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1.
A simple, effective and low cost solid phase extraction procedure was standardized for the trace and ultra-trace level determination of rare earth impurities, such as, Ce, Dy, Sm, Gd, Eu, Er etc. which act as neutron poisons, in nuclear grade uranium oxide (U3O8?>?99.9% by weight). The method involves selective separation of these elements as their fluorides with the help of activated charcoal from major uranium matrix followed by determination by ICP-MS and high resolution ICP-OES. The residual uranium content of the solution was <10???g/mL. The recovery of REEs ranges from 85 to 105%. The method was validated with nuclear grade uranium oxide standards CRM-I to CRM-V (BARC, Mumbai, India) in addition to some synthetic standards. The RSD of the method was ±12% (n?=?3).  相似文献   

2.
A robust microwave-assisted acid digestion procedure followed by inductively coupled plasma-mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 °C), high pressure (200 psig), acid digestion (HNO3, HF and H3BO3) with 20 min dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu and Dy in ambient PM2.5 in an industrial area of Houston, TX.  相似文献   

3.
A 100-fold preconcentration procedure based on rare-earth elements (REEs) separation from water samples with an extraction chromatographic column has been developed. The separation of REEs from matrix elements (mainly Fe, alkaline and alkaline-earth elements) in water samples was performed loading the samples, previously acidified to pH 2.0 with HNO3, in a 2 ml column preconditioned with 20 ml 0.01 M HNO3. Subsequently, REEs were quantitatively eluted with 20 ml 7 M HNO3. This solution was evaporated to dryness and the final residue was dissolved in 10 ml 2% HNO3 containing 1 μg l−1 of cesium used as internal standard. The solution was directly analysed by inductively coupled plasma mass spectrometry (ICP-MS), using ultrasonic nebulization, obtaining quantification limits ranging from 0.05 to 0.10 ng l−1. The proposed method has been applied to granitic waters running through fracture fillings coated by iron and manganese oxy-hydroxides in the area of the Ratones (Cáceres, Spain) old uranium mine.  相似文献   

4.
A syringe-driven chelating column (SDCC) was applied to develop an on-line preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) method for preconcentration and determination of rare earth elements (REEs) in seawater samples. The present on-line preconcentration system consists of only one pump, two valves, an SDCC, an ICP-MS, several connectors, and Teflon tubes. Optimizations of adsorption pH condition, sample loading flow rate, and integration range were carried out to achieve optimum measurement conditions for REEs in seawater sample. Six minutes was enough for a preconcentration and measurement cycle using 10 mL of seawater sample, where the detection limits for different REEs were in the range of 0.005 pg mL−1 to 0.09 pg mL−1. Analytical results of REEs in a seawater certified reference material (CRM), NASS-5, confirmed the usefulness of the present method. Furthermore, concentrations of REEs in Nikkawa Beach coastal seawater were determined and discussed with shale normalized REE distribution pattern.  相似文献   

5.
Hsieh HF  Chen YH  Wang CF 《Talanta》2011,85(2):983-990
This paper describes a simple method for simultaneous preconcentration and matrix reduction during the analysis of rare earth elements (REEs) in water samples through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). From a systematic investigation of the co-precipitation of REEs using magnesium hydroxide, we optimized the effects of several parameters - the pH, the amount of magnesium, the shaking time, the efficiency of Ba removal, and the sample matrix - to ensure quantitative recoveries. We employed repetitive laser ablation to remove the dried-droplet samples from the filter medium and introduce them into the ICP-MS system for determinations of REEs. The enrichment factors ranged from 8 to 88. The detection limit, at an enrichment factor of 32, ranged from 0.03 to 0.20 pg mL−1. The relative standard deviations for the determination of REEs at a concentration of 1 ng mL−1 when processing 40 mL sample solution were 2.0-4.8%. We applied this method to the satisfactory determination of REEs in lake water and synthetic seawater samples.  相似文献   

