Conditions affecting the release of thorium and uranium from the tailings of a niobium mine.

Determinations of the mobility of metals from tailings is a critical part of any assessment of the environmental impacts of mining activities. The leaching of thorium and uranium from the tailings of different processing stages of a niobium mine was investigated for several pH, ionic strengths and concentrations of natural organic matter (NOM). The pH of the leaching solution did not have a noticeable impact on the extraction of Th, however, for pH values below 4, increased U mobilization was observed. Similarly, only a small fraction of Th (0.05%, ≤15 µg kg-1) and U (1.22%, ≤6 µg kg-1) were mobilized from the tailings in the presence of environmentally relevant concentrations of Ca, Mg or Na. However, in the presence of 10 mg L-1 of fulvic acid, much higher concentrations of ca. 700 µg kg-1 of Th and 35 µg kg-1 of U could be extracted from the tailings. Generally, colloidal forms of Th and dissolved forms of U were mobilized from the tailings, however, in the presence of the fulvic acid, both dissolved and colloidal forms of the two actinides were observed. Single Particle ICP-MS was used to confirm the presence of Th (and U) containing colloids where significant numbers (up to 107 mL-1) of Th and U containing colloids were found, even in 0.2 µm filtered extracts. Although mass equivalent diameters in the range of 6-13 nm Th and 6-9 nm for U could be estimated (based upon the presence of an oxyhydroxide), most of the colloidal mass was attributed to larger (>200 nm) heterocomposite particles.

Dispersion and solubility of In, Tl, Ta and Nb in the aquatic environment and intertidal sediments of the Scheldt estuary (Flanders, Belgium).

Certain specialty elements are indispensable in modern technologies for their particular properties. Yet, potential risks associated to the release of these elements at any stage, remains unknown. Therefore, the dispersion of indium (In), thallium (Tl), tantalum (Ta) and niobium (Nb) in the aquatic environment of the Scheldt estuary (Flanders, Belgium) was studied. Maximum concentrations in intertidal sediments of 101 ± 15 µg kg-1 for In, 481 ± 37 µg kg-1 for Tl, 88 ± 19 µg kg-1 for Ta and 1162 ± 4 µg kg-1 for Nb appeared on the sampling location closest to the river mouth, i.e. 57.5 km upstream. Their distribution in the intertidal sediments depends on the physicochemical sediment characteristics along the flow of the river Scheldt. The same was the case for most other metals and aluminum as their occurrence also correlated (p < 0.05) with the occurrence of In, Tl and Nb. While in general, studied elements correlate to the OM content and sulfur and phosphorus herein included, a relative enrichment of In, Tl and Nb was seen at Rupelmonde (92.0 km from the river mouth). Mainly the intertidal sediment silt fraction is capable of retaining the elements by exchanging with other ions in the mineral interlayer. Increasing salinity towards the river mouth can furthermore induce the formation of insoluble chloride species. Overall, the solubility of In, Tl, Ta and Nb appeared extremely low upon extraction of pore water from intertidal sediments saturated to 100% field capacity.

Interinstrumental transfer of a fast short-end injection capillary electrophoresis method: Application to the separation of niobium, tantalum, and their substituted ions.

The interinstrumental transfer of a short-end CE method was studied. A model separation of the hexameric forms of niobium, tantalum, and their substituted ions (Nb6-x Tax with 0 ≤ x ≤ 6) was selected as test case. The method was first optimized on a Beckman instrument and in a second step transferred to an Agilent instrument. The transfer needed updated guidelines that tackled differences in effective capillary length, 8.5 (Agilent) versus 10 cm (Beckman), because of instrumental different capillary cartridges. Differences in effective length lead to migration time and separation efficiency inequalities, illustrated by a decrease in resolution between the substituted ions. The difference in effective length was overcome by adapting the lift offset parameter of the Agilent instrument. The lift offset default setting is 4 mm and by increasing this parameter both the inlet and outlet lifts are lowered and thus the detection window can be displaced and consequently the effective length was increased. The decrease in effective length difference and the effect on the separation efficiency was investigated and led finally to a restored separation of the substituted ions. The adaptation of the lift offset parameter during short-end injection methods was added to earlier developed guidelines to facilitate interinstrumental method transfer of CE methods.

