The adsorption of Cr(III) was studied at pH 1, 2, 3, 4, 6, 8, and 10 on chlorite and kaolinite and at pH 1, 2, 3, and 6 on illite. The amount of chromium adsorbed on chlorite varied from 3.1 × 10–5 mole/ g at pH 1 to 16.6 × 10–5 mole/g at pH 4, and on illite from 4.9 × 10–5 mole/g to 9.2 × 10–5 mole/g at pH 1 and 3, respectively. Kaolinite adsorbed 3.7 × 10–5 mole Cr/g at pH 1, 2, and 3 and 5.5 × 10–5 mole Cr/g at pH 4. Measurements of the Cr 2p core-level binding energies indicate that chromium is probably adsorbed as a Cr(III) aqua ion at pH values below 4. The binding energies for the Cr 2p level for samples prepared above pH 4 compare favorably with the value determined for chromium hydroxide and lead to the conclusion that the chromium species present at pH 6, 8, and 10 is chromium hydroxide.

Three samples of bluish chromium-bearing dickite and chromium-bearing kaolinite were examined by X-ray powder diffraction, chemical analysis, electron microprobe, optical, and infrared techniques to determine whether chromium is part of the mineral structure or present in an impurity phase. Two of the samples studied contain a single dominant chromium-bearing phase (either dickite or kaolinite); the third contains equal proportions of both minerals. The optical absorption and infrared spectra are consistent with the presence of octahedrally coordinated chromium. The range of Cr3+-Al3+ substitution is rather limited: up to 0.06 atoms per unit cell. The electron microprobe study revealed the presence of very rare, minute grains of chromite, as well as a uniform distribution of chromium in dickite and kaolinite, indicating that chromium occupies octahedral sites in the structure of these minerals.

The nature of Cr(NH3)63+ and Cr(en)33+ (en = ethylenediamine) adsorbed on chlorite, illite, and kaolinite has been studied by X-ray photoelectron spectroscopy (XPS). The interaction of the chromium complexes with the clays began at pH 3. During the 7-day interaction time the pH of the complex-clay suspension increased to 8 for illite and chlorite. For kaolinite the pH increased to about 3.6 with Cr(NH3)63+ and to 6.4 with Cr(en)33+. These pH changes appear to be associated with a clay-catalyzed hydrolysis of the chromium-amine complexes. XPS binding-energy data for adsorbed chromium indicate that the dominant species are chromium aqua complexes. Nitrogen/chromium atom ratios, calculated from the XPS photopeak intensities, are less than 6:1 for complexes adsorbed on the clays, suggesting that chromium complexes are initially adsorbed but subsequently hydrolyze to produce aqua-chromium surface species.

Hydroxychromium montmorillonites were prepared from solutions containing chromium nitrate and varying amounts of NaOH. The reactant Cr ions were hydrolyzed and, in some experiments, were dimerized to a significant extent. The extent of polymerization in the product formed from a solution containing a maximum amount of [Cr2(H2O)8(OH)2]4+ was compared with that in products obtained from solutions containing monomer, [Cr(H2O)5OH]2+, and lesser amounts of the dimer. Despite the uncertainty about the nature and amounts of product interlamellar species, the catalytic effect of the montmorillonite interlayer on the hydrolysis and polymerization of Cr(III) appears to be independent of the nature of the reactant species. The validity of this conclusion depends to a large extent on the reliability of water determination in the clay mineral species, which is estimated to be no better than 5%. The assumption that H2O+ is 'combined’ and H2O— is 'free’ water is shown to be partially true, thereby causing some uncertainty in the interpretations of interlayer compositions.

When 1-hexene was adsorbed by Cr3+-montmorillonite at room temperature, all evidence of C=C(str) vibrations was lost. Protonation of the alkene occurred, and the secondary carbocation formed was bound at a site on the primary coordination sphere of the interlayer cation. Some of the hydrogen atoms of these primary-sphere water molecules were involved in strong hydrogen bonds to the silicate sheets, whereas others did not form such bonds, but were free and directed into the interlayer space. These latter hydrogen atoms were labile and protonated the alkene molecules.