6.
Qiang Fu  Qiuquan Wang 《Talanta》2007,72(4):1248-1254
A newly synthesized alkyl phosphinic acid resin (APAR) was used for on-line preconcentration of trace rare earth elements (REES, lanthanides including yttrium) and then determined by inductively coupled plasma mass spectrometry. REEs in seawater could be on-line concentrated on the APAR packed column (4.6 mm i.d. × 50 mm in length), and eluted from the column with 0.5 mL 0.1 mol L−1 nitric acid within 30 s. An enrichment factor of nearly 400 was achieved for all REEs when the seawater sample volume was 200 mL, while the matrix and coexisting spectrally interfering ions such as barium, tin and antimony could be simultaneously separated. The detection limits of this proposed method for REEs were in the range from 1.43 pg L−1 of holmium to 12.7 pg L−1 of lanthanum. The recoveries of REEs were higher than 97.9%, and the precision of the relative standard deviation (R.S.D., n = 6) was less than 5%. The method has been applied to the determination of soluble REEs in seawater.  相似文献   

7.
Understanding the properties that determine the distribution and behavior of trace impurities in Si wafers is critical to defining and controlling the performance, reliability, and yields of integrated microelectronic devices. It remains, however, an intrinsically difficult task to determine trace impurities in Si because of the minute concentrations and extremely high levels of matrix involved. In this study, we used an electrodialyzer for the simultaneous on-line removal of the silicate and acid matrices through the neutralization of the excessive hydrogen ion and selectively separation of acid and silicate ions by the combination of electrode reaction as a source of hydroxide ions with the anion exchange membrane separation. To retain the analyte ions in the sample stream, we found that the presence of moderate amounts of nitric acid and hydrazine were necessary to improve the retention efficiency, not only for Zn2+, Ni2+, Cu2+, and Co2+ ions but also for CrO42− ion. Under the optimized conditions, the interference that resulted from the sample matrix was suppressed significantly to provide satisfactory analytical signals. The precision of this method was ca. 5% when we used an electrodialyzer equipped with an anion exchange membrane to remove the sample matrix prior to performing inductively coupled plasma mass spectrometry (ICP-MS); the good agreement between the data obtained using our proposed method and those obtained using a batchwise wet chemical technique confirmed its accuracy. Our method permits the determination of Zn, Ni, Cu, Co, and Cr in Si wafers at detection limits within the range from 2.2 × 1015 to 9.0 × 1015 atoms cm−3.  相似文献   

8.
Cao X  Yin M  Li B 《Talanta》1999,48(3):517-525
A method was developed for the determination of rare earth impurities in high purity Gd(2)O(3) by inductively coupled plasma mass spectrometry (ICP-MS). The matrix suppression effect of Gd(2)O(3) on signals of rare earth impurities was compensated for by Re internal standardization. The spectra overlap interferences from GdH, GdO, GdOH(n) (n=1-3) on Tb, Tm, Yb and Lu were eliminated by 2-thylhexylhydrogen-2-ethylhexy phosphonate (EHEHP) extraction chromatographic separation. The detection limits for REEs were 0.005-0.017 ng ml(-1) in solution and 0.002-0.05 mug g(-1) in solid. Recoveries of spiked sample for REEs were from 88 to 121% with the precision of 1.0-7.5% RSD. Determination of trace REEs in two Gd(2)O(3) samples were performed. The method can be applied to analysis of 99.99-99.9999% high purity Gd(2)O(3).  相似文献   

9.
Dwinna Rahmi 《Talanta》2007,72(2):600-606
The multielement determination of trace metals in seawater was carried out by inductively coupled plasma mass spectrometry (ICP-MS) with aid of a down-sized chelating resin-packed minicolumn for preconcentration. The down-sized chelating resin-packed minicolumn was constructed with two syringe filters (DISMIC 13HP and Millex-LH) and an iminodiacetate chelating resin (Chelex 100, 200-400 mesh), with which trace metals in 50 mL of original seawater sample were concentrated into 0.50 mL of 2 M nitric acid, and then 100-fold preconcentration of trace metals was achieved. Then, 0.50 mL analysis solution was subjected to the multielement determination by ICP-MS equipped with a MicroMist nebulizer for micro-sampling introduction. The preconcentration and elution parameters such as the sample-loading flow rate, the amount of 1 M ammonium acetate for elimination of matrix elements, and the amount of 2 M nitric acid for eluting trace metals were optimized to obtain good recoveries and analytical detection limits for trace metals. The analytical results for V, Mn, Co, Ni, Cu, Zn, Mo, Cd, Pb, and U in three kinds of seawater certified reference materials (CRMs; CASS-3, NASS-4, and NASS-5) agreed well with their certified values. The observed values of rare earth elements (REEs) in the above seawater CRMs were also consistent with the reference values. Therefore, the compiled reference values for the concentrations of REEs in CASS-3, NASS-4, and NASS-5 were proposed based on the observed values and reference data for REEs in these CRMs.  相似文献   

