P. M. Gandhi

Nano-cerium vanadate: a novel inorganic ion exchanger for removal of americium and uranium from simulated aqueous nuclear waste.

Cerium vanadate nanopowders were synthesized by a facile low temperature co-precipitation method. The product was characterized by X-ray diffraction and transmission electron microscopy and found to consist of ∼25 nm spherical nanoparticles. The efficiency of these nanopowders for uptake of alpha-emitting radionuclides (233)U (4.82 MeV α) and (241)Am (5.49 MeV α, 60 keV γ) has been investigated. Thermodynamically and kinetically favorable uptake of these radionuclides resulted in their complete removal within 3h from aqueous acidic feed solutions. The uptake capacity was observed to increase with increase in pH as the zeta potential value decreased with the increase in pH but effect of ionic strength was insignificant. Little influence of the ions like Sr(2+), Ru(3+), Fe(3+), etc., in the uptake process indicated CeVO4 nanopowders to be amenable for practical applications. The isotherms indicated predominant uptake of the radioactive metal ions in the solid phase of the exchanger at lower feed concentrations and linear Kielland plots with positive slopes indicated favorable exchange of the metal ions with the nanopowder. Performance comparison with the other sorbents reported indicated excellent potential of nano-cerium vanadate for removing americium and uranium from large volumes of aqueous acidic solutions.

Removal of americium from aqueous nitrate solutions by sorption onto PC88A—Impregnated macroporous polymeric beads

The removal of Am (III) ions from aqueous solutions was studied by solid-liquid extraction using indigenously synthesized Extractant Impregnated Macroporous Polymeric Beads (EIMPBs). These beads were prepared by an in situ phase inversion method using polyethersulfone (PES) as base polymer and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) as an extractant. The synthesized EIMPBs were characterized by FTIR, TGA and SEM techniques. The batch equilibration study using these beads for the uptake of Am (III) was carried out as a function of parameters, like pH, equilibration time, Am (III) concentration, etc. The blank polymeric beads, without PC88A, have shown negligible sorption of Am (III) under the experimental conditions. The experimental data on the sorption behavior of Am (III) on the polymeric beads fitted well in the pseudo-second-order kinetics model. The synthesized polymeric beads exhibited very good sorption capacity for Am (III) at pH 3. The reusability of the beads was also ascertained by repetitive sorption/desorption of Am (III) up to 10 cycles of operation, without any significant change in their sorption characteristics.

Solvent Extraction of Pu(IV) Using TBP: A Comparative Study of n-dodecane and a Room Temperature Ionic Liquid

The extraction of Pu(IV) from nitric acid medium using TBP has been compared with two diluents using n-dodecane and a RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethanesulphonyl)imide (C4mimTf2N). Kinetics of extraction was slower in RTIL compared to n-dodecane. The mechanism of extraction was found to be cation exchange at lower acidity which changes to the formation of a neutral complex at higher acidity greater than 1M HNO3 for RTIL. Back extraction of Pu from the loaded organic phase was equally effected using 0.1M oxalic acid and a mixture of guanidine carbonate and EDTA as strippant from both the extraction systems under study. Radiation stability and reusability studies showed promise for future application.

Studies on Transport of Anionic Complex of Plutonium From Nitric Acid Medium across ALIQUAT 336/n-Paraffin Liquid Membrane

The present studies deal with the application of the supported liquid membrane (SLM) technique for the separation and purification of plutonium from other impurities in nitric acid medium using anion exchanger Aliquat 336 (a quaternary ammonium salt)/ n-paraffin as a carrier. The effects of feed acidity, stripping agent, and membrane pore size and membrane thickness on the transport behavior of anionic complex of plutonium have been studied in detail. An attempt has been made to establish the mechanism for plutonium transport and model the physicochemical transport of plutonium across SLM. Transport of anionic complex of plutonium increased with increase in carrier concentration upto 10% (w/v), while with further increase in carrier concentration, decrease in transport of plutonium was observed. The PTFE membrane with 0.45 µm pore size and 80 µm thickness was found to be most suitable for the transport of plutonium. The effect of membrane thickness indicates that the transport phenomenon is diffusion controlled. Transport behavior of plutonium, uranium, and other fission products from actual feed solution of ion exchange method obtained in PUREX process was also tested and the result clearly indicates that Aliquat 336 has high selectivity for plutonium and it can be used for the separation and purification of plutonium by the supported liquid membrane technique.

Studies on the partitioning of actinides from high level liquid waste solution employing supported liquid membrane with Cyanex-923 as carrier

The present paper deals with the studies on the partitioning of actinides from high level liquid waste solution of PUREX origin employing supported liquid membrane technique. The process uses solution of Cyanex-923 in n-dodecane as a carrier with poly tetra fluoro ethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Transport studies are carried out for 241Am under different experimental conditions to optimize the transport parameters such as feed acidity, carrier concentration, effect of uranium, trivalent metal ion and salt concentration in the feed. Studies indicated good transport of actinides across the membrane from nitric acid medium. Under the optimized conditions the transport of 241Am is studied from a uranium depleted synthetic PHWR-HLLW and finally the technique has been used for the partitioning of alpha emitters from an actual research reactor-HLLW. High concentration of uranium in the feed is found to retard the transport of americium, suggesting the need for prior removal of uranium from the waste.

