Inductively Coupled Plasma Mass Spectrometry Measurement Research Articles

Age dating of liquid 90Sr–90Y sources

In the context of age dating of 90Sr, the selective adsorption of zirconium ions from the mixture with strontium and yttrium by adsorbents based on TiO2 with a chemically modified surface was investigated. The general features of the separation process of strontium, yttrium, and zirconium in batch conditions were determined. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to analyze the initial and residual concentrations of the studied cations. Separation of 90Zr and 90Sr from a liquid source containing 90Sr–90Y using adsorbents based on TiO2 was performed for the first time. The ratio of 90Zr/90Sr was measured, and the age of liquid 90Sr–90Y sources was determined. In addition, we studied the age dating of 90Sr–90Y sources using a combination of liquid-scintillation counting of 90Sr and ICP-MS measurement. The results of both methods – the method of age-dating with the chemical separation of isotopes and the combination of LSC and ICP-MS analysis – agree very well and thus serve for cross-validation. Moreover, the combination of the two methods increases the confidence in the age-dating results of 90Sr–90Y sources.

Silver nanoparticle-cellulose composite for thin-film microextraction of Cd and Pb as dithiocarbamate derivatives followed by inductively-coupled plasma mass spectrometry determination

• AgNPs-cellulose composite was efficient for enrichment of Cd(II) and Pb(II) in waters. • Sample filtration was simple and fast approach to accomplish preconcentration. • LODs in the range of ng/L were obtained following ICP-MS measurement. • Affinity of S from the APDC complex toward Ag is demonstrated by SEM-EDS spectra. • Good recoveries are achieved when the method is applied to water and urine samples. Preconcentration of Cd and Pb at ultratrace level in waters following filtration through silver nanoparticles-cellulose composites used for thin-film microextraction was performed. The new procedure was based on the formation of pyrrolidine dithiocarbamate (APDC) derivatives, which showed a large affinity toward the AgNPs. For this purpose, cellulose filters modified with AgNPs were prepared in situ upon reduction of silver ions by sodium tetrahydroborate. The effect of several experimental parameters such as the kind of derivatization agent and its concentration, sample pH, desorption conditions and volume of filtered sample was assessed. Cd and Pb were quantitated in the eluates by inductively coupled plasma-mass spectrometry (ICP-MS). Filters were characterized by scanning electron microscopy (SEM) in backscattering electron mode and combined with energy dispersive X-ray spectrometry, showing the presence of Ag and S in the cellulose filter. The repeatability expressed as relative standard deviation (RSD,%) was 1.4% for Cd and 5.8% for Pb. Methodological detection limits were 0.6 and 8.5 ng/L for Cd and Pb, respectively. The method was applied to several environmental waters.

Rapid method for sequential determination of Pu and Am in soil and sediment samples by sector-field inductively coupled plasma mass spectrometry

New method was developed to analyze Pu and Am sequentially for soil and sediment by inductively coupled plasma mass spectrometry (ICPMS). The developed method uses conc. HNO3 to leach Pu and Am, Fe(OH)3 coprecipitation to remove alkali and alkaline metals, extraction chromatographic separation using UTEVA, DGA and TEVA resins to remove interfering elements (IEs) and separate Pu and Am from each other, and sector field-ICPMS to measure Pu and Am. The analysis of four standard reference materials showed that both Pu isotopes and 241Am were accurately determined by this method, as a result of its excellent decontamination ability of IEs. Especially the high decontamination factor of Pu [DF(Pu), 4.2 × 102] in Am fraction and high DF(Am) (7.0 × 103) in Pu fraction sufficiently eliminated the cross interference between 241Pu and 241Am in ICPMS measurement. In addition, stable and high chemical recoveries were achieved for Pu (71–91%) and Am (70–88%). The low LODs of Pu isotopes, short analytical time (14 h) and high DFs of IEs allows this method to sequentially analyze Pu and Am, for both global fallout and nuclear accident sourced samples.

Identification of the origin of infantile saturnism based on lead isotopic and elemental ratios

BackgroundIn France, the prevalence of childhood lead poisoning is becoming rare since the avoidance of lead in paints in 1949 and the gradual replacement of water pipes. Chronic lead toxicity is well known and is well correlated to blood lead concentration. AimHere we report a case of severe lead poisoning occurring in a young female child with a pica behavior. MethodsA blood sample and four environmental samples were analyzed using inductively coupled plasma- mass spectrometry (ICP-MS). Lead concentration, lead isotopes and elemental ratios were compared. ResultsThe determination of 208Pb/206Pb, 206Pb/207Pb and Cd/Pb has allowed us to identify the origin of lead poisoning. Discussion-conclusionThe source of contamination was eliminated and the child benefited from a psychological and medical follow up. Her outcome was positive. This case illustrated the potential interest of the use of elemental and isotopic ratios for clinical practice as the ICP-MS measurement has allowed a quick response and a rapid eviction of the contamination’s source.

