Isotopic determination of selenium in biological materials with inductively coupled plasma mass spectrometry

A method for the isotopic determination of selenium in biological matrices is described. The method is based on hydride generation inductively coupled plasma mass spectrometry (ICP-MS). The development is specifically related to the requirements of stable isotope tracer studies in human subjects. The method is based on isotope dilution using 82Se as the in vitro spike and can quantify the 74Se and 77Se contents of samples. It involves wet oxidation (HNO3 - H2O2 or HNO3 - HClO4) of the 82Se-spiked matrix, reduction to selenite by boiling with HCl followed by measurement of the isotope ratios (82Se/77Se and 74Se/77Se) in the gas stream (H2Se) generated from on-line reduction of the sample selenite with NaBH4. Compared with the isotopic signal resulting from a selenite solution containing 5 ng ml-1 of Se, the total sample blank contributions at m/z = 74, 77 and 82 were less than 5% of the respective isotope signal. Worst-case absolute detection limits were 0.2-0.9 ng of Se, depending on the isotope used. Ion beam intensity ratios were measured with an over-all precision [relative standard deviation (RSD)] of 1% for both isotope pairs. Measured ratios (MRa/b) were stable during a given day's operation within the expected precision of the measurements but varied for different days. The magnitude of MRa/b was generally independent of the nature of the matrix. Highly linear relationships were found between ion beam intensity ratios (MRa/b) and the corresponding true isotope ratios for calibration solutions whose isotope ratios had been altered by as much as one order of magnitude.(ABSTRACT TRUNCATED AT 250 WORDS)     

Carbon-related matrix effects in inductively coupled plasma atomic emission spectrometry

In Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES), it has been observed that the emission intensity of some atomic lines is enhanced or depressed by the presence of carbon in the matrix. The goal of this work was to investigate the origin and magnitude of the carbon-related matrix effects in ICP-AES. To this end, the influence of the carbon concentration and source (i.e. glycerol, citric acid and potassium hydrogen phthalate), the experimental conditions and sample introduction system on the aerosol characteristics and transport, plasma excitation conditions and the emission intensity of several atomic and ionic lines of a total of 15 elements has been studied. Results indicate that carbon related matrix effects do not depend on the carbon source and they become more severe when the amount of carbon loaded into the plasma increases, i.e., when using: (i) carbon concentrations higher than 5 g L^− 1; (ii) high sample uptake rates; and (iii) efficient sample introduction systems. Thus, when introducing carbon into the plasma, the emission intensity of atomic lines with excitation energies below 6 eV is depressed (up to 15%) whereas the emission intensity of atomic lines of higher excitation energies (i.e. As and Se) are enhanced (up to 30%). The emission intensity of the ionic lines is not affected by the presence of carbon. The origin of the carbon-related interferences on the emission intensity of atomic lines is related to changes in the line excitation mechanism since the carbon containing solutions show the same aerosol characteristics and transport efficiencies as the corresponding aqueous solutions. Based on the previous findings, a calibration approach for the accurate determination of Se in a Se-enriched yeast certified material (SELM-1) has been proposed.     

Analysis of molybdenum oxide by inductively coupled plasma atomic emission and mass spectrometry

Procedures for the analysis of molybdenum oxide by of inductively coupled plasma atomic emission spectroscopy (ICP-AES) and mass spectrometry (ICP-MS) are proposed on the basis of preliminary extraction separation of molybdenum from impurity elements. To separate 39 impurity elements (Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, Cr, Mn, Fe, Co, Ni, Zn, Ga, Rb, Sr, Y, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Pb, Bi, Th, and U), the extraction of molybdenum from hydrochloric acid solutions using 5-n-pentylthio-8-hydroxyquinoline was used. The capacities of both methods ICP-AES and ICP-MS in the analysis of molybdenum oxide analysis were examined without the removal of the matrix and after the extraction separation of molybdenum.     

