Tailored bifunctional polymer for plutonium monitoring.

Monitoring of actinides with sophisticated conventional methods is affected by matrix interferences, spectral interferences, isobaric interferences, polyatomic interferences, and abundance sensitivity problems. To circumvent these limitations, a self-supported disk and membrane-supported bifunctional polymer were tailored in the present work for acidity-dependent selectivity toward Pu(IV). The bifunctional polymer was found to be better than the polymer containing either a phosphate group or a sulfonic acid group in terms of (i) higher Pu(IV) sorption efficiency at 3-4 mol L(-1) HNO3, (ii) selective preconcentration of Pu(IV) in the presence of a trivalent actinide such as Am(III), and (iii) preferential sorption of Pu(IV) in the presence of a large excess of U(VI). The bifunctional polymer was formed as a self-supported matrix by bulk polymerization and also as a 1-2 µm thin layer anchored on a microporous poly(ether sulfone) by surface grafting. The proportions of sulfonic acid and phosphate groups in both the self-supported disk and membrane-supported bifunctional polymer were found to be the same as expected from the mole proportions of monomers in polymerizing solutions used for syntheses. α radiography by a solid-state nuclear track detector indicated fairly homogeneous anchoring of the bifunctional polymer on the surface of the membrane. Pu(IV) preconcentrated on a single bifunctional bead was used for determination of the Pu isotopic composition by thermal ionization mass spectrometry. The membrane-supported bifunctional polymer was used for preconcentration and subsequent quantification of Pu(IV) by α spectrometry using the absolute efficiency at a fixed counting geometry. The analytical performance of the membrane-supported-bifunctional-polymer-based α spectrometry method was found to be highly reproducible for assay of Pu(IV) in a variety of complex samples.

Electrospray ionization mass spectrometric studies on uranyl complex with α-hydroxyisobutyric acid in water-methanol medium.

RATIONALE: Hydroxycarboxylic acids are extensively used as chelating agents in the liquid chromatographic separation of actinides and lanthanides. They are also used as model compounds to understand the binding characteristics of humic substances. A systematic study of the speciation of uranyl-α-hyydroxyisobutyric acid (HIBA) in water-methanol is essential, as it is important to understand the various mechanisms responsible for the separation of these species in liquid chromatography. METHODS: ESI-MS studies were carried out using a tandem quadrupole-time-of-flight mass spectrometer in positive and negative ion mode. The effects of solution composition, solute concentration and supporting electrolyte concentration on the ESI-MS behavior of the uranyl species were studied. Transmission parameters such as the quadrupole ion energy and collision cell energy were optimized for acquiring the spectra of uranyl-HIBA species, ensuring that the spectra reflect the solution equilibrium conditions. RESULTS: The solution composition and concentration of the uranyl salt were found to influence the major uncomplexed uranyl species. Although the ESI parameters did not influence the species distribution of uranyl-HIBA, the transmission parameters did have a significant effect. The overall trend in the complexation reaction between uranyl and HIBA was studied as a function of ligand-to-metal ratio. The species distribution obtained in positive ion mode was similar to that obtained in negative ion mode. CONCLUSIONS: The study presents the optimization of the mobile phase conditions and the ESI-MS parameters for the speciation of the uranyl-HIBA system. The methodology was applied to obtaining the distribution of complexed and uncomplexed uranyl species for monitoring the trend in the complexation reaction.

Speciation of platinum-benzoylthiourea in the gas phase using electrospray ionization mass spectrometry and density functional theory.

RATIONALE: Determining the speciation of platinum-benzoylthiourea (Pt-BTU) in the gas phase is a challenging task due to various reaction pathways and the conformational flexibility of the BTU ligand. METHODS: Electrospray ionization mass spectrometry (ESI-MS) experiments and density functional theory (DFT) based calculations were carried out to shed light on this complex reaction in the gas phase using K2 PtCl4 salt and BTU. Various Pt complexes were studied in both positive and negative ion modes of ESI-MS using a quadrupole-time-of-flight mass spectrometer. The effects of the ESI-MS experimental parameters such as capillary voltage, pH and electrolyte on the peak intensity of the Pt-BTU complex were investigated. DFT calculations employing B3LYP functional with the 6-311++G** basis set were used to characterize the geometric parameters and fragmentation patterns of various Pt complexes in the gas phase. RESULTS: In the positive ion mode, complexes with differing numbers of BTU ligands coordinated to the metal ion were observed, whereas, in the negative ion mode, no species associated with BTU or with the solvent (acetonitrile) molecules were found. It was also found that Pt forms complexes with the BTU ligand in different stoichiometric ratios. For both Pt(BTU)2 and Pt(BTU)3 complexes, the BTU ligand undergoes deprotonation followed by bi-dentate coordination. DFT calculations suggest that BTU can coordinate to Pt in both cis and trans isomeric forms, which are nearly iso-energetic with a slight preference towards the trans-isomer. The preference of trans-BTU binding is attributed to the exclusive retention of intra-molecular hydrogen bonding which is absent in the cis-form. CONCLUSIONS: Experimental and theoretical calculations have shown that the gas-phase interaction of BTU to Pt is very complex. The BTU ligand can coordinate to Pt in both mono-dentate and bi-dentate modes, the latter mode being favorable upon deprotonation of the BTU ligand. Furthermore, many close lying species with different geometric isomeric forms are found to be possible due to the presence of intra- and inter-molecular hydrogen bonding.

