Adsorption of uranyl (UO22+) ions to mineral surfaces is a potentially effective method for removing this hazardous metal from water, but other toxic trace metal ions (Xn+: Rb+, Sr2+, Cr3+, Mn2+, Ni2+, Zn2+, Cd2+) in uraniferous wastewaters compete with UO22+ for adsorption sites and thus may diminish the capacity of adsorbents to sequester UO22+. A better understanding of competitive adsorption among these metal ions and the development of better adsorbents are, therefore, of critical importance. The purpose of the present study was to synthesize and characterize magnetic adsorbents, consisting of MFe2O4 (M = Mn, Fe, Zn, Co, or Ni) nanoparticles synthesized on montmorillonite (Mnt) edge sites, and to investigate their use as adsorbents for UO22+, including competitive adsorption with trace metal ions. Selective adsorption was studied using Langmuir, Freundlich, and Dubinin-Radushkevich isotherms, and the results showed that Xn+ ions were adsorbed primarily on MFe2O4-montmorillonite surfaces, and the UO22+ ions were adsorbed on the interfaces between montmorillonite edge surfaces and MFe2O4 nanoparticles. Using the Freundlich model, the interface adsorption capacity of UO22+ reached 25.1 mg·g–1 in mixed solution. Further, the UO22+ and Cr3+ ions had a redox reaction on the interfaces with synergistic adsorption. Herein, the adsorption capacity of Cr3+ was 60.2 mg·g–1 using the Freundlich isotherm. The results demonstrated that the MFe2O4-montmorillonite with highly selective adsorption of UO22+ ions is applicable to UO22+ treatment in the presence of toxic trace metal ions.

Graphical abstract

The Maramures Basin, in the Carpathian mountain belt of northern Romania on the border with the Ukraine, belongs to the eastern part of the Pannonian Basin. In the study area, extensional tectonic movements during the Miocene were coeval with silicic and intermediate volcanism in the inner part of the Eastern Carpathians. Throughout this region, explosive events have resulted in the deposition of pyroclastic flows and ash-fall deposits interbedded with marine sediments.

Several tuff units of Badenian (15–13.6 Ma) age occurring throughout the area are extensively zeolitized. These rocks occur as massive homogeneous beds, white to pale greenish-blue, and are commonly extensively jointed. In the Bârsana-Calinesti area and along the Morii Valley, two conspicuous tuff units that can be traced over many km are separated by a calcareous sandstone bed. Most tuffs have a vitroclastic texture in which former glass shards are pseudomorphed by clay minerals and clinoptilolite. Opal-CT commonly occurs as clumps of radiating rods that produce a spherical morphology. Also, rare celadonite is found in the lower greenish tuffs. Pyrogenic crystal fragments are quartz, plagioclase and biotite. Folded muscovite plates and fragments of basement rocks are dominant among the lithic clasts. Above the Bârsana Formation, a second series of white zeolitized tuff, the Ocna Sugatag Formation, is represented by at least two different units overlying an evaporite salt deposit. A large outcrop of a massive white tuff at this locality contains abundant fine-grained clinoptilolite and cation-exchange capacity values of >160 meq/100 g. Clinoptilolite-Ca is also present in the Sighetu tuff unit in the northern part of the Maramures Basin where a distinctive horizon contains plant remains preserved in spherical concretions. Plant material and algal limestones in the same succession strongly suggest that the marine depositional environment was close inshore, and shallow-rather than deep-water conditions are inferred. A mineralogically similar, unaltered, volcanic tuff found in the Coas area suggests that the precursor glass was rhyolitic (72–74% SiO2) with a high-K calc-alkaline affinity. We conclude that pervasive zeolitization is due to the interaction between seawater and vitroclasts at an early stage after deposition.

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.

Heavy metals in the environment are a problem due to their toxicity and bioaccumulation. Adsorptive removal of heavy metals by clay minerals has garnered increasing attention due to the abundance, low cost, and exceptional physicochemical properties of the clays. The purpose of the present study was to investigate the utilization of two Turkish sepiolite samples, nodular sepiolite (NS) and industrial sepiolite (IS), as adsorbents in removing Ni2+ ions from aqueous solutions. The specific surface areas of NS and IS are 182.19 m2 g–1 and 63.78 m2 g–1, respectively. The effects of adsorbent dosage, initial pH, contact time, initial concentration, and temperature on the adsorption of Ni2+ ions onto the sepiolite samples were investigated using a batch method. The optimum adsorbent dosage was determined as 0.6 g/50 mL of adsorbent and the optimum pH value was 6.0, for both sepiolite samples. The adsorption process obeyed the Freundlich isotherm model (KF: 4.89–9.73 mg1–1/n L1/n g–1 for NS and 4.27–6.42 mg1–1/n L1/n g–1 for IS) and the pseudo-second order kinetics model (k2: 0.0049–0.0397 g mg–1 min–1 for NS and 0.0688–0.1195 g mg–1 min–1 for IS). The adsorption process was spontaneous and endothermic, and the randomness increased. The samples exhibited large adsorption capacities through three cycles of adsorption-desorption tests. The results revealed that the sepiolite samples are promising as cost-effective adsorbents for the removal of Ni2+ ions from aqueous solutions.

