Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils

Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma.     

Determination of phytic acid in urine by inductively coupled plasma mass spectrometry

An ICPMS method for the determination of phytic acid in human urine based on the total phosphorus measurement of purified extracts of phytic acid is described. Pretreatment of the sample is required to avoid interference in the ICPMS detection from other phosphorus compounds accompanying phytic acid in urine such as phosphate or pyrophosphate. This treatment consists of a simple filtration of the urine sample followed by complete separation of phytic acid from the mentioned phosphorus components using an anion-exchange solid-phase extraction. Separation/recovery conditions, optimized for standards of phytic acid prepared in water and artificial urine, were successfully applied to natural urine samples, resulting in adequate accuracy and precision. Linear range (0.02-0.6 mg of phytic acid L(-)(1)) and limit of detection (5 microg L(-)(1) phytic acid) are adequate for analysis of the usual amounts of phytic acid present in urine. Phosphate, pyrophosphate, and pH of urine samples at concentrations exceeding their normal physiological ranges do not affect the determination of phytic acid. Because of the simplicity, low sample requirement, and relatively high sample throughput (10 to 6 min per sample for runs between 50 and 100 samples, respectively), the present method presents the best alternative to current methods for phytic acid determination in urine. Results also show that the method is adequate for the differentiation of levels of phytic acid excretion from patients suffering from oxalocalcic urolithiasis and healthy controls, suggesting that low phytic acid concentrations in urine lead to elevated risk of oxalocalcic urolithiasis.     

Sources of uncertainty in isotope ratio measurements by inductively coupled plasma mass spectrometry

A model is presented describing the effects of dead time and mass bias correction factor uncertainties, flicker noise, and counting statistics on isotope ratio measurement precision using inductively coupled plasma mass spectrometry (ICPMS) with a single collector. Noise spectral analysis is exploited to enable estimation of the flicker noise parameters. For the instrument used, the flicker noise component exhibited a fairly weak frequency (t) dependence (is proportional to f -0.33+/-0.12), but was directly proportional to the total number of counts, Q. As white noise, determined by counting statistics, is given by Q0.5, the isotope ratio measurement uncertainties will actually cease to improve when Q exceeds a certain threshold. This would suggest that flicker noise could become the limiting factor for the precision with which isotope ratios can be determined by ICPMS. However, under most experimental conditions, uncertainties associated with mass discrimination and dead time correction factors are decisive. For ratios up to approximately 22 (115In/113In), optimum major isotope count rates are generally below 0.3 MHz, for which precision in the mass discrimination factor is limiting. The model derived could be used as a starting point for determining optimum conditions and understanding the limitations of single-collector ICPMS for precise isotope ratio measurements.     

Water analysis by inductively coupled plasma mass spectrometry

The major problems in the analysis of various natural and potable waters by the method of inductively coupled plasma mass spectrometry (sampling, matrix effects, and spectral interferences) are studied; recommendations for addressing them are given. New data on the use of robust conditions for spectrometer settings to increase its tolerance to matrix effects are considered. The advantages of combination of mass spectrometry with the simpler atomic emission method, which allows expanding the range of determined elements and increasing the reliability of the analysis, are discussed.     

Determination of mercury in coal by isotope dilution cold-vapor generation inductively coupled plasma mass spectrometry

A method based on isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has been developed for high-accuracy determinations of mercury in bituminous and sub-bituminous coals. A closed-system digestion process employing a Carius tube is used to completely oxidize the coal matrix and chemically equilibrate the mercury in the sample with a 201Hg isotopic spike. The digestates are diluted with high-purity quartz-distilled water, and the mercury is released as a vapor by reduction with tin(II) chloride. Measurements of 201Hg/202Hg isotope ratios are made using a quadrupole ICPMS system in time-resolved analysis mode. The new method has some significant advantages over existing methods. The instrument detection limit is less than 1 pg/mL. The average blank (n = 17) is 30 pg, which is roughly 1 order of magnitude lower than the equivalent microwave digestion procedure. The detection limit in coal is blank limited and is approximately 40 pg/g. Memory effects are very low. The relative reproducibility of the analytical measurements is approximately 0.5% for mercury concentrations in the range 10-150 ng/g. The method has been used to measure mercury concentrations in six coal reference materials, SRM 1632b (77.4 ng/g), SRM 1632c (94.3 ng/g), BCR 40 (433.2 ng/g), BCR 180 (125.0 ng/g), BCR 181 (135.8 ng/g), and SARM 20 (252.6 ng/g), as well as a coal fly ash, SRM 1633b (143.1 ng/g). The method is equally applicable to other types of fossil fuels including both crude and refined oils.     