Solute lean Ti-Nb-Fe alloys: An exploratory study.

In this study, we explored the Ti-Nb-Fe system to find an optimal cost-effective composition with the lowest elastic modulus and the lowest added Nb content. Six Ti-(31-4x)Nb-(1+0.5x)Fe ingots were prepared and Nb was substituted with Fe, starting at Ti-31Nb-1.0Fe and going up to Ti-11Nb-3.5Fe (wt%). The ingots were subjected to cold rolling, recrystallization and solution treatment, followed by water-quenching (WQ), furnace cooling (FC) or step-quenching to 350°C, which caused massive formation of isothermal ω phase. All the water-quenched alloys displayed athermal ω phase, which is apparently the result of fully collapsed ß phase. The Fe content improved the compressive strength of the alloys. In the FC alloys, substitution with Fe favored the formation of α phase instead of ω phase, giving rise to a solute-rich ß phase with a lattice parameter of 0.3249nm. Among the FC alloys, the lowest modulus of 83±4GPa was obtained in the Ti-19Nb-2.5Fe alloy, which exhibited fine and well dispersed α precipitation and absence of ω phase. DSC experiments indicated that the experimental alloys showed varying phase stability during heating.

Composition optimization of low modulus and high-strength TiNb-based alloys for biomedical applications.

The effect of chemical composition on microstructure and tensile properties of a series of low modulus Ti-Nb-Cu-Ni-Al alloys was studied. These alloys consist of primary micrometer-sized ß-Ti dendrites surrounded by intermetallic phases. The morphology of the intermetallic phases is strongly affected by composition. Due to the composite microstructure, the alloys exhibit a low Young's modulus (77-84GPa) together with a high yield strength of about 1000MPa as well as moderate tensile ductility. The results demonstrate that complete substitution of Al by Ti reduces the Young's modulus by 5%. Increasing Nb content at the expense of Ti causes a significant improvement of tensile ductility.

Development of a capillary electrophoresis method for the analysis in alkaline media as polyoxoanions of two strategic metals: Niobium and tantalum.

Tantalum (Ta) and niobium (Nb) are two strategic metals essential to several key sectors, like the aerospace, gas and oil, nuclear and electronic industries, but their separation is really difficult due to their almost identical chemical properties. Whereas they are currently produced by hydrometallurgical processes using fluoride-based solutions, efforts are being made to develop cleaner processes by replacing the fluoride media by alkaline ones. However, methods to analyze Nb and Ta simultaneously in alkaline samples are lacking. In this work, we developed a capillary zone electrophoresis (CE) method able to separate and quantify Nb and Ta directly in alkaline media. This method takes advantage of the hexaniobate and hexatantalate ions which are naturally formed at pH>9 and absorb in the UV domain. First, the detection conditions, the background electrolyte (BGE) pH, the nature of the BGE co-ion and the internal standard (IS) were optimized by a systematic approach. As the BGE counter-ion nature modified the speciation of both ions, sodium- and lithium-based BGE were tested. For each alkaline cation, the BGE ionic strength and separation temperature were optimized using experimental designs. Since changes in the migration order of IS, Nb and Ta were observed within the experimental domain, the resolution was not a monotonic function of ionic strength and separation temperature. This forced us to develop an original data treatment for the prediction of the optimum separation conditions. Depending on the consideration of either peak widths or peak symmetries, with or without additional robustness constraints, four optima were predicted for each tested alkaline cation. The eight predicted optima were tested experimentally and the best experimental optimum was selected considering analysis time, resolution and robustness. The best separation was obtained at 31.0°C and in a BGE containing 10mM LiOH and 35mM LiCH3COO.The separation voltage was finally optimized, resulting in the separation of Nb, Ta, and IS in less than 2.5min, which is three times faster than any CE method ever reported for the separation of Nb and Ta (acidic media included). Some figures of merit of the method were determined such as linearity ranges and limits of quantitation. Finally, the method was successfully applied to the analysis of a real industrial sample.

A comparative study of the cytotoxicity and corrosion resistance of nickel-titanium and titanium-niobium shape memory alloys.