10.
A rapid method for the enantiomeric purity determination of efaroxan has been developed by capillary electrophoresis (CE) using a dual cyclodextrin (CD) system. The influence of the nature and the concentration of CDs on separation parameters has been studied. High resolution (Rs = 7) and peak efficiency (104 000-121 000 theoretical plates) values were obtained for efaroxan enantiomers by adding two cyclodextrins, one neutral (7.5 mM DM-β-CD) and the other negatively charged (3 mM CM-β-CD) to the running buffer composed of 100 mM phosphoric acid-triethanolamine (pH 3). These resolution and peak efficiencies values allowed the quantitation of the (S)-enantiomer of efaroxan at very low enantiomeric excess even if the minor component migrates after the major one. This method was fully validated for the enantiomeric impurity determination of the (S)-form of efaroxan at the 0.05% level. Calibration curve, expressed by the peak areas ratio versus the enantiomeric purity was linear over the 0.05-1% enantiomeric impurity range (r2 = 0.9996). Limits of detection (LOD) and quantification (LOQ), expressed in term of (S)-enantiomer impurity were 0.02% and 0.05%, respectively. The accuracy of the method at 0.12%, 0.50% and 0.80% enantiomeric impurity levels for the (S)-form were determined. Recoveries were in 94-102% range for each quality control sample and were determined with good precision (intra-day R.S.D. = 3.54%, inter-day R.S.D. = 5.33%).  相似文献   

11.
The use of boric acid as a modifier for the determination of trace amount of indium in high purity antimony by electrothermal atomic absorption is described. It was found that the negative influence of the hydrofluoric acid, used for the digestion could not be eliminated by using stabilized temperature platform furnace (STPF) alone. Due to the high dissociation energy (D0 = 506 kJ mol−1) of indium fluoride, it is difficult to dissociate in the gas phase and hence is lost. In presence of HF (used for the dissolution of antimony), the universal Pd-Mg modifier does not work satisfactorily. Additionally, rising corrosion and reduced tube lifetime were observed when the acid digested (HF-HNO3) antimony solution was injected in to the platform. Improvement in platform life and elimination of interferences were achieved by the addition of boric acid as a chemical modifier together with ruthenium coating of the platform. Corrosive changes of the transversely heated graphite atomizer (THGA) platform surface were examined by scanning electron microscopy. The standard addition method was applied. A characteristic mass of 36 pg was obtained. The detection limit of the proposed method is around 0.04 μg g−1. The developed method was applied to the determination of indium in real samples. The data obtained by this method were in good agreement with those obtained by ICP-MS.  相似文献   

12.
A low pressure microwave assisted vapor phase dissolution procedure for silicon nitride and volatilization of in situ generated SiF4 has been developed using H2SO4, HF and HNO3 for the determination of trace impurities present in silicon nitride. Sample was taken in minimum amount (0.5 mL for 100 mg) of H2SO4 and treated with vapors generated from HF and HNO3 mixture in presence of microwaves in a closed container. An 80 psi pressure with ramp and hold times of 30 min and 60 min respectively, operated twice, resulted in 99.9% volatilization of Si. Matrix free solutions were analyzed for impurities using DRC-ICP-MS. The recoveries of Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Cd, Ba and Pb were between 80 and 100% after volatilization of Si. The blanks were in lower ng g−1 with method detection limits in lower ng g−1 to sub ng g−1 range. The method was applied for the analysis of two silicon nitride samples.  相似文献   

13.
Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration of trace and rare earth elements (REEs) in soils. Geochemical certified reference materials such as JLk-1, JB-1, and JB-3 were used for the validation of the analytical method. The measured values were in good agreement with the certified values for all the elements and were within 10% analytical error. Beach placer deposits of soils mainly from Odisha, on the east coast of India, have been selected to study selected trace and rare earth elements (REEs), to estimate enrichment factor (EF) and geoaccumulation index (Igeo) in the natural environment. Enrichment factor (EF) and geoaccumulation index (Igeo) results showed that Cr, Mn, Fe, Co, Zn, Y, Zr, Cd and U were significantly enriched, and Th was extremely enriched. The total content of REEs (ƩREEs) ranged from 101.3 to 12,911.3 µg g−1, with an average 2431.1 µg g−1 which was higher than the average crustal value of ΣREEs. A high concentration of Th and light REEs were strongly correlated, which confirmed soil enrichment with monazite minerals. High ratios of light REEs (LREEs)/heavy REEs (HREEs) with a strong negative Eu anomaly revealed a felsic origin. The comparison of the chondrite normalized REE patterns of soil with hinterland rocks such as granite, charnockite, khondalite and migmatite suggested that enhancement of trace and REEs are of natural origin.  相似文献   