Natural uranium isotopes determination in 24h-urine samples from exposed workers to enriched uranium

Individual monitoring of occupationally exposed workers to enriched uranium is mandatory, due to its radiotoxicity. The aim of this work is to determine if the use of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and an estimation method for 234U activity, could supply the information obtained by Alpha Spectrometry (AS), which is the analytical technique commonly employed in this scenario. A total of 105 samples of 24 h-urine from exposed workers were analyzed by both techniques and the obtained results were compared. 235U activity results were only quantifiable in 7 samples by AS (0.07–0.30 mBq/d) while ICP-MS quantified it in most of the cases.238U activity was measurable in 88 samples by AS and ICP-MS with wide range of results (0.11–2.4 mBq/d). For these isotopes no significant dosimetry differences were found between both techniques. However, 234U activities results obtained by AS ranged from 0.15 to 7.6 mBq/d and the isotopic ratio of 234U/238U were highly variable. 234U estimation was done with the average of these isotopic ratios and 235U and 238U ICP-MS results. Significant differences between estimated results and the ones obtained by AS were observed. Therefore, ICP-MS cannot supply the information given by AS, although can complement it. New studies must be started in order to obtain better and faster results applying radiochemical separation and ICP-MS measurement and studying the real contribution of diet in final uranium dose assessment.

Direct measurement of uranium in seawater by inductively coupled plasma mass spectrometry

A simple method for direct measurement of uranium (238U) in seawater using triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS) was established. The method provides a good analytical performance with respect to detection limit, accuracy, precision and sample throughput. During the method development and application, several interesting facts were observed: 1) Comparison results for reference material using different quantitation approaches indicate that isotope dilution (using 233U) is the most reliable to achieve accurate 238U measurement. The results obtained for direct 238U measurement in 50-fold diluted seawater samples (n = 112) also underline the difference between isotope dilution and internal (or external) standardization. 2) Appropriate dilution of seawater is important to minimize the matrix effect on the ICP-MS measurement and 20–50 dilution is recommended for natural seawater samples. 3) The sensitivity of ICP-MS was observed to increase in the beginning of sample measurement, and then decrease with the continuous injection of samples, which is believed as a consequence of matrix effect from the seawater to the ionization efficiency in the plasma. 4) When measuring samples taken from large volume of seawater stored in immovable containers for relatively long period (i.e., several months), the uranium concentration and salinity data showed slightly increasing trends with the increase of water depth in the container. Therefore, cautions need to be paid in sampling representativeness when performing 238U measurement for such long-term stored large volume samples.

Rapid method for accurate determination of actinides (U, Th, Pu and Am) in water samples for emergency response

To rapidly assess the contamination of actinides in emergency water, a method was developed to simultaneously analyze U, Th, Pu and Am. The method consists of two steps: extraction chromatographic separation using UTEVA and DGA resins and isotopic determination of actinides by inductively coupled plasma mass spectrometry (ICPMS). The whole analytical procedure takes only 8 h and high chemical recoveries of actinides were obtained. The cross spectral interferences between actinides in ICPMS measurement were sufficiently removed. The accuracy was validated by analyzing IAEA-443 seawater sample. The low limits of detection of actinides allow this method to distinguish low level contamination.

High-Performance Method for Determination of Pu Isotopes in Soil and Sediment Samples by Sector Field-Inductively Coupled Plasma Mass Spectrometry.