Monitoring of toxic elements present in sludge of industrial waste using CF-LIBS.

Industrial waste is one of the main causes of environmental pollution. Laser-induced breakdown spectroscopy (LIBS) was applied to detect the toxic metals in the sludge of industrial waste water. Sludge on filter paper was obtained after filtering the collected waste water samples from different sections of a water treatment plant situated in an industrial area of Kanpur City. The LIBS spectra of the sludge samples were recorded in the spectral range of 200 to 500 nm by focusing the laser light on sludge. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique was used for the quantitative measurement of toxic elements such as Cr and Pb present in the sample. We also used the traditional calibration curve approach to quantify these elements. The results obtained from CF-LIBS are in good agreement with the results from the calibration curve approach. Thus, our results demonstrate that CF-LIBS is an appropriate technique for quantitative analysis where reference/standard samples are not available to make the calibration curve. The results of the present experiment are alarming to the people living nearby areas of industrial activities, as the concentrations of toxic elements are quite high compared to the admissible limits of these substances.

Electrospray ionisation mass spectrometric studies for the determination of palladium after pre-concentration by disposable pipette extraction.

RATIONALE: Electrospray ionisation mass spectrometric (ESI-MS) analysis of Pd in complex matrices is difficult due to the multiplicity of matrix effects. Two different approaches, internal standard and matrix separation, were investigated for developing a reliable analytical procedure for the trace level determination of Pd in simulated high-level liquid waste (SHLLW) solutions. METHODS: An ESI mass spectrometer with a quadrupole-time-of-flight analyser was used to study the speciation of the palladium-benzoylthiourea (Pd-BTU) complex and to determine the Pd content. The Pd-BTU complex was selectively pre-concentrated using disposable pipette extraction (DPX). Extraction parameters as well as ESI-MS parameters such as concentration of BTU, acidity, composition of medium and capillary voltage, etc., were optimized based on the major species [Pd(BTU)(2)S](+). RESULTS: The method gave quantitative and selective pre-concentration of the Pd-BTU complex from SHLLW. Linearity from 5 ppb to 200 ppb and a limit of detection of 0.012 ppb were obtained for Pd. No interference from the neighboring elements, viz. ruthenium, rhodium, silver and cadmium, was observed during the determination of Pd based on the [Pd(BTU)(2)S](+) peak. The ESI signal intensity was not influenced by the presence of the many other elements in the SHLLW solution. CONCLUSIONS: Good sensitivity, tolerance to matrix concentration and the absence of interference from neighboring elements make the method very promising for the determination of Pd at low levels in complex samples. We have demonstrated the capability of ESI-MS for the quantification of Pd in complex matrices and its potential for providing data on speciation, using the Pd-BTU complex.

Scope of detection and determination of gallium(III) in industrial ground water by square wave anodic stripping voltammetry on bismuth film electrode.

Gallium(III) in ground water may cause human health hazards due to the antineoplastic and antimicrobial activities of gallium. However, the exposure limit of Ga(III) has not been set. This paper demonstrates the scope of employing the square wave anodic stripping voltammetry (SWASV) on bismuth film electrode (BiFE) for selective and sensitive detection of Ga(III) as well as its accurate and precise determination. The key parameters were optimized and the bismuth film morphology was characterized. The performance of BiFE was also compared with that of the mercury film electrode (MFE). The performance of BiFE was also studied for interferences of Zn(II), Cd(II), Tl(I) and Cu(II) ions. Gaussian peak fitting was performed to improve the calibration curve and the fitting process revealed almost similar stripping peak heights as obtained from the experimentally observed data though slight improvement in calibration was obtained from the peak area analysis. A good linear dynamic range (R(2)=0.996) was obtained in the concentration range of 20-100 µg/L with a limit of detection (LOD) of 6.6 µg/L (S/N=3) of Ga(III). A relative standard deviation of 2.9% (n=10) was obtained for 20 µg/L of Ga(III) solution. The practical analytical utility of the method was verified by the determination of Ga(III) in spiked water samples, where 100-105% recovery of Ga(III) was achieved.

Determination of uranium in seawater samples by liquid chromatography using mandelic acid as a complexing agent.

