Sorption and desorption of radiocesium by muscovite separated from the Georgia kaolin.

Radiocesium (137Cs) sorption by moderately weathered, sand-sized muscovite, obtained as a byproduct of kaolin ore processing, was observed at various concentrations of added stable Cs (0-100 µmol/L) over a 130 d period. After 18 h of batch sorption with 1 mmol/L NaCl as background electrolyte, conditional 137Cs Kd values were near 2000 L/kg across the entire range of added stable Cs. Over four succeeding months, the Kd values increased by large factors for suspensions with little added Cs but increased only slightly for the suspensions with the most added Cs. The large grains of muscovite used in this study behaved distinctly differently than previously studied, much finer illite in that highly Cs-selective but low-abundance cation exchange sites appeared to be unavailable to the aqueous Cs during the first few days of the experiment. Diffusion pathways to highly Cs-selective sites were thought to be much longer in the muscovite than in frayed edges of illite, causing the highly Cs-selective sites to be isolated from the bulk solution. The longer diffusion pathways may be due to much greater stiffness of the material bounding interlayer wedges in the muscovite than in illite. This isolation from solution led to slow uptake at trace levels of Cs though the final Kd values (after 130 d) at those levels were comparable to those found for some illite. After 130 days, the original solutions were replaced by new electrolyte solutions containing no Cs, to observe 137Cs desorption over another 130 d period. There was no indication of desorption of 137Cs from the slowly accessible, highly Cs-selective sites apparently reached by most of the 137Cs during sorption at the low Cs levels. The byproduct mica from kaolin processing might serve effectively as a chemically stable sorbent to isolate accidently released radiocesium and to hold it until the 137Cs is virtually gone.

Enrichment of cesium and rubidium in weathered micaceous materials at the Savannah River Site, South Carolina.

The enrichment of Cs and Rb relative to Ba, Sr, and K in three soils representing a range of soil maturities was determined to investigate the long-term sorption behavior of these elements in upland soils of the Savannah River Site (SRS). Elemental mass fractions normalized to upper continental crust (UCC) decreased in the order Cs > Rb > Ba > K > Sr in the soil fine fractions. Only the UCC-normalized amount of Cs was greater than unity. The UCC-normalized amounts in strong-acid extracts decreased as Cs > Rb > Ba > K ≈ Sr. In all three soil cores, the trends of the UCC-normalized amounts of acid-extractable metals were similar to trends of cation-exchange capacity (CEC) calculated from synchrotron-X-ray diffractometry measurements of soil mineralogy. Consequently, the relative enrichment of Cs and Rb is largely controlled by selective sorption to micaceous minerals, including hydroxy-interlayered vermiculite, that dominate the CEC. Where high clay content had caused retention of soil solution, amounts of acid extractable K, Sr, and Ba were enhanced. The retention of natural Cs by these three soils, which developed over many thousands of years, is a strong indicator that radiocesium will likewise be retained in SRS soils.

Long-term selective retention of natural Cs and Rb by highly weathered coastal plain soils.

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.

Mossbauer analysis of iron in clay minerals.

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.