Plutonium is extensively studied in radioecology (e.g., soil to plant transfer and radiological assessment) and geochemistry (e.g., sediment dating). Here, we reported a new chemical separation method for rapid determination of Pu in soil and sediment samples, based on the following investigations: extraction behaviors of interfering elements (IEs, for inductively coupled plasma mass spectrometry (ICPMS) measurement) on TEVA resin; decontamination of U using TEVA, UTEVA, and DGA resins; and the impact of coprecipitation on Pu determination. The developed method consists of four steps: HNO3 leaching for Pu release; CaF2/LaF3 coprecipitation for the removal of major metals and U; the proposed TEVA + UTEVA + DGA procedure for the removal of U, Pb, Bi, Tl, Hg, Hf, Pt, and Dy; and ICPMS measurement. The accuracy of this method in determining 239+240Pu activity and 240Pu/239Pu and 241Pu/239Pu isotopic ratios was validated by analyzing five standard reference materials (soil, fresh water sediment, and ocean sediment). This method is characterized by its stable and high Pu recovery (90-97% for soil; 92-98% for sediment) and high decontamination factor of U (1.6 × 107), which is the highest reported for soil and sediment samples. In addition, the short analytical time of 12 h and the method detection limits, which are the lowest yet reported in literature, of 0.56 μBq g-1 (0.24 fg g-1) for 239Pu, 1.2 μBq g-1 (0.14 fg g-1) for 240Pu, and 0.34 mBq g-1 (0.09 fg g-1) for 241Pu (calculated on the basis of a 1 g soil sample) allow the rapid determination of ultratrace level Pu in soil and sediment samples.

Analysis of Technetium Species and Fractions in Natural Seaweed Using Biochemical Separation and ICP-MS Measurement.

An extremely high accumulation and retention of technetium in marine plants, especially brown seaweed, makes it a unique bioindicator of technetium. In the present work, a novel approach was developed for the speciation analysis of technetium in seaweed, wherein a series of biochemical separations was exploited to isolate different species of technetium. Inductively coupled plasma mass spectrometry (ICP-MS) was applied for the measurement of 99Tc after thorough radiochemical preconcentration and purification. The results show that the distribution of technetium species in seaweed is relatively dispersive. Besides the inorganic species of TcO4-, most of technetium (>75%) combined with organic components of seaweed such as algin, cellulose, and pigment. This investigation could provide important fundamental knowledge for studying the processes and mechanisms of 99Tc accumulation in the natural seaweed.

The use of solution nebulization ICP-MS combined with particle screening and micro-sampling for analysis of individual uranium-bearing particles

Solution nebulization inductively coupled plasma mass spectrometry (ICP-MS) was applied to the analysis of uranium isotope abundance ratios in individual particles. Particle screening was carried out before ICP-MS analysis using two different techniques: irradiation with thermal neutrons and fission track observation (so-called “fission track technique”) on the one hand and automated particle measurement (APM) in secondary ion mass spectrometry (SIMS) on the other hand. Uranium-bearing particles localized by the screening techniques were sampled individually by micro-sampling devices inside a scanning electron microscope and deposited on clean silicon wafers for subsequent chemical dissolution and ICP-MS measurement. The micro-sampling enables us to avoid polyatomic ion interferences and measure some uranium-bearing particles at the same time in isotopic analysis. Using both methods, particles from certified reference materials and a real-life sample taken at a nuclear facility were measured to evaluate the performance of the methods. Using ICP-MS combined with the fission track technique, the uranium isotope abundance ratios were successfully determined for individual particles with diameters ranging from 1.2 to 2.4 μm in a certified reference material (NBL CRM U100). The analysis of the real-life sample using ICP-MS combined with the fission track technique gave 235U/238U isotope abundance ratios between 0.0246 and 0.0376. When APM was used as the particle screening method for the real-life sample, 235U/238U isotope abundance ratios ranging from 0.0259 to 0.0432 were obtained. These values were higher than those obtained by a well-established method for particle analysis (SIMS). From these results, it can be concluded that both techniques allow selection and analysis of the uranium particles with the highest 235U abundance, which is the most important for nuclear safeguards.

Rapid Determination of Technetium-99 in Large Volume Seawater Samples Using Sequential Injection Extraction Chromatographic Separation and ICP-MS Measurement

An automated method was developed for rapid determination of (99)Tc in large volume seawater samples. The analytical procedure involves preconcentration of technetium with coprecipitation, online separation using extraction chromatography (two TEVA columns) implemented in a sequential injection setup, and measurement of (99)Tc by inductively coupled plasma mass spectrometry (ICP-MS). Chromatographic behaviors of technetium, molybdenum, and ruthenium were investigated, and the mechanism of adsorption and elution of TcO(4)(-) on a TEVA column using HNO(3) was explored. The results show that not only NO(3)(-) but also acidity (or concentration of H(+)) of the loading or eluting solution affect the adsorption and desorption of TcO(4)(-) on TEVA resin. Decontamination factors of more than 1 × 10(6) for ruthenium and 5 × 10(5) for molybdenum are achieved. Chemical yields of technetium in the overall procedure range from 60% to 75% depending on the sample volumes, and a detection limit of 7.5 mBq/m(3) (or 11.5 pg/m(3)) for 200 L of seawater was obtained. Compared with the conventional analytical procedure, the developed method significantly reduces analytical time. A batch of samples (n > 4) can be analyzed within 24 h. The method has been successfully applied for rapid and automated determination of low level (99)Tc in large volume seawater samples. The analytical results of seawater samples collected in Denmark show a good agreement with the values obtained using the conventional method.

