Rapid and reliable assaying of Tc-99 in sediment samples with novel MTPN polymeric resin.

The paper describes a new method for the rapid determination of Technetium (Tc) in sediment samples using solid-phase extraction chromatography (SPEC) with a novel methyl triphenyl phosphoniumnitrate (MTPN) resin. The effectiveness of the resin in selectively recovering Tc was evaluated in both batch and column mode and exploited for rapid analysis of 'Tc'. The procedure involves the acid digestion of samples, pre-concentration of fission products in supernatant and co-precipitation of actinides with Fe(OH)3, followed by selective recovery of Tc by SPEC using a column filled with MTPN resin. The recovered Tc was then radiometrically assayed using beta counting. The method was validated using IAEA certified reference materials and was found to provide reliable and reproducible results for the activity concentration of Tc-99 in sediment samples within 24 h.

Evaluation of BenzoDODA grafted polymeric resin for rapid and reliable assaying of plutonium in sediment samples.

The paper reports a new rapid radioanalytical procedure for the determination of plutonium (Pu) in sediments by solid phase extraction chromatography (SPEC) using Bis-(2-ethylhexyl) carbamoyl methoxy phenoxy-bis-(2-ethylhexyl) grafted resin, abbreviated as Benzodioxodiamide (BenzoDODA) grafted resin. The resin was synthesized and evaluated for its sorption behaviour towards Pu in batch and column mode to determine its efficacy for selective recovery of Pu from sediment samples. The analytical procedure was based on the radiochemical separation of samples by acid digestion, followed by preconcentration of actinides by co-precipitation with Fe(OH)3 and finally selective recovery of Pu by SPEC using a column filled with BenzoDODA grafted resin. Pu was then radiometrically assayed by preparing alpha disc sources with electro-deposition followed by alpha spectrometry. The method was further validated with IAEA reference materials. This method gives reliable and reproducible results for the activity concentration of Pu in sediment samples within 24 h.

Probing and understanding interaction of Eu(III) with γ- alumina in presenceof malonic acid.

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions. With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid, in the present study, Eu(III), malonic acid (MA) and γ-alumina are considered as representatives of trivalent actinides, low molecular weight natural occurring organic acid and aluminol sites, respectively. The influence of MA on sorption of Eu(III) by γ-alumina was elucidated by batch sorption, spectroscopic techniques and surface complexation modeling, for the first time. Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed on γ-alumina revealed the presence of two inner-sphere surface complexes. Batch sorption for binary (alumina-Eu(III)) and ternary (alumina-Eu(III)-MA) systems were investigated as a function of pH, Eu(III) concentration and sequential addition of Eu(III)/MA. The pH edge for Eu(III) sorption shifts to higher pH with increasing Eu(III) concentration. In ternary systems, Eu(III) sorption is significantly enhanced at pH < 4.5. Eu(III) speciation on γ-alumina is independent of addition sequence of Eu(III)/MA. Time resolved fluorescence spectroscopy of Eu(III) sorbed on γ-alumina exhibited two surface species, XOEu2+ and (YO)2Eu+. The enhancement in I616/I592 and lifetime for ternary systems, as compared to binary system, at low pH, indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems. The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems, using code FITEQL 4.0, by considering the surface species identified by spectroscopic techniques.

Delineating the influence of picolinic acid on Eu(iii) sorption by γ-alumina.

The present study aims at understanding the sorption mechanism of Eu(iii) by γ-alumina in the presence of picolinic acid (PA), a decontaminating agent used in the nuclear industry, through batch sorption studies, spectroscopy and surface complexation modeling. PA is weakly sorbed by γ-alumina, with the sorption increasing with pH up to 4.5 and decreasing with further increase in pH. Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR) measurements indicate that PA forms an inner sphere surface complex on γ-alumina. The presence of PA does not affect Eu(iii) sorption by γ-alumina at low [Eu(iii)], while it drastically reduces Eu(iii) sorption at high [Eu(iii)]. Similar Eu(iii) sorption profiles with different addition sequences of Eu(iii) and PA suggest identical Eu(iii) surface species for Eu(iii) sorption on γ-alumina in the presence of PA which has been validated by time resolved fluorescence spectroscopy (TRFS). TRFS measurements of Eu(iii) sorbed on γ-alumina in the absence (binary systems) and presence of PA (ternary systems) exhibited two components 1 & 2. The lifetime value of component 1 in ternary systems is enhanced compared to that in binary systems signifying the formation of new surface species containing Eu(iii), PA and the γ-alumina surface whereas the similarity of component 2 in both the binary and ternary systems reveals an almost identical coordination environment of Eu(iii) in the two types of system. Using the spectroscopic information obtained from TRFS, Eu(iii) sorption, at high [Eu(iii)], in ternary systems has been successfully modeled by considering Eu(iii) bridged PA surface species at both low and high affinity sites of γ-alumina. At low [Eu(iii)] both PA and Eu(iii) bridged ternary surface complexes only at high affinity sites of γ-alumina could describe the Eu(iii) sorption adequately.