Determination of aluminum and silicon in biological materials by inductively coupled plasma atomic emission spectrometry with electrothermal vaporization

An atomic emission spectrometric method is described for the determination of trace elements in microvolume samples especially of biological materials. Based upon the arrangement of a commercial electrothermal vaporizer and a 40-MHz inductively coupled plasma, the direct determination of aluminum and silicon in human body fluids such as urine and serum and aluminum in hemodialysis solution is performed. The instrumental system involves vaporizing the sample from a modified graphite electrode followed by atomization and excitation of the vapors in the ICP discharge. Compromise experimental conditions are reported and calibration functions compared. Limits of detection in 5-μl samples were 8 pg Al and 2.5 ng Si, and after preconcentration of Al with a poly(acrylamidoxime) resin, the detection limit was 1 pg Al. Recovery of 5 μg $\text{Si}\text{ml}$ and 10 ng $\text{Al}\text{ml}$ from aqueous and synthetic standards was 80–85% and 96–103%, respectively.     

Analysis of biological reference materials, prepared by microwave dissolution, using inductively coupled plasma mass spectrometry

A procedure has been developed for the analysis of biological materials by inductively coupled plasma mass spectrometry (ICP-MS). Fast, efficient and complete sample digestion is achieved by a combined microwave-nitric acid/open beaker-nitric acid-hydrogen peroxide procedure. The ICP-MS analysis is performed with an on-line five-element internal standard to correct for matrix and instrumental drift effects. Results are presented for 24 elements in three biological reference materials (National Institute of Standards and Technology Standard Reference Materials 5277a Liver and 1566 Oyster and International Atomic Energy Agency Certified Reference Material H4 Animal Muscle). For all elements significantly above the detection limit and reagent blank concentrations, good agreement exists between ICP-MS and certified values.     

Particle sample introduction system for inductively coupled plasma–atomic emission spectrometry

Development and characterization of a new, relatively inexpensive, computer-controlled, particle sample introduction (PSI) system for programmable delivery of small amounts of diluted powdered samples into an inductively coupled plasma (ICP) and measurement by atomic emission spectrometry (AES) is described. The PSI was developed for use with non-hygroscopic particles, in particular those with a particle weight in the ng range (i.e., with a diameter in low μm-range) and for solids that can be converted to a powder (i.e., a collection of particles). In this first report on PSI–ICP–AES, linearity of calibration curves and plasma loading concerns were addressed using three modes of operation. In the first mode, the PSI operated similar to a nebulizer and it delivered to the plasma for a period of 5–10 s a relatively constant amount of particles diluted with graphite. In the second mode, the PSI delivered to the plasma a small “puff” of a diluted sample, thus generating a transient, time-domain signal with duration of about a second. In the third mode, an even smaller “puff” was delivered to the plasma and, using high-speed data acquisition (in the kHz range), time-resolved emission signals from individual, μm-diameter and ng-weight particles were observed. Thus, the PSI can also be thought of as a nano-particle (i.e., ng rather than nm) sample introduction system. Similarly, the high-speed, wide-bandwidth single-channel time-resolved data acquisition mode enabled the determination of particle-size distribution. In addition, a dual-channel (or dual-element) mode enabled homogeneity studies on a per-individual-particle basis. In all modes, linear calibration curves were obtained (provided that plasma loading was avoided). Per-cent relative standard deviation ranged between 3.1% and 4.2% for Ni in certified reference materials but was as high as 50% for heterogeneous soil samples. Tungsten emission signals from refractory tungsten carbide powders were enhanced using mixed gases and by modifying the chemical environment of the ICP using SF₆. Furthermore, when coupled with high-speed data acquisition, PSI brought unique capabilities to ICP–AES for homogeneity studies from individual ng-weight particles and for the determination of particle size distributions. Overall, it was concluded that PSI is an attractive alternative to powder sample introduction systems described in the literature.     