BenzoDODA grafted polymeric resin—Plutonium selective solid sorbent

A new ligand grafted polymeric resin (BenzoDODA SDVB) was synthesized by covalently attaching plutonium selective ligand (BenzoDODA) on to styrene divinyl benzene (SDVB) polymer matrix. BenzoDODA SDVB resin was evaluated for separation and recovery of plutonium(IV) from nitric acid medium. Sorption of Pu(IV) was found to decrease with the increase in nitric acid concentration, with very small sorption above 7.0M HNO3. Sorption kinetics was fast enough to achieve the equilibrium within 60min of contact where the kinetic data fitted well to pseudo-second-order model. Sorption isotherm data fitted well to Langmuir model suggesting chemical interaction between the BenzoDODA moiety and plutonium(IV) ions. Sorption studies with some of representative radionuclides of high level waste showed that BenzoDODA SDVB is selective and therefore could be a promising solid sorbent for separation and recovery of plutonium. Further, the theoretical calculations done on BenzoDODA SDVB resin suggested Pu(NO3)4·BenzoDODA (1:1) sorbed complex conformed to generally observed square antiprism geometry of the plutonium complexes, with contributions from oxygen atoms of four nitrate ions as well as from four oxygen atoms present in BenzoDODA (two phenolic ether oxygen atoms and two carbonyl oxygen atoms of amidic moiety).

Evaluation of Novel Solvent Systems Containing Calix-crown-6 Ligands in A Fluorinated Solvent for Cesium Extraction from Nitric Acidic Feeds

Several commercial calix-crown-6 ligands such as: calix[4]arene-bis-crown-6 (CC), calix[4]arene-bis-benzo-crown-6 (CBC), calix[4]arene-bis-naphtho-crown-6 (CNC), and bis-(octyloxy)calix[4]arene-mono-crown-6 (CMC) have been evaluated for their Cs uptake ability from nitric acid feed solutions in a novel solvent system. The calix-crown-6 ligands were made soluble in phenyl trifluoromethyl sulphone (PTMS) and 1 × 10−3 M solutions were used for metal ion extraction from nitric acid feed solutions. The extraction efficiency of the calix-crown-6 ligands was found out to be: CBC > CNC > CMC ˜ CC, which was attributed to trends of their partition coefficients. CNC was considered to be the most suitable extractant in view of its better organophilicity. The effects of concentrations of nitric acid and Cs carrier in feed were also investigated. Studies carried out using variation of ligand concentration yielded an extracted species of the type [CsL+][NO3−]org. Stripping of Cs(I) from the loaded organic phase was found to be possible when the organic phase contained minute quantities of Alamine 336. Co-current extraction and stripping studies were also carried out using CNC as the extractant.

Liquid – Liquid Extraction and Pertraction of Eu(III) from Nitric Acid Medium Using Several Substituted Diglycolamide Extractants

Solvent extraction and supported liquid membrane (SLM) transport properties of Eu(III) from nitric acid feed conditions were investigated using several substituted diglycolamide (DGA) extractants such as N,N,N′N′-tetra-n-octyl diglycolamide (TODGA), N,N,N′N′-tetra(2-ethylhexyl) diglycolamide (T2EHDGA), N,N,N′N′-tetra-n-hexyl diglycolamide (THDGA), N,N,N′N′-tetra-n-pentyl diglycolamide (TPDGA), and N,N,N′N′-tetra-n-decyl diglycolamide (TDDGA). Effects of feed acidity and phase modifier composition on Eu(III) extraction were investigated using the DGAs and the nature of extracted species were ascertained by slope analysis method. The Eu(III) distribution ratio (DEu) values were found to decrease in the presence of iso-decanol. In general, the DEu values decreased with increased alkyl chain length of the DGA. The extracted species contained only 2 extractant molecules when TPDGA and TDDGA were used while for TODGA about four extractant molecules were found to be present in the extracted species. The supported liquid membrane transport of Eu(III) was studied under varying experimental conditions using the five DGA extractants. Transport studies using 0.1 M DGA as the extractant suggested the trend as TDDGA > TODGA > T2EHDGA ∼ THDGA which significantly changed to TPDGA > THDGA > TODGA > TDDGA > T2EHDGA in the presence of 30% iso-decanol as the phase modifier. The permeability coefficient (P) values were also determined with membranes of varying pore sizes.

Adsorption of actinides within speleothems

Abstract Stalagmites and stalactites, as observed within natural caves, may develop inside geological repositories during constructional and post-operational periods. It is therefore important to understand actinide sorptionwithin such materials. Towards this, experimental studies were carried out with 233U, 238Np (VI), 238Np (IV), 239Pu and 241Am radiotracers using natural speleothem samples collected from the Dharamjali cave of the Kumaon Lesser Himalayas, India. Petrological/mineralogical studies showed that natural speleothems have three general domains: (1) columnar calcite; (2) microcrystalline calcite; and (3) botryoidal aragonite - each with ferruginous materials. Results showed that all domains of speleothems can take up >99% actinides, irrespective of valence state and pH (1-6 range) of the solution. However, distribution coefficients were found to be at a maximum in aragonite for most of the actinides. Such data are very important for long-term performance and safety assessments of the deep geological repositories planned for the disposal of high-level nuclear wastes.

Partitioning of actinides from high-level liquid waste employing supported liquid membrane technique using TOPO in n-dodecane as carrier

AbstractThis paper describes the studies on the partitioning of actinides from high-level liquid waste of PUREX origin employing supported liquid membrane technique. The process uses solution of tri-n-octyl phosphine oxide in n-dodecane as a carrier with polytetrafluoroethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Transport of 241Am has been studied as a function of various parameters such as acidity of feed, concentration of carrier, effect of uranium concentration, effect of trivalent ions and salt concentration in the feed in order to optimize efficient transport conditions. The studies indicated good transport of actinides like uranium, neptunium, plutonium and americium across the membrane from nitric acid medium. Under the optimized conditions, the transport of 241Am is also studied from a uranium-depleted synthetic pressurized heavy water reactor-high-level liquid waste (HLLW). Also the technique has been used for the partitioning of alpha em...