14.
The usage of a variety of sorbents has been shown as promising matrix removal/preconcentration strategies for the determination of rare earth elements (REEs) in various natural water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES). The sorption efficiency of various zeolites (clinoptilolite, mordenite, zeolite Y, zeolite Beta), ion-exchangers (Amberlite CG-120, Amberlite IR-120, Rexyn 101, Dowex 50W X18) and chelating resins (Muromac, Chelex 100, Amberlite IRC-718) towards REEs was investigated in terms of solution pH, shaking time and sorbent amount. The results have shown that most of the materials can take up REEs at a wide pH range. The experiments were continued with clinoptilolite, zeolite Y and Chelex 100 and it was demonstrated that all three materials displayed very fast kinetics for REE sorption (higher than 96% in 1 min). Desorption from the sorbents was realized with 2.0 M HNO3 for clinoptilolite and 0.1 M HNO3 for zeolite Y and Chelex 100. Only the lower concentration range (0.01-2.0 mg l−1) of matrix-matched standards were used in quantitation although the calibration graphs were linear at least up to 10.0 mg l−1 for all REEs studied. The limit of detection (3 s) without preconcentration was 0.1, 1.0, and 0.2 μg l−1 for Eu, La, and Yb, respectively. The validity of the method with the selected sorbents was checked through spike recovery experiments.  相似文献   

15.
In this paper, an ordered mesoporous alumina coating was prepared and applied to capillary microextraction (CME) of trace Co, Ni and Cd for the first time. The coated capillary was used for on-line coupling CME with inductively plasma mass spectrometry (ICP-MS) for the determination of trace metals of Co, Ni and Cd. The porous structure of Al2O3 coating was examined by SEM and TEM. The effects of the extraction parameters including pH, sample flow rate and volume, elution solution and interfering ions on the recovery of analytes have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.33, 1.5 and 1.4 ng L−1 for Co, Ni and Cd, respectively, with a preconcentration factor of 10 times. The precisions for all investigated elements were 2.7, 4.1 and 2.5% (c = 0.05 ng L−1, n = 7), for Co, Ni and Cd, respectively, and the sample frequency was 8 h−1.The proposed method was successfully applied for the analysis of trace metals in water, rice and urine samples with the recovery of 94-105%. In order to validate the proposed method, two certified reference materials of GBW 0913 human urine and NIES No.10-b rice flour were analyzed, and the determination values are in good agreement with the certified values. The ordered mesoporous Al2O3 coated capillary can be used more than 20 times without decreasing the extraction efficiency.  相似文献   

16.
The use of boric acid as a modifier for the determination of trace amount of rubidium in high purity cesium chloride matrix by electrothermal atomic absorption is described. It was found that the negative influence of the chloride matrix could not be eliminated using stabilized temperature platform (STPF) alone. Due to the high dissociation energy (D0 = 427 kJ mol−1) of rubidium chloride, it was difficult to dissociate in the gas phase and hence is lost. Elimination of interferences was achieved by the addition of boric acid as a chemical modifier. Diluted cesium chloride samples (5%, m/v) were analyzed applying the standard addition method. The characteristic mass of 24 pg was obtained. The detection limit of the proposed method is around 26 ng g−1. The developed method was applied to the determination of traces of rubidium in high purity cesium chloride samples. The data obtained by this method were in good agreement with those obtained by other independent method like FAAS.  相似文献   

