Vaibhavi V. Raut

Simultaneous determination of trace amounts of borate, chloride and fluoride in nuclear fuels employing ion chromatography (IC) after their extraction by pyrohydrolysis

An accurate and sensitive method based on the combination of pyrohydrolysis-ion chromatography (PH-IC) is proposed for the simultaneous separation and determination of boron as borate, chloride and fluoride in nuclear fuels such as U(3)O(8), (Pu,U)C and Pu-alloys. The determination is based on the initial pyrohydrolytic extraction of B, Cl and F from the samples as boric acid, HCl and HF, respectively, which are subsequently separated by ion chromatography (IC). The proposed method significantly improves the existing analytical methodology as it combines the determination of boron, a critical trace constituent in nuclear materials, along with F(-) and Cl(-) for chemical quality control measurements. Various experimental parameters were optimized to achieve maximum recoveries of the analytes during the pyrohydrolysis and to get better ion chromatographic (IC) separation of borate, F(-) and Cl(-) along with other anions such as CH(3)COO(-), NO(2)(-), NO(3)(-), Br(-), PO(4)(3-) and SO(4)(2-). Recoveries of more than 93% could be obtained for all the analytes in the sample (0.5-1.5 g) at 1200+/-25K and distilled with pre-heated steam at the flow rate of 0.3 mL/min. An isocratic elution with a mobile phase of 0.56 M d-mannitol in 6.5mM NaHCO(3) was used for the IC separation. The detection limits for B (as borate), F(-) and Cl(-) were 24, 13 and 25 microgL(-1), respectively. Precision of about 5% was achieved for determination of boron, Cl(-) and F(-) in the samples containing 1-5 ppm(w) of boron, and 10-25 ppm(w) of Cl and F. The method was validated with reference materials and successfully applied to the nuclear fuels. The methodology is easy to adapt on routine basis.

Supercritical Carbon Dioxide Extraction of Uranium from Acidic Medium Employing Calixarenes

Various calixarenes were evaluated for the supercritical fluid extraction of uranium from nitric acid medium. The extraction efficiency was found to be affected by various parameters, namely pressure, temperature, CO2 flowrate, extraction time, and molarity of nitric acid. The addition of HPFOA (pentadecafluoro-n-octanoic acid) for the production of CO2-phillic fluorinated counter ion enhanced the extraction efficiency. Under optimized conditions (pressure of 200 atm, temperature of 323 K, 30 minutes of static time followed by 30 minutes of dynamic time, CO2 flowrate of 2 mL min−1, nitric acid molarity of 0.1 M) for uranium: calixarene: HPFOA mole ratio of 1:5:10, highest extraction efficiency could be obtained with p-tert.-butyl calix[6]arene (79.9%). Solvent extraction study with hexane as the organic phase indicated the formation of [UO2 (calixarene)]2+. In order to assess the suitability of the developed method to extract uranium in the presence of a host of other ions, extraction efficiency for other metal ions was estimated.

Whole genome transcriptome analysis of rice seedling reveals alterations in Ca2+ ion signaling and homeostasis in response to Ca2+ deficiency

Ca(2+) is an essential inorganic macronutrient, involved in regulating major physiological processes in plants. It has been well established as a second messenger and is predominantly stored in the cell wall, endoplasmic reticulum, mitochondria and vacuoles. In the cytosol, the concentration of this ion is maintained at nano-molar range. Upon requirement, Ca(2+) is released from intra-cellular as well as extracellular compartments such as organelles and cell wall. In this study, we report for the first time, a whole genome transcriptome response to short (5 D) and long (14 D) term Ca(2+) starvation and restoration in rice. Our results manifest that short and long term Ca(2+) starvation involves a very different response in gene expression with respect to both the number and function of genes involved. A larger number of genes were up- or down-regulated after 14 D (5588 genes) than after 5 D (798 genes) of Ca(2+) starvation. The functional classification of these genes indicated their connection with various metabolic pathways, ion transport, signal transduction, transcriptional regulation, and other processes related to growth and development. The results obtained here will enable to understand how changes in Ca(2+) concentration or availability are interpreted into adaptive responses in plants.

Separation behavior of U(VI) and Th(IV) on a cation exchange column using 2,6‐pyridine dicarboxylic acid as a complexing agent and its application for the rapid separation and determination of U and Th by ion chromatography

The retention behavior of U and Th as their 2,6-pyridine dicarboxylic acid (PDCA) complexes on a cation exchange column was investigated under low pH conditions. Based on the observed retention characteristics, an ion chromatographic method for the rapid separation of uranium and thorium in isocratic elution mode using 0.08 mM PDCA and 0.24 M KNO(3) in 0.22 M HNO(3) as the eluent was developed. Both uranium and thorium were eluted as their PDCA complexes within 2 min, whereas the transition and lanthanide metal cations were eluted as an unresolved broad peak after thorium. Under the optimized conditions both U and Th have no interference either from alkali and alkaline earth elements up to a concentration ratio of 1:500 or from other elements up to 1:100. The detection limits (LOD) of U and Th were calculated as 0.04 and 0.06 ppm, respectively (S/N=3). The precision in the measurement of peak area of 0.5 ppm of both U and Th was better than 5% and a linear calibration in the concentration range of 0.25-25 ppm of U and Th was obtained. The method was successfully applied to determine U and Th in effluent water samples.