Complexation of U(VI) with Cucurbit[5]uril: Thermodynamic and Structural investigation in aqueous medium.

The assessment of cucurbituril (CBn) for selective removal of actinides from nuclear waste streams requires comprehensive understanding of binding parameters and coordination of these complexes. The present work is the first experimental report on complexation of actinide ion with Cucurbit[5]uril (CB5) in solution. The thermodynamic parameters (ΔG, ΔH and ΔS) for complexation of CB5 with U(VI) in formic acid water medium were determined using microcalorimetry and UV-Vis spectroscopy. The enthalpy and entropy of complexation revealed the partial binding of U(VI) to CB5 portal. The partial binding was confirmed by spectroscopic techniques viz. extended X absorption fine structure spectroscopy (EXAFS), 1H and 13C NMR. The EXAFS χ(r) versus r spectra for U-CB5 complex has been fitted from 1.4 to 3.5 Šwith two oxygen shells and a carbon shell. The presence of three carbon atom in secondary shell shows the involvement of only three carbonyl oxygens directly bonding to U(VI) which is in contrast to that calculated from gas phase DFT calculation of unhydrated system. The combined effect of hydration and formic acid encapsulation led to the enhanced stability of partially bound U(VI) to CB5. In the present work the binding of formic acid has also been studied by fluorescence spectroscopy. ESI-MS data shows the unusual stabilization of U(VI) by CB5 in gas phase.

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution.

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i=1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO>IANO>NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

Complexation of thorium with pyridine monocarboxylate-N-oxides: Thermodynamic and computational studies.

The feed wastes and waste water treatment plants are the major sources for the entry of N-oxides into the soils then to aquatic life. The complexation of actinides with potentially stable anthropogenic ligands facilitate the transportation and migration of the actinides from the source confinement. The present study describes the determination of thermodynamic parameters for the complexation of Th(IV) with the three isomeric pyridine monocarboxylates (PCNO) namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO). The potentiometric and isothermal calorimetric titrations were carried out to determine the stability and enthalpy of the formations for all the Th(IV)-PCNO complexes. Th-PANO complexes are more stable than Th-NANO and Th-IANO complexes which can be attributed to chelate formation in the former complexes. Formation of all the Th-PCNO complexes are endothermic and are entropy driven. The geometries for all the predicted complexes are optimized the energies, bond distances and charges on individual atoms are obtained using TURBOMOLE software. The theoretical calculation corroborated the experimental determinations.

Stability, speciation and spectral properties of NpO2+ complexes with pyridine monocarboxylates in aqueous solution.

Neptunyl ion as NpO2+ is the least reacting and most mobile radioactive species among all the actinides. The picolinic acid used for decontamination is co-disposed along with the radioactive waste. Thus, in long term storage of HLW, there is high possibility of interaction of actinides and long lived fission products with the picolinate and can cause migration. The complexation of NpO2+ with the three structural isomers of pyridine monocarboxylates provides an insight to explore the role of hetero atom (nitrogen) with respect to key binding moiety (carboxylate). In the present study, the log ß values, speciation and spectral properties of NpO2+ complexes with pyridine monocarboxylates viz. picolinate, nicotinate and isonicotinate, have been studied at 298K in 0.1M NaClO4 medium using spectrophotometry. The complexation reactions involving protonated ligands are always accompanied by protonation/deprotonation process; thus, the protonation constants of all the three pyridine monocarboxylates under same conditions were also determined by potentiometry. The spectrophotometric data analysis for complexation of NpO2+ with pyridine monocarboxylates indicated the presence of ML and ML2 complexes with log ß values of 2.96±0.04, 5.67±0.08 for picolinate, 1.34±0.09, 1.65±0.12 for nicotinate and 1.52±0.04, 2.39±0.06 for isonicotinate. The higher values of log ß for picolinate were attributed to chelation while in other two isomers, the binding is through carboxylate group only. Density Functional Theory (DFT) calculations were carried out to get optimized geometries and electrostatic charges on various atoms of the complexes and free pyridine monocarboxylates to support the experimental data. The higher stability of NpO2+ nicotinate and isonicotinate complexes compared to simple carboxylates and the difference in log ß between the two is due to the charge polarization from unbound nitrogen to the bound carboxylate oxygen atoms.