17.
A sensitive and rapid on-line method has been developed for the determination of trace amounts rare earth elements (REEs), lanthanum, cerium, neodymium and yttrium, by microwave plasma torch-atomic emission spectrometry (MPT-AES) combined with micro-column separation/preconcentration. A strong basic cinnamene anion exchange resin is used for matrix elimination and enrichment of the analytes. The adsorbed metal ions are subsequently eluted from the column and transferred into the detector with nitric acid solution for simultaneous multi-element determination. Various factors influencing the separation/preconcentration, sample flow rate, loading time, acidity and eluent flow rate, concentration, have been studied in detail. Under the optimized conditions, the detection limits for lanthanum, cerium, neodymium and yttrium based on three times of standard deviations of blank by 7 replicates are 0.89, 2.02, 1.56 and 0.78 μg·L 1, and the relative standard deviations are determined as 1.54, 4.29, 4.95 and 3.90%, respectively. The proposed method has been applied to the analysis of the four REEs in high purity Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Yb2O3, and Lu2O3 samples with a recovery range of 95.1-104.8%.  相似文献   

18.
A simple high performance liquid chromatographic method for the determination of process-related impurities in bulk drug of the central anticholinergic compound pridinol mesylate, has been developed and validated. Spectroscopically characterized synthetic impurities were used as standards. The chromatographic separation was optimized employing an experimental design strategy, and was achieved on a C18 column with a mobile phase containing 50 mM potassium phosphate buffer (pH 6.4), MeOH and 2-propanol (20:69:11, v/v/v), delivered at a flow rate of 1.0 mL min−1. UV detection was performed at 245 nm. The optimized method was thoroughly validated, demonstrating to be selective, when the chromatogram was recorded with a diode-array detector and peak purities were evaluated (>0.9995). The method is robust and linear (r2 > 0.99) over the range 0.05-2.5% (5-250% with regards to the 1% specification limit for both process-related impurities); it is also precise, regarding repeatability (RSD ≤ 1.5% for all of the analytes) and intermediate precision aspects and LOQ values for the impurities are below 0.01%. Method accuracy, evidenced by low bias of the results and analyte recoveries in the range of 99.1-102.7%, was assessed at five analyte concentration levels. The usefulness of the determination was also demonstrated through the analysis of different lots of pridinol mesylate bulk substance. The results indicate that the method is suitable for the quality control of the bulk manufacturing of pridinol mesylate drug substance.  相似文献   

19.
A method for the determination of iron in indium phosphide (InP) wafer is proposed. In the present experiment, an on-line matrix separation system using an ion exchange column was combined with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of ng g−1 level of iron. In the on-line matrix separation, indium and iron in the sample solution was passed through a strongly-basic anion exchange resin column with the 9 M HCl carrier solution, where indium was eluted from the column and iron was adsorbed on it. Then, iron was eluted with the carrier solution of 0.3 M HCl containing 1 ng ml−1 cobalt, and it was directly introduced into the ICP-MS nebulizer. In ICP-MS measurement, cobalt in the carrier solution was used as an internal standard to correct the change in sensitivity due to matrix effect, and the peak area integration was performed to quantify iron and cobalt in the integration time range of 20-60 s from the start of the cobalt solution flow. The detection limit (3σ) for iron was 3 ng g−1, and the recoveries for iron in the 0.8, 2.4, and 8.0% indium solutions were almost 100%. The method was applied to the determination of iron in commercially available iron-doped InP wafers. The obtained results for InP wafer samples with the high iron concentration were in good agreement with those obtained by graphite furnace atomic absorption spectrometry (GFAAS).  相似文献   

20.
Lai Y  Wang Q  Yang L  Huang B 《Talanta》2006,70(1):26-31
Subcellular distribution of rare earth elements (REEs, including 14 lanthanides and yttrium) in a newly discovered REE hyperaccumulator, Pronephrium simplex (P. simplex), was determined by a chemical sequence extraction followed by ICP-MS analysis. Results showed that most REEs are associated with cell wall and proteins, and REEs concentration in the proteins, 2899.5 μg g−1, is much higher than those in the cell wall; in the chloroplast of P. simplex, REEs distribute almost equally in chloroplast membrane and thylakoid, while most REEs in the thylakoid are binding with photosystem II (PS II); a new REE-binding peptide in the lamina of P. simplex, which can accumulate REEs up to 3000 μg g−1 and has higher affinity with light REEs, was characterized, indicating that its molecular mass is 5073 Da, and may have β-sheet structure; isoelectrofocusing electrophoretic photograph indicated that it is acidic peptide with IP of 3.7. Such information should be useful for understanding of both the storage and physiological role of REEs in P. simplex and further studies on the phytoremediation of REEs contaminated environments.  相似文献   

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