Nickel-titanium (NiTi) shape memory alloys (SMAs) are commonly used in a range of biomedical applications. However, concerns exist regarding their use in certain biomedical scenarios due to the known toxicity of Ni and conflicting reports of NiTi corrosion resistance, particularly under dynamic loading. Titanium-niobium (TiNb) SMAs have recently been proposed as an alternative to NiTi SMAs due to the biocompatibility of both constituents, the ability of both Ti and Nb to form protective surface oxides, and their superior workability. However, several properties critical to the use of TiNb SMAs in biomedical applications have not been systematically explored in comparison with NiTi SMAs. These properties include cytocompatibility, corrosion resistance, and alterations in alloy surface composition in response to prolonged exposure to physiological solutions. Therefore, the goal of the present work was to comparatively investigate these aspects of NiTi (49.2 at.% Ti) and TiNb (26 at.% Nb) SMAs. The results from the current studies indicate that TiNb SMAs are less cytotoxic than NiTi SMAs, at least under static culture conditions. This increased TiNb cytocompatibility was correlated with reduced ion release as well as with increased corrosion resistance according to potentio-dynamic tests. Measurements of the surface composition of samples exposed to cell culture medium further supported the reduced ion release observed from TiNb relative to NiTi SMAs. Alloy composition depth profiles also suggested the formation of calcium phosphate deposits within the surface oxide layers of medium-exposed NiTi but not of TiNb. Collectively, the present results indicate that TiNb SMAs may be promising alternatives to NiTi for certain biomedical applications.

Assessment of radionuclide and metal contamination in a thorium rich area in Norway.

The Fen Central Complex in southern Norway, a geologically well investigated area of magmatic carbonatite rocks, is assumed to be among the world largest natural reservoirs of thorium ((232)Th). These rocks, also rich in iron (Fe), niobium (Nb), uranium ((238)U) and rare earth elements (REE), were mined in several past centuries. Waste locations, giving rise to enhanced levels of both radionuclides and metals, are now situated in the area. Estimation of radionuclide and metal contamination of the environment and radiological risk assessment were done in this study. The average outdoor gamma dose rate measured in Fen, 2.71 µGy h(-1), was significantly higher than the world average dose rate of 0.059 µGy h(-1). The annual exposure dose from terrestrial gamma radiation, related to outdoor occupancy, was in the range 0.18-9.82 mSv. The total activity concentrations of (232)Th and (238)U in soil ranged from 69 to 6581 and from 49 to 130 Bq kg(-1), respectively. Enhanced concentrations were also identified for metals, arsenic (As), lead (Pb), chromium (Cr) and zinc (Zn), in the vicinity of former mining sites. Both radionuclide and heavy metal concentrations suggested leaching, mobilization and distribution from rocks into the soil. Correlation analysis indicated different origins for (232)Th and (238)U, but same or similar for (232)Th and metals As, Cr, Zn, nickel (Ni) and cadmium (Cd). The results from in situ size fractionation of water demonstrated radionuclides predominately present as colloids and low molecular mass (LMM) species, being potentially mobile and available for uptake in aquatic organisms of Norsjø Lake. Transfer factors, calculated for different plant species, showed the highest radionuclide accumulation in mosses and lichens. Uptake in trees was, as expected, lower. Relationship analysis of (232)Th and (238)U concentrations in moss and soil samples showed a significant positive linear correlation.

Testing the corrosion resistance of stainless steels during the fermentation of probiotic drink.

BACKGROUND: Over recent years, food producers have devoted much attention to the production of safe foods. Simultaneously, using advanced process technologies, it has been necessary to carefully select materials for use in process equipment. Milk and its products are exposed to metal surfaces from the time they are processed, through the various stages of handling and manufacture, to the packaging of the finished products for market. The selection of suitable materials for daily use in the dairy industry cannot be governed solely by their price and mechanical properties but must also take into consideration their influence on the quality of milk products. RESULTS: This paper presents the results of testing the corrosion resistance of three stainless steels during the fermentation of a specific probiotic drink, kefir. Experiments were conducted using preliminarily activated kefir grains as a starter culture. Corrosion resistance was studied using a gravimetric and two electrochemical methods. The two steels showing the best corrosion performance differed mainly in their Mo and Nb contents. CONCLUSION: The results indicated that Nb played the most protective role against corrosion during kefir fermentation, since the steel containing Nb but no Mo showed the lowest corrosion rate.