Preconcentration of platinum group metals on modified silicagel and their determination by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry in airborne particulates

Modified silicagel (C18) was studied for separation and preconcentration of platinum group metals (Ru, Rh, Pd, Os, Ir and Pt) as ion associates of their chlorocomplexes with cation of onium salt N(1-carbaethoxypentadecyl)-trimethyl ammonium bromide. Sample containing HCl and the onium salt was pumped through the column. After elution with ethanol the eluate was evaporated in the presence of HCl. Resulting aqueous solutions were analysed with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Recovery values of 1-20 mug Pt and Pd from 50 ml of synthetic pure solution were 100+/-3 and 100+/-1%, respectively, however, they diminished with increasing sample volume and in the presence of the real sample matrix or nitrate ions. Samples of engine soot (NIES No. 8), decomposed by low pressure oxygen high-frequency plasma, and airborne particulates from dust filters of meteorological stations, leached with HNO(3) and H(2)O(2), were analysed. A reasonable agreement was found between ICP-MS and ICP-AES results for airborne dust samples and the values comparable with those in literature were determined in NIES No. 8.     

Dissolution of Al-Fe materials and analysis by inductively coupled plasma – atomic emission spectrometry

A technique was developed for the dissolution of Al-Fe materials containing difficult to dissolve Al₂O₃. The developed procedure uses HCl and HNO₃ for initial sample attack followed by digestion with a mixture of H₃PO₄ and H₂SO₄ at 200 °C. This procedure was employe to dissolve Al-Fe material samples before the determination of Al and Fe. Minor and trace elements (B, Cr, Cu, Mo, Si, Zr) were determined after dissolution in HCl and HNO₃. Results of a round robin study verified the procedure accuracy. The developed methods have the required accuracy and precision to be used as a quality control procedure for Al-Fe materials analysis. Received: 9 February 1998 / Revised: 1 April 1998 / Accepted: 4 April 1998     

Dissolution of Al-Fe materials and analysis by inductively coupled plasma – atomic emission spectrometry

A technique was developed for the dissolution of Al-Fe materials containing difficult to dissolve Al₂O₃. The developed procedure uses HCl and HNO₃ for initial sample attack followed by digestion with a mixture of H₃PO₄ and H₂SO₄ at 200?°C. This procedure was employe to dissolve Al-Fe material samples before the determination of Al and Fe. Minor and trace elements (B, Cr, Cu, Mo, Si, Zr) were determined after dissolution in HCl and HNO₃. Results of a round robin study verified the procedure accuracy. The developed methods have the required accuracy and precision to be used as a quality control procedure for Al-Fe materials analysis.     

Spectral interferences in the determination of trace elements in environmental materials by inductively coupled plasma atomic emission spectrometry

This paper deals with spectral interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES) encountered with environmental materials. These samples normally contain high concentrations of aluminium, calcium, magnesium, iron, titanium, potassium and sodium. The investigations cover: (a) spectral data for Al, Ca, Mg, Fe, Ti, K and Na as interferents for 200 pm wide windows centred (±100 pm) around the prominent lines of As, B, Ba, Be, Cd, Cr, Cu, Hg, Mn, P, Pb, Sb, Se, Sn, Tl, U and Zn; (b) a data base of Q-values for line interference [Q_Ij(λ_a)] and Q-values for wing background interference [Q_Wj(Δλ_a)] for two values of the excitation temperature 6200 K and 7200 K. The lines free or negligibly influenced by line interference were selected for analyte determination. Q-values were used for calculation of correction factors under a spectral line without the measurement of a reference blank at the wavelength of the prominent analysis lines. The accuracy of ICP-AES with the Q-concept as a basic methodology is checked by the analysis of a certified reference material IAEA/Sediment SD-N-1/2/. The precision of the method is characterised by an RSD of 0.6–1.7%. Extraction of trace elements soluble in aqua regia was used as a decomposition method. This article is an electronic publication in Spectrochimica Acta Electronica (SAE), a section of Spectrochimica Acta, Part B (SAB). The hardcopy text is accompanied by an electronic archive, stored on the SAE homepage at http://www.elsevier.nl/locate/sabe. The archive contains the tabular material of this article in electronic form.     