Determination of heavy metals and rare earth elements in environmental samples by ICP-MS after solid phase preconcentration with chelating resin fibers and anion exchanger filters.

A solid phase collection/concentration method using anion exchanger filters and a small syringe packed with chelating resin fibers is adopted as a preconcentration tool for trace elements and a separation tool for matrices in aqueous samples prior to the measurement by inductively coupled plasma-mass spectrometry (ICP-MS). The effects of fiber volume, sample volume, eluent volume, and sample flow rate on metal recoveries were investigated in detail to obtain optimum pretreatment conditions. Several heavy metals (HMs) such as, V, Mn, Co, Ni, Cu, Zn, Ga, Cd, Pb, Th and U, as well as 14 rare earth elements (REEs) in sample solutions at pH 6 were quantitatively collected on the solid phase. These adsorbed elements were completely recovered by eluting with 2 ml of 1.0 M nitric acid. At pH 6, more than 99% of alkali and alkaline earth metals in sample solutions were eliminated. The proposed method was evaluated by analyzing two standard reference materials (SRM): peach leaves (NIST 1547) and pond sediment (NIES No. 2). The solid samples were decomposed by microwave-heating and pressurizing acid digestion technique, and then treated by the proposed syringe-type pretreatment method, followed by the ICP-MS measurement. The analytical results for HMs in the SRMs obtained by the present method agreed well with the certified values.

Determination of trace iron in indium phosphide wafer by on-line matrix separation and inductively coupled plasma mass spectrometry

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 (3 σ) 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).

Determination of 232Th in urine by ICP-MS for individual monitoring purposes.

Thorium is naturally occurring in various ores used for industrial purposes and has numerous applications. This paper sets out to investigate urine analysis as a suitable monitoring approach for workers potentially exposed to thorium. Due to its biokinetic behavior and its low solubility, urinary concentrations are generally very low, requiring therefore high sensitivity analytical methods. An analytical procedure has been developed for detecting 232Th concentrations of below 1 mBq L(-1) quickly and easily. Due to the long half-life (1.41 x 10(10) y) of 232Th, the potential of a procedure based on urine sample dilution and ICP-MS (inductively coupled plasma-mass spectrometry) measurement was investigated first. Two dilution factors were chosen: 100, which is more suitable for long-term measurement trials, and 20, which increases sensitivity. It has been shown that a 100-fold dilution can be used to measure concentrations of below 1 mBq L(-1), whereas a 20-fold one can be used to reach concentrations of below 0.06 mBq L(-1). Then, on the basis of the limitation of the procedure based on urine dilution, the suitable field of application for the different procedures (100-fold and 20-fold dilution and also a chemical purification followed by an ICP-MS measurement) was determined in relation to monitoring objectives.

超音波Q-スイッチ連続発振型Nd:YAGレーザーを用いた鉄鋼のレーザーアブレーションとその誘導結合プラズマ質量分析への応用

A cw Q-switched Nd : YAG laser has been applied to a laser ablation system for the direct analysis of steels by inductively coupled plasma mass spectrometry (ICP-MS). The YAG laser used produced fine particles (particles size, about 0.02μm) at relatively high ablation rate (maximum 22μg s-1) ; and that was important feature to improve sensitivity and precision.Selective vaporization of volatile elements was occurred in the ablation process, but the magnitude was low. The use of iron as an internal standard was effective to improve accuracy and precision. Good accuracy was obtained for trace elements such as B, As, Nb, Sn and so on. On the other hand, precision ranged from 5 to 10(RSD, %) for the most of elements (isotope contents, 10200 μg g-1). Detection of Si, Al and P were problematic due to molecular interferences and some contaminations in ICP-MS measurement. But the limits of other 14 elements were excellent (0.01 μg g-1 for Nd5.6 μg g-1 for Ni at the effective integrating time of 0.18 s). It was found that the laser ablation analysis without standards has enough accuracy to apply semiquantitative analysis.