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Fe type clay minerals, Fe–montmorillonite, are expected to form in the nuclear waste repositories over a span of few years owing to the interaction of corrosion products from overpack and/or canister with bentonite consisting of montmorillonite (Mt) as the major clay mineral. Therefore, it is important to understand the properties of altered clay minerals, Fe–Mt. In the present study, the sorption behaviour of 133Ba(II), one of the high-yield fission products of uranium-based fuels and analogue of 90Sr (t1/2 = 28.5 y), on Fe(II)–Mt and Fe(III)–Mt has been investigated. Retention behavior of Ba(II) on Fe–Mt has been studied at varying pH (3–9), ionic strength (0.001 M–1 M) and Ba(II) concentration (10−9–10−3 M) by batch sorption method. The distribution coefficient (Kd) of Ba(II) on Fe–Mt was found to be nearly independent of pH while it decreased with increasing ionic strength indicating ion exchange as the dominant Ba(II) sorption mode on Fe–Mt. Adsorption isotherm of Ba(II) exhibited linearity in the entire Ba(II) concentration range. A comparison of Ba(II) sorption behavior on Fe–Mt and Na–Mt has been made. The Fe released from both Fe(III)–Mt and Fe(II)–Mt was measured in all the sorption experiments and was found to be much less in the case of Fe(III)–Mt (≤ 1.7 ppm) when compared to Fe(II)–Mt (~ 25 ppm). The modeling of Ba(II) sorption profiles on Fe–Mt and Na–Mt has been carried out using FITEQL 4.0.

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.

Bentonite is the candidate buffer and backfill material in the deep geological repositories. Montmorillonite (Mt) is the major clay minerals of bentonite. Over a long period of time, the interaction of corrosion products from overpack and/or cansister with clay minerals is expected to result in formation of Fe(III)-Mt, a plausible alterated product. In this context, it is important to understand the properties of Fe-Mt in comparison with original clay mineral, Na-Mt. In the present study, sorption behavior of Cs(I), long lived fission product (135Cs, t1/2 = 2.3 × 106 years; 137Cs, t1/2 = 30.1 years) with high fission yield, on Fe(III)-Mt is investigated. Batch sorption studies are conducted at varying pH (3–9), ionic strength (0.001–1 M) and Cs(I) concentration (10−10 to 0.05 M). The distribution coefficient (Kd) of Cs(I) on Fe(III)-Mt was found to be independent of pH except at low pH, indicating ion exchange mechanism as dominant interaction mode for Cs(I). It was further verified by ionic strength variation which depicted decrease in Cs(I) sorption with increasing ionic strength. Adsorption isotherm of Cs(I) was found to be linear over the concentration range of 10−10 to 10−3 M Cs(I). The Fe released from Fe(III)-Mt during the Cs(I) sorption was found to be not more than 0.2 ppm. However, on lowering the pH and increasing the ionic strength, the Fe release increased. Furthermore, the apparent diffusion coefficient for Cs(I) in Fe(III)-Mt has been determined.

Arsenic (As) and cadmium (Cd), two major carcinogenic heavy metals, enters into human food chain by the consumption of rice or rice-based food products. Both As and Cd disturb plant-nutrient homeostasis and hence, reduces plant growth and crop productivity. In the present study, As/Cd modulated responses were studied in non-basmati (IR-64) and basmati (PB-1) rice varieties, at physiological, biochemical and transcriptional levels. At the seedling stage, PB-1 was found more sensitive than IR-64, in terms of root biomass; however, their shoot phenotype was comparable under As and Cd stress conditions. The ionomic data revealed significant nutrient deficiencies in As/Cd treated-roots. The principal component analysis identified NH

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 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.

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 (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.

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 pH4.5. 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.

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.

Citric acid is one of the low molecular weight organic acids which are ubiquitous in nature. In this study the sorption of citric acid at titania (anatase)/water interface was investigated using batch adsorption experiment and attenuated total reflectance – Fourier transform infrared spectroscopy (ATR-FTIR) over wide experimental conditions of pH, surface loading and ionic strengths. The batch adsorption experiment showed typical anionic characteristics; higher sorption was observed at lower pH values and sorption decreases with increasing pH. Strong dependence of sorption on ionic strength shows formation of citrate surface species in outer-sphere binding mode. At lower pH, ATR-FTIR spectra of aqueous citrate differs from that of sorbed citrate ions indicating lowering of pK a values of surface sorbed citrate compared to that present in solution. Detailed analysis of FTIR spectra of sorbed citrate in light of that of aqueous and Ca(II)/Eu(III) complexed citrate revealed formation of an inner sphere complex of citrate on anatase surface along with the outer sphere complex. Wavenumber difference between the asymmetric and symmetric COO – peaks (Δυ = 159 cm –1) implies inner-sphere complex in bidentate bridging mode. These results help in explaining the sorption behaviour of Eu(III) on anatase in presence of citric acid.

Two separate ion chromatography methods were developed for the determination of calcium and iron in silicon and uranium silicide. A cation exchange separation with conductivity detection was developed for Ca. A reversed phase column modified with 50 mM camphor-10-sulphonic acid was used for separating Fe. Iron was detected photometrically. Linear calibrations for Ca (0.1–10 ppm) and Fe (0.5–25 ppm) were performed. Limits of detections for Ca and Fe are 0.03 and 0.2 ppm, respectively. The precision of the methods are better than 2 % for Ca at 0.2 ppm and Fe at 2 ppm.

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.

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.

Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.

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...

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.

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 ± 25 K 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 6.5 mM NaHCO 3 was used for the IC separation. The detection limits for B (as borate), F − and Cl − were 24, 13 and 25 μg L −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.

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).

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.