Sorption of U(VI) on clay and related minerals has been inspected experimentally and computationally because of its central role in safety considerations of geological repositories for highly radioactive waste. Np(V), which also has long half-life isotopes, has received considerably less attention. The purpose of the present study was to investigate computationally the adsorption of Np(V) on a clay-mineral surface and to compare it to adsorption of U(VI). As a sample case study, adsorption of Np(V) at the (110) edge surface of the common clay mineral montmorillonite was modeled. The density functional approach and periodic supercell models were applied. Mono- and bidentate adsorption complexes with coordination numbers 4 and 5 were inspected and compared to corresponding U(VI) species. While U(VI) prefers bidentate adsorption complexes with varying coordination numbers, Np(V) is more stable when monodentate-coordinated with a coordination number of four. In line with its smaller hydrolysis constant in aqueous solution, Np(V) shows a lower tendency to form monohydroxides on the mineral surface compared to U(VI). As no experimental geometry parameters are available for Np(V) adsorbed on montmorillonite, the results were compared tentatively to EXAFS data for adsorption at kaolinite and good agreement for the geometry changes due to adsorption was found for the more preferred adsorbed species.

Sonic anisotropy of clay resulting from particle orientation was studied by means of velocity measurements on anisotropically consolidated kaolinite. Samples were prepared from a kaolin-water slurry under consolidation pressures ranging from 80 to 400 psi, with two distinct stress histories. Directional velocity measurements were made over a wide range of water contents as saturated samples were allowed to dry by evaporation to water contents below the shrinkage limit. Directional variation was most pronounced with partial saturation, when directional velocities differed by as much as a factor of two. The degree of sonic anisotropy is seen to correlate with variation in the shrinkage limit, showing a systematic dependence on particle orientation, but no unique relation to consolidation stress exists because of the overriding influence of stress history.

The reaction of phlogopite with a trimethylsilylating reagent yielded organosilicate compounds which are soluble in various organic solvents. Gas chromatographic analysis of the soluble products indicates that they consist of the trimethylsilylated derivatives of silicic acids which have been formed in the decomposition of phlogopite by hydrochloric acid and that silicic acids formed by the acid attack are monomelic and also oligomeric. The increase of the ratio of GC peak areas of monomer derivative to dimer one with an increase of the reaction time shows that silicic acids in the reaction system tend to depolymerize. The difference between phlogopite and biotite in the ease of trimethylsilylation also is discussed.

The present study investigated the use of local and affordable clinoptilolite for the removal of persistent dyes from water. To improve its adsorption capacity, Na-clinoptilolite was modified chemically with two N-terminated siloxanes (molar mass: 2600 and 11000 g/mol) and used to adsorb the dye phenol red. The results of Fourier-transform infrared spectroscopy (FTIR) showed that N-terminated siloxanes were grafted successfully onto clinoptilolite. Examination by X-ray diffraction and scanning electron microscopy supported the suggestion of modifications observed by FTIR. The modified clinoptilolite showed improved adsorption properties for phenol red: up to 0.32 mg of phenol red were removed per g of clinoptilolite modified with N-terminated siloxanes from water, while HCl-treated clinoptilolite removed only 0.15 mg after 4 h. Langmuir and Freundlich models were used to obtain isotherm parameters. Results (with R2 > 0.84) from pseudo-first and pseudo-second order equations suggested that adsorption could have involved chemisorption and physisorption, probably because of the mineral-organic nature of the materials prepared.

