Aishwarya S. Kar

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.

Retention behaviour of Cs(I), Sr(II), Tc(VII) and Np(V) on smectite-rich clay

The smectite-rich natural clay is being considered as a backfill and buffer material for Indian repository programme. In the present study, batch sorption measurements have been performed at trace concentrations for one of the minor actinide elements [Np(V)] and for the long lived fission products, Cs(I), Sr(II), and Tc(VII) on purified and conditioned smectite-rich clay at varying conditions of pH and ionic strength. In case of Cs(I) and Sr(II) the sorption was found to increase with pH. At any pH the sorption was found to decrease with increasing ionic strength of the suspension maintained with NaCl. Further, at any pH the sorption of Sr(II) is less than the corresponding value for Cs(I). This is indicative of effect of size selectivity on the sorption by the clay. Tc(VII), on the other hand, is poorly retained by the clay, which can be explained in terms of the negative charge on the TcO4− ion, which has negligible interaction with the predominantly negatively charged clay surface. In the case of Np(V), the sorption was found to increase albeit, slowly compared to Cs(I) and Sr(II) with pH, and it with no effect of ionic strength on the sorption at all pH values. This suggests that Np(V) primarily interacts with the surface sites via inner sphere complexation mechanism.

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.

Characterization of high level waste for minor actinides by chemical separation and alpha spectrometry

The high level waste (HLW) generated from the reprocessing of the spent fuel of pressurized heavy water reactor has been characterized for the minor actinides. The radiation dose of the waste solution was reduced by radiochemical separation of cesium from HLW by solvent extraction with chlorinated cobalt dicarbollide dissolved in 20% nitrobenzene in xylene. Minor actinides (Np, Pu, Am, Cm) in the high level waste were assayed by alpha spectrometry following radiochemical separation. The gross alpha activity determined by liquid scintillation agrees well (within 10%) with the cumulative quantities of actinides determined by alpha spectrometry.

Role of the humic acid for sorption of radionuclides by synthesized titania

Abstract Present work reports on synthesis, characterization and application of titania powder (anatase) for sorption of 137Cs (monovalent), 133Ba (divalent) and 154Eu (trivalent) radionuclides in the presence and absence of humic acid (Aldrich). In order to obtain a detailed sorption behavior of all the three aforementioned radionuclides, a series of experiments were conducted with respect to effect of pH, humic acid (HA), and concentration of radionuclides. Sorption studies of 137Cs, 133Ba and 154Eu onto synthesized titania have been carried out over a wide range of pH scale varying from 3 to 11 in the presence and absence of Aldrich Humic acid (2 mg/L). Sorption of all the three radionuclides rises sharply with the pH of the suspension with saturation value of ∼ 70%, 80% and 85% respectively for monovalent, bivalent and trivalent radionuclides. Humic acid could not make any influence for sorption of 137Cs, but significantly altered with respect to 133Ba and 154Eu sorption. The sorption data at various concentrations were fitted with Freundlich isotherm model.

Distribution coefficients of radionuclides around uranium mining area and effect of different analytical parameters on their determination

Macroscopic batch sorption study has been carried out to measure distribution coefficient (Kd) of uranium, thorium and their daughter products, radium and polonium, on soil samples collected from a proposed uranium mining site in India. Results showed high Kd values for Th(IV) and Po(IV) (log Kd ~4), while lower Kd values were obtained for U(VI) with the site ground water as aqueous medium compared to the synthetic water. Ra(II)–Kd has been found dependent on soluble Ca(II) content of the water samples. Determination of Kd values in an inter-comparison manner involving different estimation methodology produced a consistent data set.

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 Å with 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.

