stimulated anaerobic Fe(II) oxidation. These results suggest that anaerobic bacteria involved in both oxidation and reduction of Fe exist in these subsurface clay formations, and might have had an influence on post-depositional weathering reactions.

Eighteen purified kaolin samples from Thai Ultisols were studied by X-ray diffraction, X-ray fluorescence, transmission electron microscopy and BET methods. Minor amounts of inhibited vermiculite, quartz and anatase were general contaminants of the kaolins which had an average chemical composition of 403 g kg−1 Al2O3, 550 g kg−1 SiO2, 25.3 g kg−1 Fe2O3, 15.6 g kg−1 TiO2 and 4.65 g kg−1 K2O on an ignited basis. Appreciable concentrations of Mn, Co, Ni, Cu, Zn, As and Pb were present and most of the Ni, Cu and Zn in the original clay fraction was retained in the deferrated kaolin concentrate. It was not possible to determine if these elements are present as structural ions in kaolin crystals.

The kaolins exhibited a variety of crystal morphologies ranging from sub-micron, euhedral, hexagonal plates to anhedral plates and tubes. Their specific surface areas ranged from 15.9 to 61.4 m2g−1 (mean 44.9 m2g−1) and surface area increased with decrease in crystal size. The cation exchange capacity of the kaolins ranged from 7.2 to 23.4 cmolc kg−1 and surface charge density from 0.16 to 0.99 C m−2 but these values are sensitive to the presence of contaminants. Structural iron ranged from 12.4 to 44.8 g kg−1 Fe2O3 and there was an increase in structural defects towards the soil surface associated with an increase in the amount of structural iron.

Chrysotile from Thetford Mines in Quebec, Canada was treated first with mild formic or oxalic acid at concentrations of 0.5 to 2.0 N at 200°C in Teflon-lined 12.0 mL Parr bombs. The reaction products were identified by X-ray diffraction as a poorly crystalline Fe-bearing kerolite-like 2:1 layer silicate (which will be described as a kerolitic precipitate or a kerolitic mesophase in this report). Electron microscopic examination showed a thin foily morphology for this kerolitic mesophase that may have formed by the following reaction:(1)

$\mathop {{\rm{M}}{{\rm{g}}_{\rm{6}}}{\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{{8_{\left( {\rm{s}} \right)}}}}}\limits_{{\rm{chrysotile}}} + 6.02{{\rm{H}}^{\rm{ + }}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{F}}{{\rm{e}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} \to \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}} \cdot n}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} {{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{3}}{\rm{.55M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)}$

The magnetite impurity in the initial chrysotile asbestos served as the source of Fe in the above reactions. Subsequently, this kerolitic precipitate was reacted with 0.2 N NaOH for 48–96 h at 200°C and a highly crystalline smectite was formed with the same foily morphology as the kerolitic precipitate. X-ray spectral analyses of the kerolitic mesophase and smectite suggest the following reaction to have taken place:(2)

$\eqalign{ & \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}}}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} \cdot n{{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{0}}{\rm{.53M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{NaO}}{{\rm{H}}_{\left( {{\rm{aq}}} \right)}} + 0.01{\rm{F}}{{\rm{e}}^{{\rm{3 + }}}}_{\left( {{\rm{aq}}} \right)} \to \cr & \;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\mathop {\;\;{\rm{N}}{{\rm{a}}_{0.54}}\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.99}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.01}}}^{{\rm{2 + }}}} \right)\left( {{\rm{S}}{{\rm{i}}_{{\rm{3}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{3 + }}}} \right){{\rm{O}}_{10}}{{\left( {{\rm{OH}}} \right)}_{{\rm{2}}\;\left( {\rm{s}} \right)}}}\limits_{{\rm{saponite}}} + 0.54{\rm{S}}{{\rm{i}}^{{\rm{4 + }}}}_{\left( {{\rm{aq}}} \right)} \cr} $

The reaction products, a kerolitic mesophase and smectite, possess a non-fibrous habit in contrast to the fibrous (asbestiform) morphology of chrysotile.

