Sorption study of long-lived 94Nb on laterite: Effects of physicochemical parameters on sorption.

Zr-Nb alloy is used as the pressure tube in pressurized heavy water reactors (PHWR). Prolonged neutron irradiation of the pressure tubes leads to the formation of a long-lived radioisotope 94Nb. Thus, the discharged pressure tubes possess huge 94Nb activity which persists for a prolonged period.If these discharged pressure tubes come in contact with ground water, 94Nb isotope may leach and migrate and this can lead to a long-term radiological impact in the environment.In the present study, we have explored the capability of laterite as a filler material for the containment and retarding the migration of 94Nb. In this regard, detailed characterization of the laterite soil was carried out using energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD), fourier transform infra-red spectrometry (FTIR), total cation exchange capacity determination, zeta potential measurement and thermogravimetric analysis (TGA). The sorption study of 94Nb on laterite was carried and the effects of different physico-chemical parameters like pH, ionic strength, temperature and equilibration time were evaluated. Ionic strength, temperature and time dependent sorption studies assist to explore the probable sorption mechanism of 94Nb on laterite, which helps in understanding the migration behaviour of 94Nb in natural aquatic environment. This study suggests that laterite is a promising material in containment of 94Nb isotope owing to its good cation exchange behaviour in the acidic medium and ability to form surface complex in the neutral medium.

Utilization of thermal neutron induced in-situ chain reactions and the (n,p) reaction with fast neutrons for compositional characterization of lithium titanate.

A methodology has been developed for the complete compositional characterization of lithium titanate (LTO) using neutron activation, which is quite challenging and no literature report is available so far. The concept of thermal neutron induced in-situ chain reactions 6Li(n,α)3H and 16O(3H,n)18F has been used for the determination of Li and O through the measurement of 18F activity. The method is capable of analyzing Li and O in percentage level as reported in the present analysis of two types of lithium titanate samples. Spectroscopic interference of the elements which can directly or indirectly affect the outcome, were evaluated meticulously. Determination of Ti was carried out using fast neutron activation through the product isotopes like 47Sc, 48Sc, generated via (n,p) nuclear reactions. Fast neutron activation methodology seems to be advantageous for Ti determination over thermal neutron activation, as it offers self validation through different isotopes and multiple gamma lines.

Evidences on As(III) and As(V) interaction with iron(III) oxides: Hematite and goethite.

Arsenic, which is ubiquitous in nature, was found associated with iron oxides in soils and sediments. Our interest was to utilize the same mechanism for the sorptive removal of arsenic from groundwater. The iron(III) oxides: hematite, goethite, were synthesized, characterized and sorption studies of arsenic [As(III) and As(V)] were carried out in batch mode. For studying the evidence of the interaction between arsenic and iron oxide during the process of sorption, a new electrochemical method was developed. Differential pulse voltammetry (DPV) study indicated that the sorbed arsenic species is redox active on the surface of the sorbent. X-ray photoelectron spectroscopy (XPS) measurement was performed for confirmation of the changes occurring to the oxidation states of iron as well as arsenic after the sorption. XPS studies confirmed that the behavior of arsenic species on hematite/goethite was similar and occurs via a partial redox reaction. During sorption of As(III), a partial oxidation occurs resulting in As(V) species, simultaneously the Fe(III) present in the iron oxide gets reduced to Fe(II). However, during the sorption of As(V), there occurs a Fe(II) oxidation followed by As(V) reduction. Based on the results, a mechanistic scheme for sorption of arsenic on iron(III) oxides as sorbents was proposed.

Effect of different physico-chemical factors on sorption of Pa(V) on iron oxides.

The effects of different physico-chemical parameters on sorption of protactinium (Pa) on three different iron oxides (goethite, hematite and magnetite) were studied. The sorption of Pa(V) on all the three iron oxides was low at pH 1, increased to ~ 90% at neutral pH and then decreased slightly above pH 9. Presence of humic acid increases the sorption of Pa(V) on iron oxides in acidic medium whereas sorption is reduced in basic medium. The classical methods like ionic strength, time and temperature dependent sorption studies have been used for the elucidation of the sorption mechanism of Pa(V) on iron oxides. Physisorption in acidic pH and chemisorption in basic pH are the most probable mechanisms. The study demonstrates that classical method alone can be used for the sorption mechanism investigations in the circumstances where it is difficult to have spectroscopic evidences.