The name volkonskoite was first used in 1830 to describe a bright blue-green, chromiumbearing clay material from the Okhansk region, west of the Ural Mountains, U.S.S.R. Since that time, the name has been applied to numerous members of the smectite group of clay minerals, although the reported chromium content has ranged from 1% to about 30% Cr2O3. The name has also been applied to some chromian chlorites. Because volkonskoite has been used for materials that differ not only in their chromium content but also in their basic structure, the species status of the mineral has been unclear.

To resolve this uncertainty, two specimens of volkonskoite from (1) Mount Efimiatsk, the type locality in the Soviet Union (USNM 16308) and (2) the Okhansk region in the Perm Basin, U.S.S.R. (USNM R4820), were examined by several mineralogical techniques. Neotype sample 16308 has the following structural formula:

$({\text{Ca}}_{0.11}{\text{Mg}}_{0.11}{\text{Fe}}^{2+}{\hspace{0.17em}}_{0.03}{\text{K}}_{0.02})({\text{Cr}}_{1.18}{\text{Mg}}_{0.78}{\text{Fe}}^{3+}{\hspace{0.17em}}_{0.29}\text{Ca}{}_{0.02})({\text{Si}}_{3.50}{\text{Al}}_{0.51}){\text{O}}_{10}{(\text{OH})}_2\cdot 3.64{\text{H}}_2\text{O}.$

Sample R4820 has the following structural formula:

$({\text{Ca}}_{0.25}{\text{Mg}}_{0.05}{\text{Fe}}^{2+}{\hspace{0.17em}}_{0.01}{\text{K}}_{0.03}{\text{Mn}}_{0.01})({\text{Cr}}_{1.07}{\text{Mg}}_{0.75}{\text{Fe}}^{3+}{\hspace{0.17em}}_{0.35}({\text{Si}}_{3.59}{\text{Al}}_{0.43}){\text{O}}_{10}{(\text{OH})}_2\cdot 4.22{\text{H}}_2\text{O}.$

Mössbauer spectroscopy indicates that 91% and 98% of the iron is present as Fe3+ in samples 16308 and R4820, respectively. X-ray powder diffraction patterns of both samples have broad lines corresponding to minerals of the smectite group.

On the basis of these data, volkonskoite appears to be a dioctahedral member of the smectite group that contains chromium as the dominant cation in the octahedral layer. Smectites containing less than this amount of octahedral chromium should not be called volkonskoite, but should be named by chemical element adjectives, e.g., chromian montmorillonite, chromian nontronite.

In environments contaminated with Cr, the interlayers of expandable layer silicates may serve as sinks for this potentially toxic element. As a means of determining the potential for smectites to serve as sinks for Cr, the precipitation products of Al and Cr in the interlayers of a montmorillonite were examined. Five montmorillonite (SWy-1) clay suspensions were treated with preweighed amounts of AlCl3 and CrCl3 to give five Al/(Al + Cr) molar ratios (1.0, 0.67, 0.5, 0.33, 0) with a total trivalent cation (M3+) concentration of 600 cmol(+)/kg clay. The clay-cation suspensions were titrated with 0.1 N NaOH to give a NaOH/M3+ molar ratio of 2.5. Analysis of the solid-phase reaction products showed that the cation exchange capacity and specific surface of all clays were reduced. Chromium reduced the exchangeability of the interlayers while Al increased the thermal stability. X-ray diffraction analysis revealed that all Al-containing interlayer materials formed similar gibbsitelike polymers. Data from infrared spectroscopy indicated that both Al and Cr were present within the same polymer. Differential thermal analysis and thermogravimetric tracings showed that the rapid collapse of the interlayer in the Cr end-member upon heating was due to a low-temperature loss of hydroxyls. It was not possible to identify all interlayer structures in the Cr end-member. Data from X-ray photoelectron spectroscopy showed all Cr to be Cr(III). Displacement of the interlayer material became more difficult as Cr content increased. The least exchangeable interlayers, therefore, may be found in environments containing the most Cr.