Standardization of 68Ge-68Ga using 4πß(LS)-γ coincidence counting system for activity measurements.

68Ga has great scope for use in future for positron emission tomography (PET) imaging due to its very fast blood clearance and fast target localization, even though at present 18F is widely used. 68Ge in equilibrium with 68Ga (68Ge-68Ga) can also be used as a surrogate for 18F calibration, as 18F source standardization can be done at national metrology institute (NMI) but, these standards cannot be sent to nuclear medicine centers (NMCs) across India for calibration of isotope calibrators, due to the short half-life of 18F (110min). Providing 68Ge-68Ga standards to NMCs requires that first standardization must be carried out at NMI (BARC in India) to provide traceability to the measurements carried out at NMCs. In the present work, standardization of 68Ge-68Ga was carried out using 4πß(LS)-γ coincidence counting system and CIEMAT/NIST efficiency tracing technique. The decay scheme correction factors for two gamma windows were calculated by Monte Carlo technique using general purpose code FLUKA. The activity concentration values were normalized by the activity concentration obtained by 4πß(LS)-γ coincidence counting system using window-1. The final result reported to BIPM for 4πß(LS)-γ coincidence counting was calculated by taking arithmetic mean of activity concentrations obtained for two gamma windows. The normalized activity concentration obtained by 4πß(LS)-γ coincidence counting was 0.998±0.005 and that obtained using CIEMAT/NIST efficiency tracing was 1.002±0.007 which are in excellent agreement within uncertainty limits.

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay.

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay, proposed as a backfill material in the Indian geological repository, was studied using the out-diffusion method. Radiotracers (22)Na, (137)Cs, (85)Sr and (154)Eu were used; the first three are carrier-free enabling experimental work at sub-micromolar metal ion concentration, and Eu(III) tracer (154)Eu was used at sub millimolar concentration. An out-diffusion methodology, wherein a thin planar source of radioactivity placed between two clay columns diffuses out, was used to obtain the apparent diffusion coefficient (Da) values. This methodology enabled determination of diffusion coefficient even for strongly sorbing (154)Eu. Da values for (22)Na, (137)Cs, (85)Sr and (154)Eu were 2.35 (±0.14) × 10(-11), 2.65 (±0.09) × 10(-12), 3.32 (±0.15) × 10(-11) and 1.23 (±0.15) × 10(-13) m(2) s(-1), respectively. Da values were found to be in fair agreement with literature data reported for similar mineralogical sediments. Sorption of radionuclides on the clay was also determined in the present study and differences in Da values were rationalized on the basis of sorption data. Distribution ratios (Kd) for Cs(I) and Eu(III) were higher than that for Sr(II), which in turn was higher than that for Na(I).

Performance demonstration of 4πß(LS)-γ coincidence counting system for standardization of radionuclides with complex decay scheme.

A standardization of (134)Cs and (131)I was carried out in order to demonstrate the performance and applicability of the 4πß(LS)-γ coincidence counting system for standardization of radionuclides with complex decay scheme. The coincidence analyzer, capable of analyzing coincidence between beta and two gamma windows simultaneously, was developed and used for the standardization. The use of this dual coincidence analyzer has reduced the total experimental time by half. The activity concentrations obtained using the 4πß(LS)-γ coincidence counting system, a 4πß(PC)-γ coincidence counting system, and the CIEMAT/NIST method are in excellent agreement with each other within uncertainty limits and hence demonstrates its performance for standardization of radionuclides decaying with complex decay scheme. Hence use of this 4πß(LS)-γ coincidence counting system can be an alternative method suitable to standardize radionuclides with complex decay scheme with acceptable precision.

Complexation of Eu(III) with cucurbit[n]uril, n = 5 and 7: a thermodynamic and structural study.