The determination of uranium at different stages of the recovery process as well as in seawater is important in its recovery study. A previous study developed a high-performance liquid chromatography (HPLC) method for uranium determination in seawater using α-hydroxy isobutyric acid as a chelating agent. However, this method causes turbidity in process samples containing high amounts of iron, resulting in the clogging of the HPLC column. In the present work, use of mandelic acid as a chelating agent for uranium has been explored. Elution conditions were optimized for the separation of iron [Fe(III)] and uranium [U(VI)] by studying the effect of an ion interaction reagent, the concentration of mandelic acid, and methanol content in the mobile phase. Different parameters were optimized to develop off- line pre-concentration of uranyl-mandelate on the reversed stationary phase. The method offers quantitative recovery of uranium and linearity in the U(VI) concentration range of 0.5 ppb to 500 ppb and can be used for the determination of U(VI) in process samples with Fe/U amount ratios up to 3,000. The method has been successfully used for the determination of U(VI) in seawater samples and process samples. The developed methodology was validated by comparing the results with those of isotope dilution-thermal ionization mass spectrometry.

A critical evaluation of different isotope correlations for the determination of (242)Pu.

Different correlations are evaluated for the determination of (242)Pu in Pu generated from PHWR reactors with an average burn-up of about 10,000 MWd/TU. It is shown that the correlations involving ratios of Pu isotopes, except for (241)Pu, provide data with better confidence compared with those involving the atom% abundance. These correlations are also attractive when the decay period of the given sample is not known. In addition, it is shown that instead of using (239)Pu atom% abundance alone (Swinhoe et al., 2010), either (240)Pu atom% or a linear combination of (239)Pu and (240)Pu gives abundance of (242)Pu with better reliability. The uncertainty due to different decay periods also remains unaffected when using the correlation involving both (239)Pu and (240)Pu atom%. The present conclusions are based on Pu isotopic composition data from PHWR reactors ((239)Pu 65-75%) whereas those reported by other investigators are for PWR and BWR types of reactors.

Fractionation correction methodology for precise and accurate isotopic analysis of boron by negative thermal ionization mass spectrometry based on BO2(-) ions and using the 18O/16O ratio from ReO4(-) for internal normalization.

A novel approach to obtain a fractionation free (11)B/(10)B isotope ratio based on oxygen isotopes determined in situ from the same filament loading by N-TIMS is described. The method uses only a few nanograms of B to produce BO(2)(-) ions. First, the oxygen isotopes are determined at a lower filament temperature using ReO(4)(-) ions and employing (187)Re/(185)Re for internal normalization. Subsequently, the filament temperature is increased to get sufficient BO(2)(-) ions and predetermined (18)O/(16)O isotopes from the same filament loading is used to correct for boron mass fractionation. The validity of the method has been demonstrated by analyzing a NIST-SRM-951 boron isotopic certified standard, two synthetic B mixtures, and two coral reference materials. An average analytical precision of 0.6 per thousand (n = 6) has been demonstrated. This is an important and crucial step forward in making the application of BO(2)(-) ions by N-TIMS routine in coral, foraminifera, and other samples where only limited amounts of boron are available. This new method does not require any additional effort in loading or in carrying out the mass spectrometric analysis but eliminates the need of assuming a fixed (18)O/(16)O ratio and thus provides higher accuracy for applications in paleo-oceanography, geochemistry, and cosmo-chemistry.

Laser-induced breakdown spectroscopy for determination of uranium in thorium-uranium mixed oxide fuel materials.

Laser-induced breakdown spectroscopy (LIBS) has been developed for determining the percentage of uranium in thorium-uranium mixed oxide fuel samples required as a part of the chemical quality assurance of fuel materials. The experimental parameters were optimized using mixed oxide pellets prepared from 1:1 (w/w) mixture of thorium-uranium mixed oxide standards and using boric acid as a binder. Calibration curves were established using U(II) 263.553 nm, U(II) 367.007 nm, U(II) 447.233 nm and U(II) 454.363 nm emission lines. The uranium amount determined in two synthetic mixed oxide samples using calibration curves agreed well with that of the expected values. Except for U(II) 263.553 nm, all the other emission lines exhibited a saturation effect due to self-absorption when U amount exceeded 20 wt.% in the Th-U mixture. The present method will be useful for fast and routine determination of uranium in mixed oxide samples of Th and U, without the need for dissolution, which is difficult and time consuming due to the refractory nature of ThO(2). The methodology developed is encouraging since a very good analytical agreement was obtained considering the limited resolution of the spectrometer employed in the work.

Reversed-phase liquid chromatography using mandelic acid as an eluent for the determination of uranium in presence of large amounts of thorium.