The content of kaolinite plus halloysite is differentiated quantitatively from chlorite by differential dissolution, even in those samples wherein each mineral has 500°C heat instability of the 7 Å peak. This differentiation is possible because the structures of kaolinite and halloysite are destroyed on loss of the 7 Å peak, producing amorphous material which is rapidly soluble in 0.5 N NaOH, whereas the chlorite structure remains largely intact with only partial dehydration of the octahedral layer. The amorphous residue of kaolinite-halloysite is dissolved from the other mineral components of the heated sample with sodium hydroxide and the dissolved silica and alumina are allocated to kaolinite. The percentages of kaolinite thus obtained for Elliott, B3–C horizon, 2–0.2 μ fraction, are 3.8 and 3.7 based on silica and alumina, respectively. Similarly, the percentages of kaolinite obtained for Buchanan, B1 horizon, 2-0.2 μ fraction, are 14.9 and 13.8 based on silica and alumina, respectively. Collapse of the vermiculite basal spacing to 10 Å on K saturation and heating to 300°C, together with the clear differentiation of kaolinite by differential dissolution analysis (D.D.A.) above, removed the possibility of misinterpretation of the chlorite-like diffractometer tracing by kaolinite and vermiculite occurring together. Other clays, from Davidson and Susquehanna soils, had 44 and 42 to 43 percent kaolinite, based on silica and alumina, respectively. The vermiculite and montmoril-lonite contents of soil clay samples are quantitatively determined by specific surface. The mica percentages are based on the K2O after exclusion of potassium in feldspars. Water loss in the 400°C-to-ignition range gives an important quantitative basis for chlorite.

Montmorillonite and K-feldspar deposits of potential economic interest occur in the Late Oligocene-Miocene tuffs of the Vizcarra Formation in the state of Durango, Mexico. The two minerals were formed separately from rhyodacitic to rhyolitic pyroclastic deposits in a closed hydrologie system and diagenetically altered following two different patterns. In material deposited on dry land the glass was completely replaced by K-feldspar, and the interstices between the replaced glass bubbles and shards were filled with chalcedony, quartz, and albite. Pyroclastic material deposited in an alkaline lacustrine environment were diagenetically altered to montmorillonite, which formed the bentonitic tuffs widely exposed beneath the K-feldspar-rich tuff. These bentonitic tuffs contain as much as 85% montmorillonite plus authigenic chalcedony and quartz. Pyrogenic sanidine, quartz, and oxybiotite, coarse glass shards, and clastic grains make up about 8% of the clay-rich tuffs. The composition of the montmorillonite corresponds to the formula (Si3.88Al0.12)(Al1.41Mg0.59)O10(OH)2(Ca0.07Mg0.11,Na0.28K0.06). The montmorillonite is dioctahedral, the surface acidity is of the Lewis type, and the clay swells to one- and two-layer complexes. The cation-exchange capacity is 64 meq/100g; base exchange is Ca2+, 15; Mg2+, 20; Na+, 4.1; and K+, 1.0 meq/100 g. Its interlamellar charge is 18.6 microcoulombs/cm2. Dacitic pyroclastics were deposited later at higher elevations along the margins of the basin. Percolating solutions apparently removed a siliceous leachate from the dacitic glass and partially altered it to clinoptilolite.

Dyestuffs and other reagents which exhibit characteristic colors when adsorbed on clay granules frequently have been employed as aids in clay identification. The colors generally are believed to result from pleochroic effects and acid-base or oxidation-reduction reaction mechanisms. Certain aniline dyes, solutions of which vary in color according to their hydrogen ion content, may be used to indicate the relative acidity of clay.surfaces as well as to heighten the natural pleochroism of kaolin minerals. When n clay sample has been pretreated with acid, the colors assumed by the adsorbed dye depend on the characteristic base exchange capacities of the various clay mineral groups present.

Aromatic diamines, amino phenols, and other compounds which can be oxidized to colored semiquinone cations permit particularly sensitive and positive identification of members of the montmorillonoid family and certain other three-layer clay minerals. Theories concerning the nature of this apparently catalytic oxidation on clay surfaces are inadequate to explain the reactions. New concepts and additional experimental information are needed.

The Brunauer-Emmett-Teller (BET) theory models the effective specific surface area and water content of solids as a function of the relative vapor pressure of water. A modified form of the BET equation has been used successfully to model water activity in concentrated electrolyte solutions as a function of electrolyte concentration. This modified form, referred to here as the Stokes-Robinson BET model, is based on the electrolyte molality rather than on the mass of solute sorbed. The present study evaluates the Stokes-Robinson form of the BET equation to model water-sorption data on two smectites with different layer charges. One smectite was saturated with Na+ and another with Na+, Ca2+, or Mg2+. These results are compared to the Stokes-Robinson BET results of aqueous electrolyte solutions. Given published data on cation exchange capacities and water-vapor sorption isotherms for various clays, the molality of the aqueous phase in contact with the clay surface is calculated and related to water activity. The Stokes-Robinson BET model was found to describe accurately the water activity as a function of cation molality below water activities of 0.5 for the smectites. Good relative agreement was obtained between the number of water binding sites predicted by the model and the experimental data reported in the literature for other smectites. Water molecules were found to have a significantly greater affinity for montmorillonite than electrolyte solutions with the same cation molality as the montmorillonite interlayer. This modified BET approach simplifies water-activity modeling in highly saline environments because the same equation can be used for both the liquid- and mineral-surface phases.