Cucurbit[n]urils (CBn) are a new class of macrocyclic cage compounds capable of binding organic and inorganic species, owing to their unique pumpkin like structure comprising of both a hydrophobic cavity and a hydrophilic portal. The thermodynamics of the complexation of Eu(III) with CBn of a different cavity size viz. cucurbit[5]uril (CB5) and cucurbit[7]uril (CB7) has been studied by UV-Vis spectroscopy and calorimetry at 25 °C whereas the structure of the complexes was investigated using time resolved fluorescence spectroscopy (TRFS) and extended X-ray absorption fine structure spectroscopy (EXAFS) in a formic acid-water mixture (50 wt%). This is the first report on the structural investigation of Eu-CBn complexes in solution. The thermodynamic data (ΔG, ΔH and ΔS) for Eu(III) complexation with CBn reveal the formation of a 1 : 1 complex with CB5, while both 1 : 1 and 1 : 2 complexes are observed with CB7. The signatures of these species are observed in ESI-MS measurements, which corroborates with the species postulated in thermodynamic studies. The complexation reactions are found to be driven by ΔS as ΔH is either small negative or positive indicating the formation of inner sphere complexes, which is in line with TRFS and EXAFS results. These studies show that Eu(III) caps one of the CB5 portals by binding with all the carbonyl groups in the 1 : 1 Eu-CB5 complex, whereas in the 1 : 1 Eu-CB7 complex, Eu(III) interacts with only a few of the carbonyl groups of CB7. The computational studies (DFT calculations) on Eu-CB5 and Eu-CB7 complexes further support the experimental data.

Studies on separation and purification of fission (99)Mo from neutron activated uranium aluminum alloy.

A new method has been developed for separation and purification of fission (99)Mo from neutron activated uranium-aluminum alloy. Alkali dissolution of the irradiated target (100mg) results in aluminum along with (99)Mo and a few fission products passing into solution, while most of the fission products, activation products and uranium remain undissolved. Subsequent purification steps involve precipitation of aluminum as Al(OH)3, iodine as AgI/AgIO3 and molybdenum as Mo-α-benzoin oxime. Ruthenium is separated by volatilization as RuO4 and final purification of (99)Mo was carried out using anion exchange method. The radiochemical yield of fission (99)Mo was found to be >80% and the purity of the product was in conformity with the international pharmacopoeia standards.

Separation of no-carrier-added rhenium from bulk tantalum by the sodium malonate-PEG aqueous biphasic system.

The aqueous biphasic system (ABS) involving sodium malonate-polyethylene glycol (PEG) phases has been applied for the first time for separation of no-carrier-added (183)Re (T1/2=70 d) from α-particle irradiated bulk tantalum target. The various ABS conditions were applied for investigating the separation by varying pH, temperature, PEG-molecular weight, concentration of salt. The extraction pattern was hardly affected by change in pH and the molecular weight of PEG. One step separation of nca (183)Re from Ta was achieved at the optimal conditions of (i) 50% (w/w) PEG-4000-2 M sodium malonate, 40 °C and (ii) 50% (w/w) PEG-4000-3 M sodium malonate, room temperature (27 °C).

Investigation of the extraction complexes of palladium(II) with novel thiodiglycolamide and dithiodiglycolamide ligands by EXAFS and computational methods.

The structure of the extraction complexes of palladium(II) with novel ligands, namely, N,N,N',N'-tetra-(2-ethylhexyl) thiodiglycolamide (T(2EH)TDGA) and N,N,N',N'-tetra-(2-ethylhexyl) dithiodiglycolamide (DTDGA), have been determined by extended X-ray absorption fine structure spectroscopy (EXAFS). The interpretation of the EXAFS data is well supported by theoretical calculations of the complex geometry based on density functional theory (DFT). T(2EH)TDGA, having one thioetheric 'S' atom, forms a square planar complex with the Pd(II) ion, exhibiting 2: 1stoichiometry with one sulphur atom and one carbonyl oxygen atom from each T(2EH)TDGA molecule interacting with Pd(II) at distances of 2.24 and 2.04 Å, respectively. On the other hand, DTDGA, having two 'S' atoms in addition to two carbonyl groups, forms a square planar complex with Pd(II), exhibiting 1: 1stoichiometry, wherein both the sulphur atoms and the carbonyl oxygen of DTDGA interact with Pd(II) at distances of 2.29 and 2.05 Å, respectively. The slight distortion from the perfect square planar geometry could be attributed to the steric hindrance imposed by the bulky alkyl group of the amidic moieties. DFT calculations for the Pd-ligand complexes show that the Pd(II)-DTDGA complex with 1: 1stoichiometry is energetically more stable than the Pd(II)-T(2EH)TDGA complex with 1: 2stoichiometry. Among the two possible Pd(II)-T(2EH)TDGA complex geometries, the cis configuration appears more favorable. The methodology of fitting the EXAFS data has been validated by fitting the EXAFS data of a Pd(II)-aquo complex which showed square planar geometry with two axial water molecules constituting the secondary hydration sphere.

Development of liquid scintillation based 4πß(LS)-γ coincidence counting system and demonstration of its performance by standardization of 6°Co.