Study on the identification of organic and common anions in the pyrohydrolysis distillate of mixed uranium-plutonium carbide for the interference free determination of chlorine and fluorine by ion chromatography

Abstract Identification of various soluble organic acids formed during the pyrohydrolysis of uranium-plutonium mixed carbide [(U,Pu)C] was carried out using ion chromatography. This has significant importance as the soluble organic acids can cause severe interferences during the ion chromatography separation and determination of Cl− and F− in the pyrohydrolysis distillate of (U,Pu)C. Determination of Cl and F is important in the chemical quality control of nuclear materials as these two elements can cause corrosion and hence, their concentrations in all nuclear materials are restricted to certain specified values. Since the pyrohydrolysis distillates contain both inorganic and organic acid anions, for the sake of separating and identifying organic acid anions from the common inorganic anions, three independent isocratic elutions using varying concentrations of NaOH eluent were employed for the separation of weakly, moderately and strongly retained anions. It was observed that pyrohydrolysis of (U,Pu)C also produced soluble organic acids as in the case of nitric acid dissolution of UC. The present investigation revealed the presence of formic, acetic, propionic, butyric, oxalic acid anions in the pyrohydrolysis distillate of (U,Pu)C in trace or ultra-trace concentrations. The presence of each organic acid identified in the chromatogram was confirmed with spike addition as well as by separating them by capillary electrophoresis method. The presence of lower aliphatic acids viz. formic and acetic acids was reconfirmed by carrying out an independent separation with tetraborate eluent. It is suggested that nitric acid being formed during pyrohydrolysis could be responsible for the formation of organic acids. Based on the findings, an ion chromatography separation method has been proposed for the interference-free determination of chloride and fluoride in pyrohydrolysis distillate of (U,Pu)C.

Separation of Boron from Borated Paraffin Wax by Pyrohydrolysis and Alkali Extraction Methods and Its Determination Using Ion Chromatography

A method based on the pyrohydrolysis extraction of boron and its quantification with ion chromatography was proposed for paraffin waxes borated with H3BO3 and B4C. The optimum pyrohydrolysis conditions were identified. Wax samples were mixed with U3O8, which prevents the sample from flare up, and also accelerates the extraction of boron. Pyrohydrolysis was carried out with moist O2 at 950°C for 60 and 90 min for wax with H3BO3 and wax with B4C, respectively. Two simple methods of separation based on alkali extraction and melting wax in alkali were also developed exclusively for wax with H3BO3. In all the separations, the recovery of B was above 98%. During IC separation, B was separated as boron-mannitol anion complex. Linear calibration was obtained it between 0.1 and 50 ppm of B, and LOD was calculated as 5 ppb (S/N = 3). The reproducibility was better than 5% (RSD).

Separation and determination of trace thorium in uranium matrix using chelation ion chromatography

ABSTRACT A simple chromatographic method for the determination of trace thorium in uranium matrix has been reported after studying the retention behavior of U(VI) and Th(IV) as their 2,6-pyridine dicarboxylic acid (PDCA) complexes on a reversed phase column. The method does not require pre-separation of uranium matrix. A mobile phase consisting of PDCA, KNO3, and HNO3 in 5% methanol was used. A calibration plot was constructed in the presence of uranium matrix (r2 = 0.9978). The precision of the method is 5% at 1 ppm of Th and LOD was obtained at 0.1 ppm (S/N =3). The accuracy of the method was checked by comparing the results with neutron activation analysis.

Development of ion chromatography and capillary electrophoresis methods for the determination of Li in Li–Al alloy

Two methods were developed for determination Li content in Li–Al alloy by employing ion chromatography (IC) and capillary electrophoresis (CE) without any prior separation of Al matrix. In absence of suitable certified reference material the two methods were used to validate each other. Using a high capacity column and a weaker eluent methane sulphonic acid, it was possible to separate Li in IC without eluting strongly retained Al. The method showed good precision and sensitivity and was extended for analysis of routine samples. In the case of CE using imidazole as co-ion, Li was detected in CE by indirect detection. In view of no interference from Al, samples were analyzed without any matrix separation. The CE method was used successfully for sample analysis and results were compared with IC results.

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.