Microwave desolvation for acid sample introduction in inductively coupled plasma atomic emission spectrometry

This study deals with the behaviour of a microwave desolvation system (MWDS) with acid solutions in inductively coupled plasma atomic emission spectrometry. Hydrochloric, nitric, sulphuric and perchloric acids at different concentrations (up to 0.6 mol l⁻¹) have been tested. Sample uptake rate (Q_l) was also varied. The parameters evaluated for each variable were analyte and solvent transport rates and emission intensity. The combination of low acid concentrations (0.05–0.1 mol l⁻¹) and low liquid flows (0.4 ml min⁻¹) leads to the highest analyte transport rate and emission signal and to the lowest solvent transport rate. For Q_l higher than 1.9 ml min⁻¹, the use of an impact bead is advisable. Among the acids tested, sulphuric and perchloric acids give rise to higher emission intensities than hydrochloric acid and nitric acid. Nonetheless, the limits of detection (LODs) obtained with the MWDS are about the same magnitude irrespective of the solution employed. The LODs reached when using the MWDS are similar to those obtained with a desolvation system based on infrared heating of the aerosol.     

Semi-automatic determination of tin in marine materials by continuous flow hydride generation inductively coupled plasma atomic emission spectrometry

 A semi-automated continuous flow hydride generation system with inductively coupled plasma atomic emission spectrometry (ICP-AES) was used for the determination of tin in marine materials. The effects of acids (H₂SO₄ and HCl) were studied. The analytical parameters were thoroughly investigated. Under optimized conditions, the detection limit is 0.4 ng/ml. Interferences from transition elements were investigated and seven masking reagents were tested. L-cysteine hydrochloride monohydrate (1%) was used to mask the interferences from foreign ions. Finally, the accuracy, checked with a marine standard reference material obtained from the National Research Council (NRC), was within the certified value. Received: 23 April 1996/Revised: 8 July 1996/Accepted: 15 July 1996     

Direct determination of major elements in solid plant materials by electrothermal vaporization inductively coupled plasma atomic emission spectrometry

The present work demonstrates the capability of electrothermal vaporization (ETV) to become an important tool of solid sample introduction in ICP-AES for plant sample analysis. Direct determination of Al, Ca, Fe, K, Mg, Mn, Na and Zn was investigated in powdered plant samples. Obtaining good results for major elements in plant samples was governed by some special operating conditions. The sensitivity of the method necessitated the use of ICP in radial view configuration. The behavior of elements during vaporization was studied between 500 and 2600 °C. External calibration was carried out using solid external (cellulose) spiked with aqueous standard solutions. However, performances of the analytical method were found dependent of argon flow rates. Analytical accuracy of the method was tested in three reference materials. Analytical results agreed with certified values when cellulose was used in calibration. However, K could not be determined because of excessive sensitivity. Without cellulose, it was found that Fe results were underestimated and Zn results overestimated. Relative standard deviations varied from 3 to 23%. Limits of detection varied from 1 to 80 ng g⁻¹ from one element to the other for a typical mass sample of 2 mg.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Matrix-induced shift effects in axially viewed inductively coupled plasma atomic emission spectrometry

In order to study matrix effects and efficiency of internal standardization with an axially-viewed ICP-AES system, a large number of elements with atomic lines in the 2.9–7.8-eV excitation energy range and ionic lines in the 7.7–16.5-eV energy sum range were selected and matrix effects were evaluated using a multichannel detector having a wavelength coverage in the range 167–785 nm. Na and Ca were selected as interferent elements at a concentration of up to 10 g l⁻¹, along with nitric acid, up to a concentration of 20% (v/v). Several operating conditions were used, ranging from robust conditions (1500 W, 0.65 l min⁻¹ for the carrier gas) to non-robust conditions (800 W, 1.2 l min⁻¹). Under robust conditions, a rather flat, depressive effect was observed for ionic lines and atomic lines. This depressive effect was mainly assigned to the aerosol transport and filtering phenomena and was element or acid concentration-dependent. Within this depressive effect, some small departures from the flat effect were observed. However, these small effects exhibited the same patterns over the interferent element concentration range of 1–10 g l⁻¹, i.e. these effects were shifted as a function of the interferent concentration rather than multiplied. A consequence is that internal standardization to compensate for matrix effects on ionic lines was found to be more efficient when based on additive (i.e. shift) effects rather than on multiplicative (i.e. proportional) effects. Under non-robust conditions, signal compensation was found to be inefficient.     