Bijvoet in solution reveals unexpected stereoselectivity in a Michael addition.

The absolute configuration of small crystallizable molecules can be determined with anomalous X-ray diffraction as shown by Bijvoet in 1951. For the majority of compounds that can neither be crystallized nor easily be converted into crystallizable derivatives, stereocontrolled organic synthesis is still required to establish their absolute configuration. In this contribution, a new fundamental methodology for resolving the absolute configuration will be presented that does not require crystallization. With residual dipolar coupling enhanced NMR spectroscopy, ensembles of a limited number of structures are created reflecting the correct conformations and relative configuration. Subsequently, from these ensembles, optical rotation dispersion (ORD) spectra are predicted by DFT calculations and compared to experimental results. The combination of these two steps reveals the absolute configuration of a flexible molecule in solution, which is a big challenge to chiroptical methods and DFT in the absence of NMR spectroscopy. Here the absolute stereochemistry of the product of a new Michael addition, synthesized via a niobium(V) chiral enolate, will be elucidated by using the new methodology.

Quantitative microscopy characterization of hydrous niobium phosphate into bleached cellulose.

In this research the spatial distribution characterization of niobium phosphate into bleached cellulose was carried out combining processing and images analysis obtained by SEM and statistical methodologies. The objective is to investigate the deposit composition and phosphate morphology by using complementary analytical techniques. Based on the proposed methodology, parameters of niobium phosphate agglomerates (size and shape) and fiber morphology were evaluated depending on gray-levels (average luminance and fiber type): fiber characteristics (morphology) were measured. For the test method proposed, a specific region of cellulose/NbOPO(4) x nH(2)O composite was analyzed. This method involves area fraction measuring with a conditional probabilistic analysis. The analyzed fields were divided in different ways, called 'Scanning' and as a result, in quantitative terms, the phosphate deposition was described as spatial distribution homogeneous or inhomogeneous. The quantitative microscopy as a non-destructive testing provides relevant information when it is combined with statistic analysis.

Development of a carbon paste electrode containing benzo-15-crown-5 for trace determination of the uranyl ion by using a voltammetric technique.

The interaction of macrocyclic compounds like crown ethers and UO2(2+) has been studied by electrochemical methods. A modified carbon paste electrode incorporating benzo-15-crown-5 (B15C5) was used to evaluate the electron transfer reaction of UO2(2+) by cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. Electrochemical impedance studies showed that charge transfer resistance was less for the B15C5-modified electrode than for the plain carbon paste electrode (PCPE). On the basis of these observations, a UO2(2+)-sensitive crown ether chemically modified electrode (CME) for trace analysis was fabricated and investigated in aqueous solutions. It was found that a 5% B15C5-CME for UO2(2+) showed a better voltammetric response than did the PCPE. UO2(2+) could be quantified at sub-microg/mL levels by differential pulse voltammetry with a detection limit of 0.03 microg/mL. By differential pulse adsorptive stripping voltammetry, UO2(2+) could be quantified in the working range of 0.002-0.2 microg/mL, with a detection limit of 1.1 microg/L. Simultaneous determination of UO2(2+), Pb(2+), and Cd(2+) was possible. The method was successfully applied to the determination of UO2(2+) in synthetic, as well as real, samples; the results were found to be comparable to those obtained by inductively coupled plasma-atomic emission spectroscopy.

Iron oxide/niobium oxide core-shell magnetic nanoparticle-based phosphopeptide enrichment from biological samples for MALDI MS analysis.

The feasibility of using niobium oxide-coated magnetic nanoparticles (NPs) as affinity probes for selectively trapping phosphopeptides from peptide mixtures including tryptic digest of caseins, serum, and cell lysate was demonstrated in this study. Phosphopeptide enrichment was rapid when subjecting these systems to microwave heating for 1 min; the probe-target species, which were readily isolated through magnetic separation, were then analyzed using matrix-assisted laser desorption/ ionization mass spectrometry (MALDI MS). Only signals for phosphopeptides were present in the resulting mass spectra. The detection limit for monophosphopeptide was as low as 5 fmol.