A single-vial, single-PMT 4πß(LS)-γ coincidence counting system has been developed at the Radiation Safety Systems Division, BARC. It has advantages of simple sample preparation, higher counting efficiency and the absence of self absorption over the conventional proportional counter based 4πß(PC)-γ coincidence counting system. The performance of the system is demonstrated by standardizing a (60)Co solution using the 4πß(LS)-γ coincidence counting system, 4πß(PC)-γ coincidence counting system and CIEMAT/NIST method and comparing the results obtained by each method. The detection efficiency of liquid scintillation counter of the 4πß(LS)-γ coincidence counting system was varied by color quenching, by chemical quenching and by varying the bias voltage applied to the LSC PMT. For the proportional counter based 4πß(PC)-γ coincidence counting system the detection efficiency was varied by source self absorption. The activity concentrations obtained using the 4πß(LS)-γ coincidence counting system, the 4πß(PC)-γ coincidence counting system and the CIEMAT/NIST method are comparable within the uncertainty limits.

Facilitated transport of Pd(II) through a supported liquid membrane (SLM) containing N,N,N',N'-tetra-(2-ethylhexyl) thiodiglycolamide T(2EH)TDGA: a novel carrier.

A novel carrier, N,N,N',N'-tetra-(2-ethylhexyl) thiodiglycolamide, T(2EH)TDGA has been studied for transport of Pd(II) from nitric acid medium across a supported liquid membrane (SLM). Pd(II) was found to be almost quantitatively transported (≈ 99.9%) within 2h from 3.0M HNO(3) medium using 0.05 M T(2EH)TDGA in n-dodecane as carrier and 0.01 M thiourea in 0.2M HNO(3) as strippant. Pd(II) transport was also studied against various parameters like feed acidity, carrier concentration, membrane pore size, etc. Palladium transport was found to be diffusion controlled and the diffusion co-efficient value was found to be 3.56 × 10(-5)cm(2)/s. Selectivity of T(2EH)TDGA for palladium over other fission products was found to be quite high, with the separation factors for Pd, with respect to different fission products being >10(3). With respect to leaching out of carrier from the membrane support, the membrane was found to be stable for six consecutive cycles. Thus, T(2EH)TDGA can be used as an efficient carrier of Pd(II) from nitric acid medium.

Preparation of spherical 57Co source for the calibration of intra-operative gamma probe.

This paper describes an electrochemical method for deposition of a thin layer of (57)Co on the outer surface of a copper sphere of 5mm diameter intended to be used as a point radioactive source. A description of the electrolytic cell, the process of deposition and the assay of the (57)Co activity are presented. About 1.48MBq (∼40µCi) of (57)Co could be deposited using the described method. The quality of the prepared source in terms of nonleachability, uniform distribution of activity and stability, which are necessary attributes to be ensured before application were evaluated and found to be satisfactory.

Effect of humic acid on sorption of technetium by alumina.

Sorption of technetium by alumina has been studied in absence as well as in presence of humic acid using (95)Tc(m) as a tracer. Measurements were carried out at fixed ionic strength (0.1M NaClO(4)) under varying pH (3-10) as well as redox (aerobic and reducing anaerobic) conditions. Under aerobic conditions, negligible sorption of technetium was observed onto alumina both in absence and in presence of humic acid. However, under reducing conditions (simulated with [Sn(II)] = 10(-6)M), presence of humic acid enhanced the sorption of technetium in the low pH region significantly and decreased at higher pH with respect to that in absence of humic acid. Linear additive as well as surface complexation modeling of Tc(IV) sorption in presence of humic acid indicated the predominant role of sorbed humic acid in deciding technetium sorption onto alumina.

Sorption of curium by silica colloids: effect of humic acid.

Sorption of curium by silica colloids has been studied as a function of pH and ionic strength using (244)Cm as a tracer. The sorption was found to increase with increasing pH and reach a saturation value of ∼95% at pH beyond 5.3. The effect of humic acid on the sorption of (244)Cm onto silica was studied by changing the order of addition of the metal ion and humic acid. In general, in the presence of humic acid (2 mg/L), the sorption increased at lower pH (<5) while it decreased in the pH range 6.5-8 and above pH 8, the sorption was found to increase again. As curium forms strong complex with humic acid, its presence results in the enhancement of curium sorption at lower pH. At higher pH the humic acid present in the solution competes with the surface sites for curium thus decreasing the sorption. The decrease in the Cm sorption in presence of humic acid was found to be less when humic acid was added after the addition of curium. Linear additive model qualitatively reproduced the profile of the Cm(III) sorption by silica in presence of humic acid at least in the lower pH region, however it failed to yield quantitative agreement with the experimental results. The results of the present study evidenced the incorporation of Cm into the silica matrix.