The reduction of hexavalent chromium species in aqueous solutions by interaction with Fe(II)-bearing solid surfaces was studied using a 0.96 × l0−3 M Cr(VI) solution and iron-rich clays with different Fe(II)/Fe(III) ratios, layer charge, and exchange properties, i.e., chlorite, corrensite, and montmorillonite. Experimental studies demonstrated that Fe(II)-bearing phyllosilicates reduce aqueous Cr(VI) ions at acidic pH. Chlorite and corrensite, owing to the high Fe(II)/Fe(III) ratio, are electrochemically reactive, as rapid Cr(VI) reduction indicated. In contrast, montmorillonite showed minimum to nil reactivity towards Cr(VI). Furthermore, corrensite, which is high in both Fe(II)/Fe(III) ratio and exchange capacity, adsorbs the greatest amount of chromium.

X-ray absorption spectroscopy at Al, Mg, Fe, and Cr K-edges was used to investigate the adsorbed chromium species. The montmorillonite sample, unaffected by treatment with Cr(VI) solution, displays no change at any investigated edge. Edge shape and energy also do not change for the Mg and Al spectra in corrensite, and changes are minor in chlorite. By contrast, the Fe K-edge changes both in chlorite and corrensite, and indicates an increase of Fe(III) in treated samples at the expense of pre-existing Fe(II). Cr K-edge spectra show that chlorite and corrensite sorb Cr(III), which implies its reduction from Cr(VI) in the interacting solution.

The hydrothermal synthesis of Mg-beidellite in which limited amounts of Ga and Cr are clearly shown to be incorporated into nonexchangeable positions in the clay layer framework is reported for the first time. Elemental analyses indicate that, up to at least 15 mole percent, Ga can replace Al virtually completely; Cr incorporation is more difficult. It appears that the Ga that is incorporated into the beidellite is located primarily in the octahedral sheet. Pillaring of the synthesized beidellite by replacing the Mg2+ with large AlO4Al12(OH)24(H2O)127+ ions showed that approximately 5.5 meq Al3+ was required per g of beidellite to achieve complete pillaring. This amount is very similar to that required for montmorillonite, and suggests that the cation exchange capacity (CEC) of the beidellite is about 98 meq/g.

Clay–organic interaction is an important natural process that underpins soil ecosystem services. This process can also be tailored to produce clay–organic nanocomposites for industrial and environmental applications. The organic moiety of the nanocomposites, typically represented by a toxic surfactant, could be replaced by hydrochar formed from biomolecules (e.g. glucose) via hydrothermal carbonization. The effect of montmorillonite (Mnt) and glucose dosage on hydrochar formation, however, has not been clarified. In addition, the mechanisms by which Mnt-hydrochar nanocomposites (CMnt) can detoxify and remove carcinogenic Cr(VI) from aqueous solution are not well understood. In the current study, research milestones in terms of clay–organic interactions are summarized, following which the synthesis and characterization of CMnt for Cr(VI) adsorption are outlined. Briefly, 1 g of Mnt was reacted with 75 mL of glucose solution (0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 mol L−1) by hydrothermal carbonization at 200°C for 16 h. The resultant CMnt samples were analyzed for chemical composition, functional groups, morphological features, and Cr(VI) adsorptive properties. Mnt promoted the conversion of glucose to hydrochars, the particle size of which (~80 nm) was appreciably smaller than that formed in the absence of Mnt (control). Furthermore, the hydrochars in CMnt had an aromatic structure with low hydrogen substitution and high stability (C/H atomic ratio 0.34–0.99). The weakened OH (from hydrochar) and Si–O–Si stretching peaks in the Fourier-transform infrared (FTIR) spectra of CMnt are indicative of chemical bonding between Mnt and hydrochar. The CMnt samples were effective at removing toxic Cr(VI) from acidic aqueous solutions. Several processes were involved, including direct reduction of Cr(VI) to Cr(III), complexation of Cr(III) with carboxyl and phenolic groups of hydrochar, electrostatic attraction between Cr(VI) and positively charged CMnt at pH 2 followed by indirect reduction of Cr(VI) to Cr(III), and Cr(III) precipitation.