Chitosan (CTS) modified montmorillonite (Mnt) composites (CTS-Mnt), which have been widely reported for the adsorption of heavy-metal ions and biological dyes, have not been applied to the field of mycotoxin adsorption. The current study was focused on the preparation of CTS-Mnt by calcination as a mycotoxin adsorbent for the efficient removal of aflatoxin B1 (AFB1). The CTS-Mnt samples obtained were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and nitrogen adsorption/desorption analysis. The CTS-Mnt samples prepared at various calcination temperatures exhibited varying structural configurations, surface hydrophobicities, and texture properties. The results revealed that stable CTS-Mnt speciments, obtained at <350°C, displayed superior adsorption capacity for AFB1 from a simulated gastrointestinal tract, increasing from 0.51 mg/g of raw Mnt to 4.97 mg/g. With increased calcination temperature, the effect of pH on the adsorption process of AFB1 becomes negligible. This study demonstrates that the novel CTS-Mnt has tremendous potential as an AFB1 adsorbent.

Clay mineral analyses were made of three groups of soil profiles — one developed from Peorian loess overlying Illinoian till — one associated with glacial till of Wisconsin age — one developed on deep to thin loess overlying Wisconsin till. These groups were investigated to determine the influence of parent material and intensity of weathering upon the soil profile development and clay mineral composition.

Montmorillonite, illite, and chlorite are the dominant clay minerals in all the samples studied. In known loess samples, montmorillonite is invariably the most abundant clay mineral component. In the samples of unweathered till of Wisconsin age, illite and chlorite are the abundant clay minerals.

Rehydroxylization of the anhydrous modification of dioctahedral montmorillonites can be carried out under DTA conditions with controlled atmosphere techniques. The structural character of the rehydrate prepared in this way is determined from X-ray and DTA data. The mechanism of the reactions by which the rehydrate can be formed is also considered. Thermal analysis curves of the rehydrate form of several pure mont-morillonite samples failed to show any large variation such as is shown by the curves of the original clays themselves. The possibility is considered that such large variations in the dehydroxylization curves of montmorillonites are related to structural instead of compositional variations within the sample. It is suggested that montmorillonites showing two reactions attributable to dehydroxylization may be mixtures of the rehydrate form and montmorillonite.

A closed form equation is derived for the calculation of the oriented diffraction pattern given by single particle size layer silicates having randomly interstratified interlamellar species. A general method for treating any particle size distribution is indicated and closed form results are presented for the Poisson, normal, gamma and binomial distributions. No restriction is placed on the number of interlayer types. The structure factors for these types are explicitly introduced. Graphs of two of the variables appearing in the equations applicable to particle size distributions provide a means of visualizing the effects of both interstratification and particle size on observed X-ray patterns.

Orientations of OH-vectors in structural hydroxyl groups of layer silicates were defined both from diffraction data and calculations of electrostatic energy. The comparison of the results showed that for the hydroxyls of the 2:1 layers of chlorites and micas the positions of the hydroxyl protons are mainly determined by electrostatics. For the hydroxyls of dickite, amesite, and the brucitic sheets of chlorite, the results derived by the two methods differed systematically from each other, pointing to a change in the nature of the bond in these OH-groups.

The rate of vapor-phase sorption of tetrahydrofuran (THF), tetrahydropyran (THP), and 1,4-dioxan (DIOX) onto a Wyoming montmorillonite saturated with Al3+ or Cr3+ has been studied by isothermal gravimetry in the temperature range 18° to 105°C using samples of different weights and grain-size distributions. The rate of sorption for all the cyclic ethers increased with decreasing sample and grain size, demonstrating that inter-, rather than intraparticle mass transfer was rate-determining. Optimization of the sample parameters (2 mg sample of <45-μm grain size, pretreated at 120°C yielded integral diffusion coefficients at 18°C of 0.5 × 10−14 m2/s for DIOX for the Cr3+-clay to 3.5 × 10−4 m2/s for THF for the Al3+-clay; however, no temperature or cationic dependence of the cyclic ether uptake was observed. In general, the rate of sorption of the cyclic ethers increased as THF ≥ THP > DIOX indicating that the sorption rate of THF and THP was dependent on concentration or that DIOX sorption was retarded by bidentate coordination to aluminum ions at the edges of the clay platelets.