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Naturally occurring Cs and Rb are distinctly more abundant relative to K in the highly weathered upland soils of the Savannah River Site, South Carolina, than in average rock of Earth's upper continental crust (UCC), by factors of 10 and 4, respectively. Naturally occurring Cs has been selectively retained during soil evolution, and Rb to a lesser extent, while K has been leached away. In acid extracts of the soils, the Cs/K ratio is about 50 times and the Rb/K ratio about 15 times the corresponding ratios for the UCC, indicating that relatively large amounts of natural Cs and Rb have been sequestered in soil microenvironments that are highly selective for these elements relative to K. Cation exchange favoring Cs and Rb ions, and subsequent fixation of the ions, at sites in interlayer wedge zones within hydroxy-interlayered vermiculite particles may account for the observations. The amounts of stable Cs retained and the inferred duration of the soil evolution, many thousands of years, provide new insights regarding long-term stewardship of radiocesium in waste repositories and contaminated environments. Study of natural Cs in soil adds a long-term perspective on Cs transport in soils not available from studies of radiocesium.

Isotherms were measured for sorption of naphthalene and diuron by four organoclays in equilibrium with various mixtures of methanol and water. The organoclays were prepared from Wyoming montmorillonite by replacing the natural exchangeable cations of the clay by the quaternary ammonium ions TMA (tetramethylammonium), TMPA (trimethylphenylammonium), HDTMA (hexadecyltrimethylammonium), and BDTDA (benzyldimethyltetradecylammonium). TMPA-clay showed the greatest sorptive capacity for naphthalene, while BDTDA-clay was the most effective sorbent for diuron. The sorption mechanism for each sorbate−sorbent combination was related to the arrangement of the quaternary ammonium cations in the exchanged clay and the volume fraction of methanol in solution (f c). As expected from the solvophobic theory, the linear sorption coefficients decreased log-linearly with increasing f c in the binary solvent mixture, except for TMPA-clay at f c > 0.5. In addition to solute−solvent and solvent−sorbent interactions, an additional effect involving solute-organoclay interactions influenced the sorption of naphthalene and diuron by organoclays from aqueous and mixed solvents.

The Biga Peninsula of NW Turkey is host to six major halloysite deposits in the Go¨nen, Yenice and Balya districts. Mineralization took place in areas of Permian limestone blocks where the Triassic Karakaya Complex is in contact with early Miocene calc-alkaline volcanic rocks. Hypogene halloysite mineralization was controlled by the intersection of minor faults in the vicinity of clay deposits. During the Pleistocene, activity of the North Anatolian Fault (NAF) brought ascending geothermal solutions through the fault zones to the surface, which led to hydrothermal alteration and halloysite formation. N-MORB normalized element values for each halloysite deposit and the volcanic rocks suggest genetic links. Alunite and halloysite were formed in the Turplu area where upwelling hydrothermal waters contained major H2S and SO2acids. Only halloysite mineralization occurred in outflow areas of the same fossil geothermal field.Pyrite and alunite samples from the Turplu deposits have δ34S values of 0.6–1.8% and 4.8–7.9%, respectively, with values for gypsum of 3.1–3.5%. The δ34S values of pyrite suggest that local meteoric waters had partially mixed with the dominant fluid during the closure stage of fossil hydrothermal activities. The range of δD values of halloysite samples from Turplu is –58.4 to –68.6%. The δ18O values for halloysite are in the range 16.7–18.1%. All halloysite deposits in the study areas are either overlying or adjacent to limestone blocks, and these provide excellent drainage for the discharging geothermal waters. Subsurface drainage systems in the karstic environment and the SO2-bearing thermal waters indicate the importance of acidic waters and the continuous leaching of elements in forming relatively pure hydrated halloysite. A steam-heated dissolution-precipitation model is proposed for the occurrence of all halloysite and alunite deposits. Sulphur gases (H2S-SO2) of hypogene origin rose from deep in the fault zone to the surface where they encountered oxygenated groundwater at the water table. The occurrence of H2SO4in this hydrothermal system enhanced the acidity of geothermal waters provoking advanced argillic alteration. Hypogene alunite deposits also have large P2O5contents, suggesting a parent material with a magmatic origin deeper than the alkaline tuffs. Halloysite is a fast-forming metastable precursor to kaolinite.

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Mössbauer absorption spectrography can be used to establish the presence of Fe(2)+ and Fe(3)+ in clay minerals. In the sheet structure silicates, octahedrally coordinated iron can be distinguished from tetrahedrally coordinated iron. Siderite and goethite, common contaminants of the clay minerals, can usually be detected. Goethite has a well-organized structure, though, owing to its fine grain size, it may appear to be amorphous to x-rays. The various families of clay minerals show minor differences in isomer shift and quadrupole splitting values, caused by variations in the character of the octahedral layer.