Retention studies on uranium, thorium and lanthanides with amide modified reverse phase support and its applications.

The retention behaviour of uranium and thorium was investigated on modified reverse phase supports using 3-oxo-pentanedioicacid bis-[bis-(2-ethyl-hexyl)-amide (OPAEHA), 3-oxo-pentanedioicacid bis diisobutyl amide (OPAIBA) and bis-2-ethylhexyl succinamic acid (BEHSA). alpha-Hydroxy isobutyric acid (alpha-HIBA) was employed as the complexing reagent for elution. Elution profiles of uranium and thorium were studied as a function of the modifier concentration, mobile phase composition and its pH. Based on these investigations, a novel high performance liquid chromatography (HPLC) based separation technique was developed using BEHSA modified support for the isolation and quantitative determination of lanthanides as a group in uranium matrix. Hundreds of samples obtained from pyrochemical reprocessing of molten salts containing lanthanides in uranium matrix (e.g. 1:20,000) were separated and determined within 7 min using the coated support. The advantage of the present HPLC technique lies in the simultaneous separation and assay of total lanthanides and uranium whereas other analytical methods necessitate the separation of uranium matrix prior to lanthanide assay.

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples.

A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, (31)P and (13)C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54mmolg(-1) for U(VI), 1.98, 0.63 and 0.42mmolg(-1) for Th(IV) and 1.22, 0.39 and 0.39mmolg(-1) for La(III) under optimum pH, HNO(3) and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, all the analyte ions are quantitatively eluted from the resin phase with >99.5% recovery using 1M (NH(4))(2)CO(3), as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.