Batch sorption studies of Cr(III), Ni(II), Zn(II), Cu(II) and Cd(II) were conducted on Ca-bentonite and Na-bentonite to determine their retention capacities for these metal cations commonly present in the waste waters of galvanic industries. The Langmuir model was found to describe the sorption process well, offering maximum sorption capacities of 44.4 mg Cr/g, 6.32 mg Ni/g, 5.75 mg Zn/g, 7.72 mg Cu/g, 7.28 mg Cd/g on Ca-bentonite and 49.8 mg Cr/g, 24.2 mg Ni/g, 23.1 mg Zn/g, 30.0 mg Cu/g, 26.2 mg Cd/g on Na-bentonite. The use of Na-bentonite in the purification of waste waters from Ni, Cr and acid-Zn electroplating processes was an effective treatment in small-scale and in semi-industrial-scale tests. This proves the worth of this method as an alternative to existing methods. In contrast, Nabentonite was not effective in Zn sorption from cyanide-containing waste waters.

There is a clear gap in the understanding of the desorption patterns of metals sorbed on soils and clays, despite their importance in the mobility, transport and fate of metals in natural environments. In this study, we investigated the desorption behavior of Cd, Zn and Pb sorbed on montmorillonite (Mt) and on hydroxyaluminum (HyA)- and hydroxyaluminosilicate (HAS)-Mt complexes. At pH 6.5, 2.5 g L–1 of HyA-Mt and HAS-Mt sorbed almost all of the 10–6 M Cd, Zn or Pb, while Mt under the same condition sorbed ~48, 49 and 55% of the added Cd, Zn and Pb, respectively. Based on pH50 values, the selectivity of metal sorption on Mt was Pb > Zn > Cd, and on the complexes, it was Pb ≫ Zn = Cd. In general, larger fractions of sorbed metals were remobilized from Mt than from the complexes. Again, in comparison with Pb, larger fractions of sorbed Cd and Zn were remobilized from different clays. Reducing the pHs of the equilibrium sorption systems from a fixed point (6.5) to different points (6.0, 5.5, 5.0, 4.5, and 4.0) and from different points (6.5, 6.0, 5.5, 5.0, and 4.5) to a fixed point (4.0) both yielded hysteretic metal desorption patterns. The fractions of Cd and Zn desorbed through Na and Cu exchange from the clays, especially from the complexes, were very different, indicating the existence of cation exchangeable metal sorption sites of weak and strong affinities on the complexes. Based on the EDTA-extractable fractions of Cd and Zn from HAS–Mt and HyA-Mt, it appeared that HyA–metal bonds are stronger than the HAS–metal bonds. Compared with other agents, acetic acid remobilized the highest fractions of all metals irrespective of the type of clays, with a concomitant release of Al or Al + Si. The Pb-HyA/HAS-Mt bonds were, however, still much too strong to be broken substantially by this mechanism. The results accomplished in this study suggest further attention to the fundamental understanding of the mobility, fate, bioavailability and toxicity of the concerned metals in soils and related environments.

Adsorption of the ${\text{AuCl}}_4^{-}$ complex by kaolinites of different crystallinities (Kao-1 and Kao-2) from 100 mL of AuCl3·HCl·4H2O solutions containing 10,000, 500 and 50 µg/L Au and 1 g of kaolinite was measured at pH 3 to 9 at ambient temperature and 120°C. Adsorption from the 50, 500 and 10,000 µg Au/L solutions ranged from 64 to 100% at ambient temperature and from 68 to 100% at 120°C for both kaolinites. Adsorption was pH dependent with a maximum at pH <5 and a minimum at neutral and alkaline pHs. Up to 1 mg Au/g kaolinite was adsorbed by the kaolinites at both ambient temperature and 120°C. In a separate Au adsorption experiment using 100 mL of 4000 µg Au/L solutions and 0.02 to 1.0 g of Kao-1, up to 8.55 mg Au/ g of kaolinite was adsorbed. The pH dependence of Au adsorption suggests that surface complexation of Au to alumina sites at the edges of kaolinite particles might be involved. Protonation of kaolinite surface sites might facilitate adsorption of the anionic Au complex. Both kaolinites adsorbed ~100% of added Au at low pH values, but the less crystalline kaolinite (Kao-2) adsorbed more Au at high pH. Greater Au adsorption would be expected for the less crystalline Kao-2 sample if adsorption occurred at the edges of kaolinite particles.