Historical storage budgets of organic carbon, nutrient and contaminant elements in saltmarsh sediments: biogeochemical context for managed realignment, Humber Estuary, UK.

Biogeochemical data from Welwick marsh (Humber Estuary, UK), an actively accreting saltmarsh, provides a decadal-centennial-scale natural analogue for likely future biogeochemical storage effects of managed realignment sites accreting either intertidal muds or saltmarsh. Marsh topographic profiles and progradation history from aerial photographs were combined with (137)Cs and niobium contamination history to establish and verify chronology and sediment mass accumulation. These data, combined with down-core measurements of particulate organic carbon (C(org)), organic nitrogen (N(org)), particle reactive phosphorus and selected contaminant metal (Zn, Pb, Cu, As and Nb) contents were then used to calculate sediment and chemical storage terms and to quantify changes in these over time. These data are used to help predict likely future biogeochemical storage changes at managed realignment sites in the estuary. The net effect of returning some 26 km(2) of reclaimed land to intertidal environments now (about 25% of the maximum possible realignment storage identified for the estuary) could result in the storage of some 40,000 tonnes a(-1) of sediment which would also bury about 800 tonnes a(-1) of C(org) and 40 tonnes a(-1) of N(org). Particulate contaminant P burial would be around 25 tonnes a(-1) along with approximately 6 tonnes a(-1) contaminant Zn, 3 tonnes a(-1) contaminant Pb, and approximately 1 tonnes a(-1) contaminant As and Cu. The study also shows that reclamation activities in the outer estuary since the mid-1700s has prevented, in total, the deposition of about 10 million tonnes of sediment, along with 320,000 tonnes of C(org) and 16,000 tonnes of N(org). The study provides a mid-1990s baseline against which future measurements at the site can determine changes in burial fluxes and improvement or deterioration in contaminant metal contents of the sediments. The data are directly relevant for local managed realignment sites but also broadly indicative for sites generally on the European North Sea Coast.

Computer-aided control of electrolysis of solid Nb2O5 in molten CaCl2.

Low energy production of Nb powders via computer-aided control (CAC) of two-electrode electrolysis of porous Nb2O5 pellets (ca. 1.0 g) has been successfully demonstrated in molten CaCl2 at 1123 K. It was observed that potentiostatic electrolysis of the oxide in a three-electrode cell led to a cell voltage, i.e. the potential difference between the working (cathode) and counter (anode) electrodes, that decreased to a low and stable value within 1-2 h of the potential application until the end of the electrolysis (up to 12 h in this work). The cell voltage varied closely according to the current change. The stabilised cell voltage was below 2.5 V when the cathode potential was more positive than that for the reduction of Ca2+, leading to much lower energy consumption than that of constant voltage (>3.0 V) two-electrode electrolysis, as previously reported. Using a computer to program the variation of the cell voltage of two-electrode electrolysis according to that observed in the potentiostatic three-electrode electrolysis (0.05 V vs. Ca/Ca2+), a Nb powder with ca. 3900 ppm oxygen was produced in 12 h, with the energy consumption being 37.4% less than that of constant voltage two-electrode electrolysis at 3.0 V. Transmission electron microscopy revealed thin oxide layers (4-6 nm) on individual nodular particles (1-5 microm) of the obtained Nb powder. The oxide layer was likely formed in post-electrolysis processing operations, including washing in water, and contributed largely to the oxygen content in the obtained Nb powder.

A highly selective spectrophotometric determination of niobium (V) using 3-hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1-benzopyran as a complexing agent.

3-Hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1benzopyran (HPCPB) is used as an analytical reagent for the spectrophotometric determination of niobium in trace amounts with which it forms a yellow coloured complex (4:1) in perchloric acid medium. The complex is extractable into chloroform and shows absorption maximum at 407-418 nm with a molar absorptivity of 2.79 x 10(4) L mol(-1) cm(-1) and Sandell's sensitivity equal to 0.0033 microg Nb(V) cm(-2), respectively. Beer's law holds good in the range 0-1.2 microg Nb ml(-1), with a standard deviation of +/- 0.0015 absorbance units. The method is free from the interference of a large number of elements and handles satisfactorily the analysis of various samples of varying complexity.

(23)Na multiple-quantum MAS NMR of the perovskites NaNbO(3) and NaTaO(3).