ICP-AES法测定方铅矿中多元素的方法研究

采用电感耦合等离子体原子发射光谱法(ICP-AES)进行方铅矿中多元素同时测定.通过对方铅矿样品化学处理试验建立了HCl-NH4Cl-HNO3的溶矿体系.本体系采用基体匹配、背景系数和元素干扰系数校正及元素内标法确定了最佳综合实验测试条件.本实验建立的ICP-AES法同时测定方铅矿中镉、钴、铜、铁、铟、铅、锌7种元素的方法,本方法测量相对误差RE (n=8)为1.50%～7.50%,相对标准偏差RSD (n=8)为1.7%～5.7%.经国家一级标准物质GBW 07269分析验证可以满足方铅矿单矿物样品的分析要求.     

Simultaneous determination of the constituents in Al-Ge-Si alloys by inductively coupled plasma atomic emission spectrometry

An accurate method for determination of the constituents Ge, Si, In and Mg in Al–Ge–Si based compact alloys and foil materials by ICP atomic emission spectrometry is developed. The material samples were dissolved in nitric acid–hydrofluoric acid. Optimum parameters for the simultaneous measurement of the constituent elements are worked out. To compensate the time determined sensitivity fluctuations the analytical signal was corrected by a special procedure of external standardization.     

Simultaneous determination of the constituents in Al-Ge-Si alloys by inductively coupled plasma atomic emission spectrometry

An accurate method for determination of the constituents Ge, Si, In and Mg in Al-Ge-Si based compact alloys and foil materials by ICP atomic emission spectrometry is developed. The material samples were dissolved in nitric acid-hydrofluoric acid. Optimum parameters for the simultaneous measurement of the constituent elements are worked out. To compensate the time determined sensitivity fluctuations the analytical signal was corrected by a special procedure of external standardization.     

Plasma behavior during electrothermal vaporization sample introduction in inductively coupled plasma atomic emission spectrometry

Electrothermal vaporization (ETV) sample introduction in inductively coupled plasma atomic emission spectrometry suffers from severe matrix effects. In the present study, the differences between wet and dry plasma conditions are studied. In addition, the influence of the sample composition was investigated. An inductively coupled plasma optical emission spectrometer, with detection based on charge transfer, allowed the simultaneous measurement of ionic and atomic emission line intensities during the transient signal. Mg and Cr were the test elements. The ion-to-atom line ratio increases at higher power settings, but the changes were larger when a nebulizer was used for sample introduction than with ETV sample introduction. The decrease of ion-to-atom line ratios at increasing observation height was more pronounced when ETV was used, due to the absence of water vapor. The gas flow rate showed a stronger influence for nebulization than for ETV. In the presence of a calcium matrix, lower ion-to-atom line ratios were observed, but the ratio did not change significantly within the transient emission signal. Similar line ratios were observed for different amounts of calcium matrix. The values of ion-to-atom line ratios for Mg and Cr indicate that the plasma ionization and thermal characteristics are not modified due to the presence of the calcium matrix.     

Tandem on-line continuous separation and determination of arsenic by inductively coupled plasma atomic emission spectrometry

The principle of tandem on-line continuous separation techniques as an alternative means of introducing samples into plasmas was applied to the development of a sensitive, selective and convenient method for the determination of arsenic by inductively coupled plasma atomic emission spectrometry (ICP-AES). Arsenic is continuously extracted as AsI₃ into xylene from the sample dissolved in 0.1 M potassium iodide solution in 7.2 M hydrochloric acid. The xylene phase (containing the analyte) is continuously mixed on-line with NaBH₄ in dimethylformamide and acetic acid solutions. Arsine is thus continuously generated directly from the organic phase and is separated in a gas—liquid separation device which prevents most of the xylene phase vapour from reaching the ICP. The system was optimized for the continuous extraction of AsI₃, the direct generation of arsine from xylene and the final ICP determination of arsenic. Finally, the tandem on-line continuous separation ICP detection system was applied to the determination of arsenic in real samples (white metal, cast iron, cupro-nickel and orchard leaves standard materials). Very good agreement between the experimental results and the certified values was obtained.