Studies were carried out for the separation of uranium (U) and thorium (Th) on reversed-phase (RP) C18 columns using mandelic acid as an eluent. Retention of thorium-mandelate on the unmodified stationary phase was found to be greater than that of uranyl-mandelate under the pH conditions employed. Th retention capacity of the stationary phase was determined as a function of pH and MeOH content of the mobile phase. The optimised parameters allowing U elution prior to Th were utilized for the determination of small amounts of U in the presence of large amounts of Th. The method has been used for the determination of U in synthetic samples with Th/U amount ratios up to 100,000 (10 microg/g of U) without any pre-separation, employing a particulate C18 column. Effect of concentration of ion interaction reagents (IIRs) on the retention was studied to understand the mechanism of adsorption of their mandelate complexes onto the stationary phase. The experiments conducted unequivocally prove that thorium-mandelate complex is neutral whereas uranyl-mandelate complex is anionic in nature.

Determination of boron at sub-ppm levels in uranium oxide and aluminum by hyphenated system of complex formation reaction and high-performance liquid chromatography (HPLC).

Boron, at sub-ppm levels, in U3O8 powder and aluminum metal, was determined using complex formation and dynamically modified reversed-phase high-performance liquid chromatography (RP-HPLC). Curcumin was used for complexing boron extracted with 2-ethyl-1,3-hexane diol (EHD). Separation of complex from excess reagent and thereafter its determination using the online diode array detector (DAD) was carried out by HPLC. Calibration curve was found to be linear for boron amounts in the sample ranging from 0.02 microg to 0.5 microg. Precision of about 10% was achieved for B determination in samples containing less than 1 ppmw of boron. The values obtained by HPLC were in good agreement with the data available from other analytical techniques. The precision in the data obtained by HPLC was much better compared to that reported by other techniques. The present hyphenated methodology of HPLC and complex formation reaction is interesting because of cost performance, simplicity, versatility and availability when compared to other spectroscopic techniques like ICP-MS and ICP-AES.

Direct determination of lanthanides in simulated irradiated thoria fuels using reversed-phase high-performance liquid chromatography.

Studies were carried out to develop an HPLC method for the determination of lanthanides, in presence of Th and U, without involving any pre-separation procedure for the matrix elements (Th, U). The effect of concentration of the ion interaction reagent on the retention pattern of lanthanides, thorium and uranium was studied using a reversed-phase C18 column. The chromatographic parameters were optimized for maximizing the capacity of the column to hold thorium. Dual gradient elution was used for the separation of lanthanides from a mixture of thorium and uranium present in large proportion. The method facilitates the use of a minor fission product as an internal standard for the accurate and precise quantification of lanthanides by HPLC. The developed methodology was validated by using synthetically prepared samples with different proportions of lanthanides. Studies were also carried out for the separation and determination of U and Th on a reversed-phase column. A gradient of methanol and alpha-hydroxy isobutyric acid was employed for the separation and determination of uranium in presence of large amounts of thorium.

Separation and determination of lanthanides, thorium and uranium using a dual gradient in reversed-phase liquid chromatography.

Separation and determination of lanthanides, Th and U is of great relevance in different fields of science and technology. Reversed-phase high-performance liquid chromatography (RP-HPLC) using alpha-hydroxy isobutyric acid (alpha-HIBA) as an eluent on reversed-phase column modified to cation exchanger has been reported to achieve the separation. However, under those conditions, Th and U are eluted amongst lanthanides, making their quantification difficult due to overlapping with some of the lanthanides peaks. In this work, different chromatographic parameters (concentrations of eluent and ion interaction reagent, pH, etc.) were studied systematically to arrive at optimum chromatographic conditions. Using the dual (concentration and pH) gradient conditions, lanthanides, Th and U could be separated in 11 min by RP-HPLC with sequential elution of Th and U after the elution of all the lanthanides. The separation methodology was tested using SY-3 rock sample for the separation and determination of lanthanides, Th and U. The method allows an accurate determination of these elements in a single run using a single column. Also, the method is fast and cost-effective compared to the reported methods.

Comparative evaluation of three alpha-hydroxycarboxylic acids for the separation of lanthanides by dynamically modified reversed-phase high-performance liquid chromatography.

The resolution for the three homologues of alpha-hydroxycarboxylic acids viz. lactic acid, alpha-hydroxyisobutyric acid (alpha-HIBA) and alpha-hydroxy-alpha-methylbutyric acid (alpha-H-alpha-MBA), was compared for the individual separation of 14 lanthanide elements under identical experimental conditions. Alpha-HIBA was found to be the best for separation of heavier lanthanides (Tb to Lu) while alpha-H-alpha-MBA led to a better separation for lighter lanthanides (La to Eu). All the 14 lanthanides were separated by gradient HPLC employing both alpha-HIBA and alpha-H-alpha-MBA so that there was reasonable resolution among all the peaks and the separation was completed in a short time.