Precise determination of element/calcium ratios in calcareous samples using sector field inductively coupled plasma mass spectrometry

A new method was developed for rapid and precise simultaneous determination of Mg/Ca, Sr/Ca, Mn/Ca, Cd/Ca, Ba/Ca and U/Ca ratios in foraminiferal shells using sector field inductively coupled plasma mass spectrometry (ICPMS). Element/calcium ratios were determined directly from intensity ratios using external, matrix-matched standard to correct for instrumental mass discrimination. Because of large differences in the abundance of chemical constituents of the foraminiferal shell, major elemental ratios were determined in analog mode (using (24)Mg, (43)Ca, (44)Ca, (55)Mn, and (88)Sr) whereas trace elemental ratios were determined in pulse-counting mode (using (111)Cd, (138)Ba, (238)U, and the low-abundance (46)Ca isotope). Matrix-induced variations in mass discrimination over a calcium concentration range of 2.0-24.5 mM were observed only for Mg/Ca and Cd/Ca ratios. However, these effects are negligible if the samples and standard calcium concentration are within a factor of 2-3. Multiratio method reproducibility was better than previously reported for other ICPMS methods yielding precision (1σ) of Sr/Ca = 0.45%; Mg/Ca = 0.45%, Mn/Ca = 0.8%, Cd/Ca = 1.7%, Ba/Ca = 0.7%, and U/Ca = 1.4% for foraminifera samples as small as 25 μg. Using this approach for a single-ratio analysis, Sr/Ca ratios were determined with precision of 0.06% (1σ) on carbonate samples as small as a single foraminifera shell (<10 μg). The new method is more sensitive, more precise, and simpler to use than previously available ICPMS techniques. It provides an efficient tool for simultaneous determination of several elemental ratios of paleoceanographic interest in a single foraminiferal sample, thereby reducing overall sample size requirement and analysis time.     

Speciation and identification of organoselenium metabolites in human urine using inductively coupled plasma mass spectrometry and tandem mass spectrometry

A method for speciation and identification of organoselenium metabolites found in human urine samples using high performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS) and tandem mass spectrometry (MS/MS) is described. Reversed-phase chromatographic separation was used for sample fractionation with the ICP-MS functioning as an element-selective detector, and six distinct selenium-containing species were detected in a human urine sample. Fractions were then collected and analyzed using a triple quadrupole mass spectrometer with electrospray ionization and collision-induced dissociation to obtain structural information. The first two fractions were identified specifically as selenomethionine and selenocystamine, estimated to be present at approximately 11 and 40 ppb, respectively. To the best of our knowledge, this is the first time these two metabolites have been positively identified in human urine.     

Diode laser thermal vaporization inductively coupled plasma mass spectrometry

An approach of sample introduction for inductively coupled mass spectrometry (ICPMS), diode laser thermal vaporization (DLTV) is described. The method allows quantitative determination of metals in submicroliter volumes of liquid samples. Laser power is sufficient to induce pyrolysis of a suitable substrate with the deposited sample leading to aerosol generation. Unlike existing sample introduction systems based on laser ablation, it uses a NIR diode laser rather than an expensive high-energy pulsed laser. For certain elements, this sample introduction technique may serve as an alternative to solution analysis with conventional nebulizers. Using a prearranged calibration set, DLTV ICPMS provides rapid and reproducible sample analysis (RSD ~ 10%). Sample preparation is fast and simple, and the prepared samples can easily be archived and transported. The limits of detection for Co, Ni, Zn, Mo, Cd, Sn, and Pb deposited on the preprinted paper were found to be in the range of 0.4-30 pg. The method was characterized, optimized, and applied to the determination of Co in a drug preparation, Pb in whole blood, and Sn in food samples without any sample pretreatment.     

Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry

The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible.     

A high-efficiency cross-flow micronebulizer for inductively coupled plasma mass spectrometry

A pneumatically driven, high-efficiency cross-flow micronebulizer (HECFMN) is introduced for inductively coupled plasma (ICP) spectrometries. The HECFMN uses a smaller nozzle orifice for nebulizer gas (75 microm in diameter) and a replaceable and adjustable fused-silica capillary for sample uptake. The HECFMN is optimally operated over a wide range of sample uptake rate (5-120 microL/min) at a rf power of 1100 W and nebulizer gas flow rates of 0.8-1.0 L/min when a 50 microm i.d. by 150 microm o.d. capillary is used. The aerosol quality is qualitatively examined in a simple manner, and the transport efficiencies are determined by direct filter collection. Compared with conventional cross-flow nebulizers (CFNs), the HECFMN produces much smaller and more uniform droplets and thus provides much higher analyte transport efficiencies (generally 24-95%) at the sample uptake rates of 5-100 microL/min. Several analytical performance indexes are acquired using an Ar ICPMS system. The sensitivities and detection limits measured with the HECFMN at 50 microL/min sample uptake rate are comparable to or improved over those obtained with a conventional CFN consuming 1 mL/min sample, and the precisions with the HECFMN (typically 1.1-1.7% RSDs) are slightly better than those with the CFN (1.6-2.3% RSDs). The ratios of refractory oxide ion-to-singly charged ion (CeO+/Ce+) are typically in the range from 0.7 to 3.3% for the sample uptake rates of 5-100 microL/min. The free aspiration rate of the HECFMN is 8.9 microL/min for distilled deionized water at the nebulizer gas flow rate of 1.0 L/min without any effect of pressure. The features of the HECFMN suggest good potential for HECFMN use in interfacing ICPMS with capillary electrophoresis and microcolumn high-performance liquid chromatography.     

微波辅助萃取-电感耦合等离子体质谱法检测食品中的硼砂

建立了一种应用微波辅助萃取-电感耦合等离子体质谱法检测食品中的硼砂的方法。以0.1 mol/L氨水来消除硼的记忆效应。硼含量在0～2.0μg/mL范围内线性关系良好,R=1.0000。硼砂检测限为2.0 ng/mL(σ=3),RSD小于5%,方法回收率为95.2%～103.4%。该法与GB/T21918-2008中的三种检测方法相比,具有操作简单、快速、试剂污染少的特点。可作为食品中硼砂含量的检测方法之一。     

Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry

An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.     

Analysis of high-purity materials by inductively coupled plasma mass spectrometry (Review)

A review of the works dedicated to the application of the method of inductively coupled plasma mass spectrometry (ICP-MS) to the analysis of high-purity materials (semiconductors, metals, and their oxides) and published after 2004 is presented. The limitations of this method in the analysis of such objects are discussed. Advantages and disadvantages are demonstrated for three principal ways of the application of the ICP-MS method to the analysis of high-purity materials: direct analysis of a solid sample (laser ablation and injection of a sample in the form of a suspension); preliminary dissolution of an analyte sample; utilization of the approach separating analytes and matrix.     