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.

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 distributions of illite crystal (‘fundamental particle’) thickness in <0.2 µm fractions of 13 shale samples (from the Carpathian Foredeep, Poland), obtained using the Bertaut-Warren-Averbach X-ray diffraction method (MudMaster computer program), were analyzed and interpreted in terms of the mechanism of smectite illitization. All illite crystal thickness distributions in the analyzed shales are characterized by an ‘asymptotic’ shape. The origin of the asymptotic-type distributions is explained by the heterogeneity of illite crystals in shales, i.e. superposition of different populations of crystals, those included in illite-smectite (I-S) interstratifications, and those which occur as discrete illite. The analysis of the distributions in shales shows that the most frequent thickness class of illite crystals forming I-S is 2 nm. Discrete illite is composed of thicker crystals; though crystals as thin as 2 nm can also contribute to this population. The modeling of asymptotic distributions in shales by using a number of theoretical lognormal distributions shows that with progressive diagenesis, the mean thickness of illite crystals forming the I-S component increases gradually, whereas the discrete illite does not show a clear trend.

The diverse origins of illite crystals in shales do not permit determination of the mechanism of smectite illitization from the evolution of the shape of the overall crystal-thickness distribution during diagenesis. Therefore, in order to understand the mechanism of smectite illitization in shales, an attempt was made to trace the relative gains and losses of crystals of different thicknesses during illitization. This approach indicates the following mechanism of smectite illitization in the investigated shales: dissolution of smectite monolayers accompanied by growth of 2 nm crystals which are largely of detrital origin. Nucleation of 2 nm illites seems to be very limited.

The effects of a subvolcanic intrusion on its host rocks in the Priego de Córdoba area (SE Spain) was studied by optical microscopy, X-ray diffraction and electron microscopy. The intrusion of a laccolith of stratiform dolerite in partially consolidated marly sediments at quite shallow depths below the ocean floor took place during the intracontinental rifting phase of the Subbetic zone of the Betic Cordilleras. In the first stage, contact metamorphism caused the crystallization of calc-silicate consisting of grossular andradite garnet, diopside, vesuvianite and titanite for which the upper temperature limit was 500°C. Phyllosilicates are found in a network of veins cross-cutting the carbonate and calc-silicate matrix, indicating their formation during a process of hydrothermal alteration superimposed on the contact aureole. In the area closest to the subvolcanic rocks, saponite is the main phyllosilicate although some dispersed chlorite is found. In the zone furthest from the contact, corrensite together with saponite and beidellitic smectites were observed. The presence of low-temperature phases (saponite) in the area closest to the laccolith reveals the evolution of the hydrothermal system toward cooler conditions. In the early stage, the circulation of a hot hydrothermal fluid caused the crystallization of chlorite in the area surrounding the subvolcanic body and corrensite in the more distal area, which might have begun even during the contact metamorphism stage. A cooling phase followed, resulting in the crystallization of saponite in the host rocks, and the crystallization of dioctahedral and trioctahedral smectites inside the subvolcanic body.