The loading of various phosphates on the surfaces of nanoparticles of allophane (1–2SiO2·Al2O3·5–6H2O) was investigated. The allophane used was a high-silica type with a Si/Al ratio of 0.85. The phosphate-sorption isotherm was measured using (NH4)2HPO4 solution, which showed the highest phosphate sorption of the seven phosphates examined. This sorption isotherm was in better agreement with the Langmuir equation than the Freundlich equation. The resulting maximum sorption capacity was 4.87 mmol/g and the Langmuir constant was 0.0033 L/mmol. The sorption energy (ΔG) calculated from the Langmuir constant was −2.96 kJ/mol. The amount of loaded phosphate varied greatly according to the phosphate used, being greater for orthophosphates than for polyphosphates. The amount of loaded phosphate also depended on the cation present, in the order Ca-Na-NH4-phosphate. The Si/Al ratios of the samples were decreased by orthophosphate loading due to the partial replacement of SiO4 by PO4 tetrahedra, but this effect was offset by the partial dissolution of the allophane by polyphosphate loading. The 29Si magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of all the phosphateloaded samples showed an increase of a peak at −90 ppm (the Q1–Q3 polymerized tetrahedral unit) and the decrease of a peak at −78 ppm peak (the Qo monomeric tetrahedral unit). The 31P MAS NMR spectra showed peaks at ~−10 ppm, assigned to Q2 units corresponding to polymerized tetrahedra which consisted of loaded PO4 together with Si(Al)O4. The structure changes produced in allophane by phosphate loading are discussed in light of these data.

Smectites are considered to be an important component in backfill barriers due to their marked swelling and high cation exchange capacity. Both properties are affected considerably when these clays transform under natural conditions. However, we have recently described a chemical interaction between high-activity radionuclide simulators and smectites which could prove to be effective at immobilizing radionuclides definitively. Investigating the efficiency of this mechanism, independent of bentonite ageing, is a challenge. For this purpose, the reactivity shown by a non-expandable layered aluminosilicate, muscovite, has been compared to that shown by an expandable one, beidellite. Both samples were treated hydrothermally with a solution of lutetium nitrate, and the transformations were studied by X-ray diffraction, nuclear magnetic resonance and scanning electron microscopy/energy dispersive X-ray analysis. Lutetium cations react with the silicon framework of both 2:1 layered aluminosilicates under hydrothermal conditions, and new phases, lutetium disilicate, kaolinite, boehmite and natrosilite are generated. The results demonstrate that the efficiency of the chemical mechanism is not determined by the swelling and the cation exchange capacity of 2:1 layered aluminosilicates. Thus, the rare earth disilicate formation might account for the success of the clay barrier, once bentonite has lost its swelling and cation exchange capacity.

The extremely toxic protein, ricin, is derived from castor beans and is a potential terrorist weapon. Adsorption to clays might minimize the environmental persistence and toxic effects of this toxin. Ricin adsorption to clay minerals was measured using batch adsorption isotherms. Enzyme-linked immunoassay methods were used to quantify aqueous ricin concentrations. Montmorillonite, sepiolite and palygorskite effectively adsorbed ricin from aqueous solutions and yielded mostly Langmuir-type isotherms. The monolayer adsorption capacity from a Langmuir equation fit at pH 7 was 444 g ricin/kg for montmorillonite (SWy-2), but was only 5.6 g ricin/kg for kaolinite (KGa-1b). Monolayer capacities for sepiolite (SepSp-1) and palygorskite (PFl-1) at pH 7 were 59.2 and 58.1 g ricin/kg. The high-charge montmorillonite (SAz-1) effectively adsorbed ricin at pH 7, but yielded a linear isotherm with K = 5530 L/kg. At pH 5, both montmorillonites (SWy-2 and SAz-1) yielded Langmuir-type isotherms with monolayer capacities of 694 and 641 g ricin/kg. Clay samples with higher cation exchange capacities generally adsorbed more ricin, but adsorption also followed specific surface area. X-ray diffraction of <2 μm SWy-2 treated with 470 g ricin/kg indicated expansion up to 34.6 Å at buffered pHs of 4 and 7, but not at pH 10. Furthermore, ricin adsorption was greatest at pH 4 and 7, but minimal at pH 10. Treatment with 1.41 kg of purified ricin/kg clay at pH 5 yielded a 35.3 Å peak and adsorption of ~1.2 kg ricin/kg. Similar treatment with lower-purity ricin yielded less expansion and lower adsorption. The 35.3 Å peak interpreted either as a d002 or d001 reflection indicates a 70.6 Å or a 35.3 Å ricin/SWy-2 complex. This implies that adsorption and air drying have compressed interlayer ricin molecules by 18 to 65%. Effective ricin adsorption by montmorillonite suggests that it could be used to minimize the toxic effects of dispersed ricin.