Effect of carbonate on U(VI) sorption by nano-crystalline α-MnO2

Abstract U(VI) sorption on nano-crystalline α-MnO2 was studied in NaClO4 medium as a function of pH by batch sorption method in presence and absence of carbonate and subsequently employing surface complexation modeling (SCM) to predict species responsible for U(VI) sorption. The kinetic study of U(VI) sorption on nano-crystalline α-MnO2 was carried out to fix the time of equilibration. In presence of carbonate, U(VI) sorption on nano-crystalline α-MnO2 increases with pH of the suspension, leveling off in the pH range 5–8.5 thereafter decreasing at higher pH. However, in absence of carbonate, U(VI) sorption on nano-crystalline α-MnO2 remains close to 100% at pH>5. The difference in sorption behavior of uranium in the presence and absence of carbonate can be explained in terms of uranium speciation in the two systems. The dissolution of nano-crystalline α-MnO2 was studied in presence and absence of carbonate to ascertain its role in sorption. Surface complexation modeling was satisfactorily able to explain the sorption phenomena in all the systems. In addition, U(VI) sorption on nano-crystalline α-MnO2 was compared with literature data on U(VI) sorption by δ-MnO2.

Effect of sulfate on sorption of Eu(III) by Na-montmorillonite

Abstract Smectite-rich natural clay is being evaluated as the backfill and buffer material in the Indian repository program for the nuclear high level waste disposal. In the natural clay, montmorillonite is one of the major mineral component governing the sorption behavior of various radionuclides. In the present work, influence of sulfate anion on sorption of Eu(III) by Na-montmorillonite has been investigated. The effect of pH and sulfate concentration on Eu(III) sorption by Na-montmorillonite was used to understand the mechanism of sorption process. The Eu(III) sorption by clay at varying pH was virtually pH independent at lower pH (<4), with ion exchange as the dominant mode for Eu(III) sorption. In the pH region of 4–6.5, sharp increase in sorption indicates surface complexation as predominant mechanism. At pH>6.5, the sorption attained a constant value. To deduce the mechanism of sorption of Eu(III) on Na-montmorillonite surface in presence of sulfate, ATR-FTIR spectroscopic investigations has been carried out which indicate the presence of sulfate bearing species on Na-montmorillonite surface. Using spectroscopic findings as a guide, the surface complexation modeling, in absence and presence of sulfate, was successfully carried out.

Sorption of Eu(III) on Fe–montmorillonite relevant to geological disposal of HLW

Abstract Montmorillonite (Mt) is the major clay mineral of bentonite, which is the candidate buffer material in the engineered barrier system for geological disposal of high level waste (HLW). The alteration of Mt due to its interaction with carbon steel (overpack) can produce Fe–Mt. In order to understand the basic properties of Fe–Mt, the sorption studies using Eu(III) are reported here. For this, Fe(III)–Mt was prepared by conventional cation exchange method using FeCl3 with Na–Mt. The obtained Fe(III)–Mt was then reduced to Fe(II)–Mt using ascorbic acid. Both the samples were characterized based on their X-ray diffraction, Fourier transform infrared spectra, cation exchange capacity and specific surface area. The batch sorption studies of Eu(III) were conducted for both Fe(III)–Mt and Fe(II)–Mt as a function of pH (3–10), ionic strength (0.001 M–1 M) and Eu(III) concentration (10−8–10−3 M). The distribution coefficient (Kd) was found to be higher for Fe(III)–Mt compared to Fe(II)–Mt and Na–Mt. The sudden increase in sorption in the pH range 4.5–6 and remaining constant beyond it indicates ion exchange mechanism at pH<4.5, with surface complexation mechanism dominating the sorption at pH>4.5. This is further corroborated by ionic strength dependent sorption data which shows decrease in sorption capacity of Fe–Mt with increasing ionic strength at low pH, but remaining more or less unchanged at higher pH. Eu(III) adsorption isotherm on Fe–Mt increased linearly with [Eu(III)] reaching saturation at 10−5 M and 10−4 M for Fe(III)–Mt and Fe(II)–Mt, respectively. The amount of iron released from Fe–Mt and Fe(II)/Fetotal during sorption were estimated to understand the effect on Eu(III) sorption behaviour by release of interlayer iron in Fe–Mt.