Comparing Cs+ binding affinity of Keggin type polyoxometalate and sodium Tetrakis(4-florophenyl)borate in solution and from Cs-doped pure phase vermiculite.

We assessed the aptitude of cesium (Cs+) binding by Keggin type polyoxometalates (POMs) and compared the results with the Cs+ binding by sodium tetrakis(4-fluorophenyl)-borate (Na-TFPB). In this work, we aimed to establish a system to treat radioactive Cs+ contaminated soil with POMs economically. We evaluated the effect of initial Cs+ concentration (0.1M) and precipitant (POMs and TFPB) concentrations (0.01M) on Cs+ precipitation. Our comparison of Cs+ precipitation by three different POMs and TFPB was obtained by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). We synthesized POMs molybdovanadophosphoric acid, H5PMo10V2O40 (MVPA), and silicotungstic acid, H4SiW12O40 (STA), and used commercially available phosphotungstic acid, H3PW12O40 (PTA), and TFPB. Cs-doped pure phase vermiculite was also used to demonstrate the extraction potential of Cs+ by TFPB, STA, and PTA. All the POMs and corresponding Cs-bound POMs were characterized by UV-visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray powder diffraction (XRD). In this simulation study, we demonstrated that the Cs+ removal by POMs is much more effective than TFPB and could be a promising method for the treatment of radiocesium contaminated soil.

An investigation of strong sodium retention mechanisms in nanopore environments using nuclear magnetic resonance spectroscopy.

Recent experimental research into the adsorption of various cations on zeolite minerals has shown that nanopore channels of approximately 0.5 nm or less can create an effect whereby the adsorption of ions, especially those that are weakly hydrated, can be significantly enhanced. This enhanced adsorption occurs due to the removal of hydrating water molecules which in turn is caused by the nanopore channel's small size. A new adsorption model, called the nanopore inner-sphere enhancement (NISE) effect, has been proposed that explains this unusual adsorption mechanism. To further validate this model a series of nuclear magnetic resonance (NMR) spectroscopy studies is presented here. NMR spectra were gathered for Na adsorbed on three zeolite minerals of similar chemical composition but differing nanoporosities: zeolite Y with a limiting dimension of 0.76 nm, ZSM-5 with a limiting dimension of 0.51 nm, and mordenite with a limiting dimension of 0.26 nm. The NMR experiments validated the predictions of the NISE model whereby Na adsorbed via outer-sphere on zeolite Y, inner-sphere on ZSM-5, and a combination of both mechanisms on mordenite. The strong Na adsorption observed in these nanoporous minerals conflicts with sodium's general designation as a weak electrolyte.

Calcium polysulfide treatment of Cr(VI)-contaminated soil.

Batch treatability studies for a Cr(VI)-contaminated glacial soil from a Cr plating facility were conducted using 1X and 2X the stoichiometric ratio of calcium polysulfide (CPS). The pH of the treated soil increased from 6 to 11 upon CPS addition, but progressively returned to 8-8.5 over the course of 1 year. The 1X dosage maintained a highly reducing environment up to 21 days of monitoring with the samples exposed to atmospheric oxygen, while 2X was reducing up to 180 days of curing. The EPA regulatory method for solid Cr(VI) could not reliably predict Cr(VI) in the treated solid due to ongoing reduction during the test. SPLP results showed that the CPS created an apparent Cr(VI) mobilization during the first 60 days of treatment, with subsequent decrease in soluble Cr(VI) up to 1 year of monitoring. Synchrotron micro-X-ray analyses at 60 days curing showed that Cr(VI) was predominantly bound as highly insoluble PbCrO(4) that precipitated in the interstitial pores of the soil, with very little to no Cr(VI) associated with the abundant iron oxyhydroxides. Despite its spatial accessibility and due to its low solubility, PbCrO(4) was recalcitrant to treatment, which proceeded only very slowly as judged by the SPLP data. It is concluded that, while CPS has a long residence time in the environment and is a promising reductant, in situ reduction is not an efficient treatment method for soils with highly insoluble Cr(VI) compounds, especially in surficial layers such as the one studied.