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

To better predict the fate and mobility of surfactants in the environment, sorption and desorption of a nonionic polyoxyethylene lauryl ether surfactant (Brij 35) by two smectites (Wyoming montmorillonite and Panther Creek smectite) and two interstratified mica-vermiculites (IMVs) were investigated by batch techniques, X-ray diffraction, and infrared spectroscopy. Maximum surfactant sorption by smectites ranged from 196 to 256 g kg−1, whereas the maximum sorption by the IMVs was indeterminate over the range of concentrations employed. Sorption by smectites was best described by the Langmuir model, but sorption by the IMVs showed an S-shaped isotherm, suggesting that cooperative sorption occurred. The surfactant was more readily desorbed from the IMVs than from the smectites in an initial wash with water. After two water washes, 65–75% of the initially sorbed surfactant was retained by the smectite, and 44–51% of the surfactant sorbed to the IMVs remained with the solid phase. In this study, basal spacing of the smectites increased to ≈17.5 Å near the sorption maximum, suggesting intercalation of surfactant molecules in the interlamellar regions of the clay. X-ray data also suggested that the surfactant molecules were oriented horizontally in the interlayer spaces. Greater surfactant sorption by the Casmectites gradually diminished the intensity of the 1630 cm−1 infrared band dues to hydration water, indicating that some water had been displaced by the surfactant. The surfactant was also sorbed by the IMV clays, but only on external surfaces and probably via interactions of micelles with the solid phase.

Sorption and transformation of 1-naphthol by a K-smectite (K-SWy-2) were studied using batch sorption isotherms, Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The sorbents included three preparations of the reference smectite clay (SWy-2): (1) whole clay containing naturally occurring carbonate impurities, (2) SWy-2 with the removal of carbonate impurities, and (3) the carbonate-free SWy-2 fraction amended with calcite. For the whole clay and carbonate-free clay amended with calcite, >80% of added 1-naphthol disappeared from aqueous solution within 24 h, corresponding to a sorbed concentration of ≥2 mg/g of clay. In contrast, only 35% of the added 1-naphthol disappeared from solution in the carbonate-free clay after 24 h of exposure. For the clays from the three preparations in this study, <1% of sorbed 1-naphthol could be recovered by methanol extraction from the clays. The XRD data suggested that 1-naphthol was intercalated in the smectite, but was not conclusive because the 1-naphthol sorption range (1.5–2.8 mg/g of clay) in this study had relatively minor effects on the XRD patterns. The FTIR spectra of sorbed 1-naphthol-clay complexes demonstrated structural Fe3+ reduction. The spectra also showed evidence of the transformation of 1-naphthol. It suggests that reduction of structural Fe3+ may be coupled to oxidation/polymerization of 1-naphthol. Further transformation of oxidized 1-naphthol, such as by oxidative coupling reactions, is implicated by formation of a dark gray color on the clay and the inability to extract sorbed 1-naphthol.

The serpentine subgroup mineral berthierine was synthesized as a metastable precursor of the chlorite group mineral chamosite in cold seal pressure vessels at 575°C, 0.5 GPa and fO2-conditions of the NNO buffer from a glass of almandine bulk composition. The run products were investigated with X-ray powder diffraction (XRD), Mossbauer spectroscopy and electron microprobe analysis. One run product was also investigated by high-resolution transmission electron microscopy (HRTEM) and its heat capacity measured by heat pulse calorimetry and by differential scanning calorimetry in the temperature range 5–323 K. The XRD and HRTEM investigations clearly showed that the periodicity along the c axis of this sample is 7 Å demonstrating that the serpentine subgroup mineral berthierine of composition (Fe2+1.83Fe3+0.33Al0 67)[Si1.33Al0.67O5](OH)4 has formed in the synthesis experiments.

Integration of our heat capacity data, corrected to the composition (Fe2.5Al0.5)[Si1.5Al0.5O5](OH)4 for end-member berthierine, yields a standard entropy of 284.1±0.3 J mol−1 K−1. The Cp polynomial Cp = 610.72 − 5140.0 × T−0.5 − 5.8848 × 106T−2 + 9.5444 × 108T–3 is recommended for thermodynamic calculations above 298 K involving berthierine.

The mineralogical properties of goethite and clay minerals from the Shewushan supergene gold deposit have been studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). These results show that in the weathering zone of the Shewushan supergene gold deposit the mineral assemblage is mainly composed of quartz, kaolinite, halloysite, minor illite and goethite. The coexistence of these minerals is apparently indicative of weak laterization. The Al content in goethite from XRD data is ∼10.0%, suggesting formation by weak desilicification. Observation by TEM shows that the flakes of clay minerals with larger particle size usually have extremely rounded outlines, indicating intensive dissolution of clay minerals. Halloysite is derived from the decomposition of kaolinite and the micrographs of curling, tubular, and club-shaped halloysite strongly suggest significant hydration and thus a water-saturated environment. Both the XRD data of goethite and the micrographs of the clay minerals show that the environment in Shewushan is characteristic of high [H2O] activity and high [SiO2] activity. The high dynamic hydraulic conditions may facilitate the downward migration of the primary gold particles during their mechanical concentration, resulting in the accumulation of gold in the lower portion near the water table.