Sorption of Nb(V) on pyrolusite (ß-MnO2): Effect of pH, humic acid, ionic strength, equilibration time and temperature.

The sorption of Nb(V) on pyrolusite has been studied and the effect of pH, ionic strength, humic acid, temperature and equilibration time were also investigated in a series of batch equilibrium experiments. The sorption was found to be affected by solution pH, ionic strength and humic acid. The sorption was high in neutral/near neutral pH (~96 %) but lower sorption was observed both in acidic (~55 %) and basic (~85 %) media. Sorption was decreased in acidic pH with increase of ionic strength and reverse effect was seen in basic pH although the effect is less prominent. Presence of humic acid causes enhancement of sorption in acidic pH whereas sorption declined in basic pH. The sorption process is endothermic in acid medium and exothermic in basic medium. In acid medium the sorption is entropy driven process. Kinetics of the sorption study was found to follow pseudo first order in acidic pH whereas pseudo second order in basic pH.

Study on the performance and interaction of different synthetic iron oxides for arsenic uptake using 76As radiotracer.

A radiotracer technique was employed to study the sorption of As(III) and As(V) on chemically synthesized iron oxides: magnetite (Fe3O4), goethite (α-FeOOH) and hematite (Fe2O3) by batch equilibration mode. Magnetite and goethite were found to be promising sorbents for arsenic removal and applied to real ground water from West Bengal, India. A solvent extraction method using benzene was applied for the investigation of oxidation state of sorbed arsenic. A sorption mechanism was proposed for interaction of As(III)/As(V) with iron oxides.

Interaction of niobium with iron-oxide colloids and the role of humic acid.

In this work, we report the sorption of Nb on iron oxides and the effect of humic acid. Iron oxides viz. goethite, hematite and magnetite were chemically synthesised and characterised by X-ray diffraction, particle size, surface area and zeta potential measurement. The sorption of Nb on all the three iron oxides was low (∼40%) at pH 1, increased to âˆ¼ 90% at pH 8 and decreased marginally above pH 8. The effect of humic acid on the sorption was very small. Thermodynamic parameters viz. activation energy, enthalpy, entropy, free energy and sticking probability were calculated to understand the mechanism of the sorption process. Although the enthalpy was positive, the free energy change was negative i.e. the sorption was entropy driven process. The sorption followed pseudo-second-order kinetics and sticking probability model indicated that the process was chemisorption. This study is important to understand the probable migration of 94Nb (half life 20300 y) during underground storage of radioactive waste.

Determination of impurities in graphite using synchrotron radiation based X-ray fluorescence spectrometry.

Determination of impurities namely Ca, Mn, Fe, Ni, Zn, Sr and Pb in graphite by energy dispersive X-ray fluorescence spectrometry is described using microfocused synchrotron radiation. The internal standard and standard addition methodologies were adopted for quantification and the results were compared with tube-based X-ray fluorescence spectrometry. Analysis of the results by the F and t-tests revealed their statistical equivalence. Synchrotron measurements improved the detection limits by an order of magnitude compared to the tube based technique. Cr and Zr, which were below the quantification limit in tube based technique, were also quantified by synchrotron based technique.

Zinc as a marker in viscera of suspected metal phosphide poisoning: a study by neutron activation analysis.

Zinc as a marker element in the viscera of suspected metal phosphide poisoning has been studied during the present work. Neutron activation analysis (NAA) has been employed to detect and quantify the concentration of zinc in the viscera/stomach portion. The methodology has been developed on simulated and real life viscera samples to quantify the amount of zinc using NAA. The results obtained by NAA for real-life samples have been validated using a complementary analytical technique (viz. differential pulse anodic stripping voltammetry), and the values obtained were in good agreement, within +/- 5-8%. This exercise could be useful in medico-legal field for framing a definitive opinion about zinc phosphide poisoning.