The distorted perovskites NaTaO(3) and NaNbO(3) have been studied using (23)Na multiple-quantum (MQ) MAS NMR. NaTaO(3) was prepared by high temperature solid state synthesis and the NMR spectra are consistent with the expected room temperature structure of the material (space group Pbnm), with a single crystallographic sodium site. Two samples of NaNbO(3) were studied. The first, a commercially available sample which was annealed at 900 degrees C, showed two crystallographic sodium sites, as expected for the room temperature structure of the material (space group Pbcm). The second sample, prepared by a low temperature hydrothermal method, showed the presence of four sodium sites, two of which match the expected room temperature structure and the second pair, another polymorph of the material (space group P21ma). This is consistent with powder X-ray diffraction data which showed weak extra peaks which can be accounted for by the presence of this second polymorph. Density functional theory (DFT) calculations support our conclusions, and aid assignment of the NMR spectra. Finally, we discuss the measured NMR parameters in relation to other studies of sodium in high coordination sites in the solid state.

Fast simultaneous determination of niobium and tantalum by Kalman Filter analysis with flow injection chemiluminescence method.

A fast and highly efficient Kalman Filter analysis-flow injection chemiluminescence (FI-CL) method was developed to simultaneously determine trace amounts of niobium and tantalum in geological samples. The method, without the boring process of separation and dear instruments, is suitable for field scene analysis. The mixed chemiluminescence kinetic curve was analyzed by a Kalman Filter (KF) in this method to realize the simultaneous determination of niobium and tantalum. Possible interference elements in the determination were investigated. Under the selected conditions, the detection limits (3sigma, n = 11) of niobium(V) and tantalum(V) were 2.1 x 10(-3) microg g(-1) and 4.0 x 10(-3) microg g(-1), respectively, and the relative standard deviations were 4.9% and 3.3% (n = 9). The method was applied to the determination of niobium and tantalum in geological samples with satisfactory results.

[Direct determination of Nb in titanium oxide using slurry sample introduction by axial viewing inductively coupled plasma optical emission spectrometry].

By using dispersant polyacrylate amine (NH4PAA) to disperse TiO2, effects of different dispersants, pH value and the amount of dispersant on TiO2 slurry were investigated. The pH value of the medium and the dispersant amount were optimized, and a stable and homogeneous suspension was prepared. Nb in TiO2 was determined by an axial viewing ICP-OES spectrometer. At the same time, the performance of the axial viewing ICP-OES using solid powder analysis was discussed. Under the optimum experimental conditions, the detection limit of the present method is 3.0 microg x L(-1) and the RSD is 3.1% (n = 3, c = 0.3 mg x L(-1)).

Effect of niobium content on the microstructure and thermal properties of fluorapatite glass-ceramics.

Niobium oxide has been shown to improve biocompatibility and promote bioactivity. The purpose of this study was to evaluate the effect of niobium oxide additions on the microstructure and thermal properties of fluorapatite glass-ceramics for biomedical applications. Four glass-ceramic compositions with increasing amounts of niobium oxide from 0 to 5 wt % were prepared. The glass compositions were melted at 1,525 degrees C for 3 h, quenched, ground, melted again at 1,525 degrees C for 3 h and furnace cooled. The coefficient of thermal expansion was measured by dilatometry. The crystallization behavior was evaluated by differential thermal analysis. The nature of the crystalline phases was investigated by X-ray diffraction. The microstructure was studied by SEM. In addition, the cytotoxicity of the ceramics was evaluated according to the ASTM standard F895--84. The results from X-ray diffraction analyses showed that fluorapatite was the major crystalline phase in all glass-ceramics. Differential thermal analyses revealed that fluorapatite crystallization occurred between 800 and 934 degrees C depending on the composition. The coefficient of thermal expansion varied from 7.6 to 9.4 x 10(-6)/ degrees C. The microstructure after heat treatment at 975 degrees C for 30 min consisted of submicroscopic fluorapatite crystals (200--300 nm) for all niobium-containing glass-ceramics, whereas the niobium-free glass-ceramic contained needle-shaped fluorapatite crystals, 2 microm in length. None of the glass-ceramics tested exhibited any cytotoxic activity as tested by ASTM standard F895--84.