Determination of methionine and selenomethionine in selenium-enriched yeast by species-specific isotope dilution with liquid chromatography-mass spectrometry and inductively coupled plasma mass spectrometry detection

Selenomethionine (SeMet) and methionine (Met), liberated by acid hydrolysis of selenium-enriched yeast, were quantified by liquid chromatography-mass spectrometry (LC/MS) using standard additions calibrations as well as isotope dilution (ID) based on species-specific (13)C-enriched spikes. LC inductively coupled plasma mass spectrometry (ICPMS) was also employed for the quantification of SeMet, and (74)Se-enriched SeMet was used for ID calibration. The results were evaluated to ascertain the feasibility of using these methods in a campaign to certify selenized yeast. Good agreement was found between the methods, which, when averaged, gave concentrations of 5482.2 +/- 101 and 3256.9 +/- 217.4 microg/g for Met and SeMet, respectively. This corresponds to a 1.68:1 Met-to-SeMet ratio in the yeast. Quantification by ID LC/MS and LC ICPMS yields the most precise sets of results with relative standard deviations in the range 0.5-1.3% (n = 6). A total selenium concentration of 2064.6 +/- 45.4 microg/g was obtained for this yeast material. The extraction efficiency and a mass balance budget were determined. Acid hydrolysis liberated 81.0% of the total selenium present. SeMet comprised 79.0% of the extracted selenium and 63.9% of the total selenium present in the yeast.     

Determination of thorium and uranium in ultrapure lead by inductively coupled plasma mass spectrometry

A method for the determination of U and Th at sub-ppt levels in high-purity Pb samples using extraction chromatography with ICPMS detection is described. Following acid digestion, uranium and thorium are separated from the lead matrix using UTEVA resin. Sorption and elution procedures were optimized, the potential reusability of the chromatographic resin was evaluated, and a performance comparison between prepacked and freshly prepared UTEVA column was made. Uranium could be eluted with 0.025 M HCl and Th then recovered using 0.5% oxalic acid. Recovery yields for U exceed 80% whereas those for Th were typically 60%. Procedural detection limits of 0.5 and 1.5 pg g(-)(1) were obtained for U and Th, respectively. For purposes of comparison, GD-MS analysis of samples was also performed, yielding results consistent with those generated by ICPMS but with inferior detection power.     

电感耦合等离子质谱法(ICP-MS)测定植物中的微量稀土元素

本文介绍一种新的有关植物中的微量稀土元素的分析方法。3个品种的土生植物(杉木、竹和茶树)中的微量镧系元素经过萃取与反萃取分离富集后,我们采用电感耦合等离子质谱仪成功地进行测定。本文详细地研究了各种条件对测定结果的影响。利用本方法测定植物中的微量稀土元素,6次测定结果的相对标准偏差低于5％。由于没有稀土元素的植物标准试样,为了检验本方法的准确度,我们也用同位素稀释法测定茶树中的稀土元素。两种方法所得到的结果十分一致,证明用本方法所得的结果是正确的。     

电感耦合等离子体质谱法测定饮用水中微量元素

采用电感耦合等离子体质谱法快速测定饮用水中的微量元素 ,样品处理简便 ,检出限低 ,重现性好 ,分析速度快。方法检出限为 (0 0 0 7～ 0 911) μg L ,精密度达到 0 73%～ 4 87%。     

Fe isotope variations in natural materials measured using high mass resolution multiple collector ICPMS

We present the first measurements of Fe isotope variations in chemically purified natural samples using high mass resolution multiple-collector inductively coupled plasma source mass spectrometry (MC-ICPMS). High mass resolution allows polyatomic interferences at Fe masses to be resolved (especially, (40)Ar(14)N(+), (40)Ar(16)O(+), and (40)Ar(16)OH(+)). Simultaneous detection of Fe isotope ion beams using multiple Faraday collectors facilitates high-precision isotope ratio measurements. Fe in basalt and paleosol samples was extracted and purified using a simple, single-stage anion chemistry procedure. A Cu "element spike" was used as an internal standard to correct for variations in mass bias. Using this procedure, we obtained data with an external precision of 0.03-0.11 per thousand and 0.04-0.15 per thousand for delta(56/54)Fe and delta(57/54)Fe, respectively (2sigma). Use of Cu was necessary for such reproducibility, presumably because of subtle effects of residual sample matrix on mass bias. These findings demonstrate the utility of high-resolution MC-ICPMS for high-precision Fe isotope analysis in geologic and other natural materials. They also highlight the importance of internal monitoring of mass bias, particularly when using routine methods for Fe extraction and purification.