Octadecylamine (ODA) was used to intercalate a fine-grained and a coarse-grained fraction of natural Mg-vermiculite (VER) using a low-temperature melting procedure. Mixtures of Mg-vermiculite fractions and powdered ODA in the molar ratios of 2:1, 1:1, 1:2 and 1:6 were homogenized and heated for 1, 3, 15 and 30 h at 80°C to prepare intercalated samples. X-ray powder diffraction analysis of intercalated samples was combined with molecular modeling to investigate their interlayer structure. Significant amounts of non-intercalated vermiculite and diffuse peaks with very low intensity and basal spacings close to 29 Å were identified when the lowest concentration (molar ratio VER:ODA = 2:1) was used. According to molecular modeling, this indicates the initial stage of a one-layer arrangement of distorted ODA molecules in the interlayer. If the concentration of ODA molecules and treatment time were increased, a two-layer arrangement of ODA molecules with a different ODA chain-disorder and interlayer-space saturation was identified. Interlayer ODA molecules were inclined to the vermiculite basal plane with an inclination angle for two-layer arrangements that ranged from 76 to 95°. Experimental basal spacings with these two-layer arrangements varied from 52 to 58 Å and were in agreement with molecular modeling results. A fully-saturated 58 Å two-layer ODA arrangement was identified when higher ODA concentrations (VER:ODA = 1:2 and 1:6) and 15 and 30 h treatment times were used. There was no significant difference between ODA-intercalated samples prepared using fine-grained and coarse-grained Mg-vermiculite fractions. A grafted ODA-chain nano-layer with a 49.6(2.1) Å average height was observed on the surface of thin ODA-intercalated micro-flakes using atomic force microscopy. Grafted ODA chains not only created an homogeneous surface nano-layer, but also variable-width channels between the ODA molecules.

Hydrotalcite-like layered double hydroxides (LDHs) containing different ratios of Ni2+, Cu2+, Mg2+ and Al3+ in the layers have been prepared by a new method, the key features of which are a very rapid mixing and nucleation process in a colloid mill followed by a separate ageing process. The compositions and structural parameters of the materials synthesized using the two routes are very similar, although the degree of crystallinity is slightly higher for the LDHs produced using the new method. The major advantage of the new method is that it produces smaller crystallites, having a very narrow range of distribution of crystallite size. In the conventional coprecipitation process at constant pH, the mixing process takes a considerable time during which nuclei formed at the beginning of the process have a much longer time to undergo crystal growth than those formed at the end of the process. The consequence is that a wide dispersion of crystallite sizes is obtained. In the colloid mill process, however, the mixing and nucleation is complete in a very short time and is followed by a separate ageing process.

Layered metal hydroxides exhibit non-uniform broadening of lines in their X-ray powder diffraction (XRPD) patterns, which cannot always be explained on the basis of crystallite size effects. In the case of hexagonal solids such as nickel hydroxide, DIFFaX simulations of the XRPD patterns show that: (1) stacking faults and turbostratic disorder at low (<30%) incidence selectively broaden the h0l reflections; (2) turbostratic disorder at high (>40%) incidence causes asymmetric broadening of the hk0 reflections and a complete extinction of the hkl reflections while leaving 00l unchanged; (3) interstratification selectively broadens the non-hk0 reflections; and (4) cation vacancies reduce the relative intensity of the 100 reflection. In contrast, a reduction in the thickness of the crystallites along the stacking direction of the layers selectively broadens the 00l reflections while a reduction in the disc diameter causes the progressive broadening and extinction of the hk0 reflections. Comparison with experimental data shows that several kinds of disorders have to be invoked to account for the observed broadening. DIFFaX simulations enable the quantification of the different kinds of disorder.

Natural soils change by long-term pedogenetic mechanisms, but tillage effects can also strongly affect the evolution of soils, mainly their physicochemical properties. The present paper describes the impact of fertilizers and amendments on soil mineralogy in experimental plots, without plant interaction.

The soils of the 42 plots experiment at the INRA experimental station in Versailles (France) have been managed with fertilizers without plant growth since 1929. Strong changes in pH were observed and cation exchange capacities doubled between low and high pH (from 3.6 to 8.2). Strong acidification caused more evolution in the clay particle distribution without selective action on the clay composition.

While the clay content varied only slightly, the organic matter content changed considerably, decreasing with non-organic treatment and increasing in the plot with manure treatment. The major clay minerals in the experimental plots are two disordered illite-smectite mixed-layer minerals, with minor amounts of illite/mica and kaolinite. Most treatments effected only minor changes in clay mineralogy. However the illite (non-expandable mineral) content increased in plots with K addition either as KCl treatment or in manure amendments by increasing the illite content and the illite (non-expandable layer) content of the I-S minerals. Manure changed the I-S mineral to a greater extent.