Interaction between metal Fe and a variety of natural and synthetic smectite samples with contrasting crystal chemistry was studied by scanning electron microscopy and X-ray diffraction from experiments conducted at 80°C. These experiments demonstrate an important reactivity contrast as a function of smectite crystal chemistry. An XRD method involving the use of an internal standard allowed quantification of the relative proportion of smectite destabilized as a function of initial pH conditions as well as of smectite structural parameters. In mildly acidic to neutral pH conditions, a significant proportion of metal Fe is corroded to form magnetite without smectite destabilization. Under basic pH conditions, smectite and metal Fe are partly destabilized to form magnetite and newly-formed 1:1 phyllosilicate phases (odinite and crondstedtite). More specifically, systematic destabilization of both metal Fe and smectite is observed for dioctahedral smectites while trioctahedral smectites are essentially unaffected under similar experimental conditions. In addition, smectite reactivity is enhanced with increasing Fe3+ content and with the presence of Na+ cations in smectite interlayers. A conceptual model for smectite destabilization is proposed. This model involves first the release of protons from smectite structure, MeFe3+OH groups being deprotonated preferentially and metal Fe acting as proton acceptor. Corrosion of metal Fe results from its interaction with these protons. The Fe2+ cations resulting from this corrosion process sorb on the edges of smectite particles to induce the reduction of structural Fe3+ and migrate into smectite interlayers to compensate for the increased layer-charge deficit. Interlayer Fe2+ cations subsequently migrate to the octahedral sheet of smectite because of the extremely large layer-charge deficit. At low temperature, this migration is favored by the reaction time and by the absence of protons within the di-trigonal cavity. Smectite destabilization results from the inability of the tetrahedral sheets to accommodate the larger dimensions of the newly formed trioctahedral domains resulting from the migration of Fe2+ cations.

Traditionally, land subsidence resulting from groundwater over-pumping has often been described by the theory of consolidation. The mechanism of land subsidence due to the dehydration of clay minerals has not been well addressed. Therefore, this study develops a smectite dehydration model to describe the effect of the release of water from the smectite interlayer upon land subsidence. Using a thermodynamic solid-solution model and laboratory studies of clay-water systems, a complete description of the dehydration relationships among the swelling pressure, basal spacing and mw/mc in a Na-smectite water system at 25°C under variable pressure conditions was derived. Accordingly, the evaluation model of the ‘hydration state of smectite’, and the ‘solid-solution model of smectite dehydration’ were formulated rigorously. These two models were applied to quantify the effects of smectite dehydration on the accumulated land subsidence in the Yun Lin offshore industrial infrastructure complex and in the Tai-Shi area. The result reveals that smectite dehydration is of importance in assessing and predicting land subsidence in a shallow sedimentary basin.

The sedimentary series from Academician Ridge, Lake Baikal, eastern Siberia, was examined using cation exchange capacity (CEC) to estimate the amount of expandable clay minerals (ECM) and high-temperature X-ray diffraction (HT-XRD) to determine their basic classification. The comparison of the magnetic susceptibility (MS) at sub-millennial resolution and the δl8O record of a reference Atlantic core (ODP 980) was used to create an age model. The most closely studied part of the series covered the major part of the last glacial cycle (120–20 ky BP). The HT-XRD analysis is based on monitoring the course of ECM dehydration with 5°C steps between 25 and 250°C and enabled us to improve the discrimination between ECM, chlorite and micas. The CEC obtained at millennial resolution showed that the neoformation of ECM in warmer periods of the last interglacial was either insignificant or fully compensated by their dissolution or dilution. The CEC record was correlated with the main climatic stages in the period studied. Both MS and CEC records reflected the environmental changes at about millennial resolution, including climatic instabilities between 117 and 73 ky BP (late MIS5).

We report a combined experimental and theoretical study of uranyl complexes that form on the interlayer siloxane surfaces of montmorillonite. We also consider the effect of isomorphic substitution on surface complexation since our montmorillonite sample contains charge sites in both the octahedral and tetrahedral sheets. Results are given for the two-layer hydrate with a layer spacing of 14.58 Å. Polarized-dependent X-ray absorption fine structure spectra are nearly invariant with the incident angle, indicating that the uranyl ions are oriented neither perpendicular nor parallel to the basal plane of montmorillonite. The equilibrated geometry from Monte Carlo simulations suggests that uranyl ions form outer-sphere surface complexes with the [O=U=O]2+ axis tilted at an angle of ~45° to the surface normal.