Waste brownfield-site soils contaminated with heavy metals such as Zn and Cr are of critical environmental concern because of the rapid urbanization and industrialization that is occurring in China. Thermal treatment can fix heavy metals in specific mineral structures, which might be a promising technology for remediation and reutilization of the metal-contaminated soils. The objective of the present study was to elucidate the stabilization mechanisms of Zn and Cr through thermal treatment of mixtures of ZnO + Cr2O3 to form ZnCr2O4 and to confirm that Zn and Cr were incorporated simultaneously into the spinel structure. The incorporation efficiency for Zn was quantified, with the value ranging from 70.6 to 100% over the temperature range 700–1300°C. Leaching results further confirmed that ZnCr2O4 spinel was a superior product for Zn and Cr immobilization. Then, by artificially sintering Zn- and Cr-enriched soils, both Zn and Cr were immobilized effectively (with three orders of magnitude reduction in Zn leachability) in the ZnCr2O4 spinel as the predominant product phase. In addition, multiple heavy metals such as Zn, Cu, and Cr in the actual brownfield-site soils were well immobilized after sintering, which confirmed the potential for practical application of the thermal treatment technology utilized in this study.

In classical toxicology, speciation of carbon is taken for granted and the carbon compounds responsible for toxicity are always described with the appropriate chemical nomenclature. By contrast, speciation of other elements is largely ignored and elements other than carbon are often condemned as toxic because of evidence relating toxicity to only a few of the chemical species in which they occur. In some cases, such as chromium, the distinction between oxidation states (chromium III and chromium VI) may be recognized as important. The fact that chromium VI may only be a toxicological problem in certain well defined forms, such as specific chromate salts that may cause nasal and lung cancer, and then only by the respiratory route of exposure, is largely ignored. Failure to consider properly chemical speciation of elements other than carbon can lead to poor use of our resources. Laws and regulations based on simple elemental analysis may wrongly condemn environmental media or products as toxic and prevent the use of important resources.

The composition of magmas proposed as parental to the layered suite of the Bushveld Complex, and some models for the manner of their emplacement, are reviewed briefly. Included are some contributions published in South Africa, with which overseas readers might be less familiar. Emphasis is given to the broader features of the cumulates, and the contradictions raised by whole-rock compositional, Sr-isotopic, and trace-element data that cloud their correlation with proposed parental magmas. It is concluded that the Lower, Critical and Main Zones are the derivatives of only two primary magmatic lineages, while a third was added to residual liquids from which the layered rocks above the Pyroxenite Marker were formed. Excessive amounts of olivine and chromium in the cumulates of the Lower and Lower Critical Zones in the northern sector of the Western Limb can seemingly not be accounted for by the composition and volume of the putative magmas. This is attributed to (1) this sector being a proximal facies located close to the original feeder, and/or (2) crystal-charged magma batches, expelled from a lower magma chamber, being periodically injected into and dispersed within the liquids already in place in the Bushveld chamber. Thus, ongoing changes in the bulk composition of the liquids within the chamber would not be reflected in the rinds of earlier, chilled-facies rocks. The expulsion of significant volumes of liquid residua from the chamber during cumulate deposition is not ruled out.

The Outokumpu region of Finland is notable for the large number of Cr-rich silicate and oxide phases associated with the massive sulphide deposits. In this paper analyses of Cr-rich phases in the epidote-clinozoisite and muscovite groups are presented. The muscovite-type phase shows a maximum 80% substitution of Cr for A1 on octahedral sites with a maximum 24.7 wt.% Cr2O3. Apparent complete solid solution between this extreme composition and the fuchsitic muscovites is indicated. The clinozoisite type phase has a maximum 15.4 wt.% Cr2O3, with a composition close to Ca2CrAl2Si3O12(OH). As with the micas, complete solid solution of Cr for Al in the clinozoisite structure is indicated.

Some of the physical, chemical and mineralogical characteristics of Portland cement and related materials relevant to nuclear waste immobilization are defined. The ability to condition and maintain a high aqueous pH is undoubtedly the most important factor: it precipitates many species as hydrous oxides or hydroxides. However, in the longer term, many species – cationic as well as anionic – react with one or more cement components forming solubility-limiting phases. Progress on characterization of these phases is outlined. Many of the host phases have natural equivalents and this gives comfort in respect of their likely persistence over geological time. The emerging picture of immobilization in cement suggests that cement compositions can be tailored in terms of pH, Eh and internal chemistry so as to maximize immobilization potential. Nickel, uranium and chromium and chloride are used as examples.