Spectral and non-spectral interferences in inductively coupled plasma mass-spectrometry

Inductively coupled plasma mass spectrometry of environmental and biological samples is often hampered by spectral and non-spectral interferences. Spectral interferences, caused by the limited resolution of the quadrupole mass spectrometer, can be eliminated in a variety of ways. For their identification inspection of a signal versus carrier gas flowrate is useful. Anion exchange allows the removal of most S and Cl containing compounds, which are at the origin of the majority of spectral interferences. Matrix modification, for example the addition of ethanol and subsequent optimization of the gas flow rates in a number of cases enables the reduction of the interferences to insignificant values. Often a mathematical correction based on isotopic signal ratios can be applied. Non-spectral interferences can be divided in reversible, that is occurring while the sample is being measured, and irreversible matrix effects, that is clogging of the nebulizer and sampling orifices or deposition on the torch or in the ion lens stack. The errors associated with non-spectral interferences can be eliminated by appropriate calibration procedures, adapted sample preparation or limitation of the amount of sample delivered to nebulizer, plasma and sampling devices, for example by the application of flow injection. Applications of all the elimination procedures are described for the analysis of sea-water, estuarine water, soil and sewage extracts, percolate water, urine, serum and wine.     

Fission yield measurements by inductively coupled plasma mass-spectrometry

Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. The uncertainty of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain fissioning isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.     

A mathematical correction method for spectral interferences on selenium in inductively coupled plasma mass spectrometry

Despite the fact that Se has six isotopes, its determination in biological samples by inductively coupled plasma mass spectrometry is seriously hampered by spectral interferences. The resolution of quadrupole mass analyzers is insufficient to resolve Se(+) from molecular species having the same nominal mass. A mathematical correction method based on signal ratio measurement of (78)Se(+)/(76)Se(+) and (78)Ar(+)(2)/(76)Ar(+)(2) is described. It allows us to correct for the argon dimer interference at m/z 78 and thus to determine Se down to the 1 mug/l level. The method was applied to the determination of Se in human serum. Good agreement with the certified value was obtained.     

New method for removal of spectral interferences for beryllium assay using inductively coupled plasma atomic emission spectrometry

Beryllium (Be) has been used widely in specific areas of nuclear technology. Frequent monitoring of air and possible contaminated surfaces in U.S. Department of Energy (DOE) facilities is required to identify potential health risks and to protect U.S. DOE workers from beryllium-contaminated dust. A new method has been developed to rapidly remove spectral interferences prior to beryllium measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES) that allows lower detection limits. The ion exchange separation removes uranium (U), plutonium (Pu), thorium (Th), niobium (Nb), vanadium (V), molybdenum (Mo), zirconium (Zr), tungsten (W), iron (Fe), chromium (Cr), cerium (Ce), erbium (Er) and titanium (Ti). A stacked column consisting of Diphonix Resin and TEVA Resin reduces the levels of the spectral interferences so that low level Be measurements can be performed accurately. If necessary, an additional anion exchange separation can be used for further removal of interferences, particularly chromium. The method has been tested using spiked filters, spiked wipe samples and certified reference material (CRM) standards with high levels of interferences added. The method provides very efficient removal of spectral interferences with very good accuracy and precision for beryllium on filters or wipes. This new method offers improvements over other separation methods that have been used by removing large amounts of all the significant spectral interferences with greater simplicity and effectiveness. The effective removal of spectral interferences allows lower method detection limits (MDL) using inductively coupled atomic emission spectrometry. A vacuum box system is employed to reduce analytical time and reduce labor costs.     

Simulation of atomic spectra—II. Mutual spectral interferences of rare earth elements in the inductively coupled plasma

This article is an electronic publication in Spectrochimica Acta Electronica (SAE), the electronic section of Spectrochimica Acta B (SAB). The hardcopy text, comprising the main article and an appendix, is accompanied by a diskette with a program, data files, and a manual. The text details the purpose of the work, with emphasis on the spectroscopic aspects, and the appendix provides the essential information for accessing the diskette and using program and data. Additional tutorial guidance is provided by the manual.

The program primarily concerns the simulation of the spectra of rare earth elements (REE) as interferents in 80-pm wide spectral windows centred about the wavelengths of 26 prominent lines of Ce, La, Nd, Pr, and Sm. The program essentially covers the model described in Spectrochim. Acta 43B, 1365 (1988) and the database is identical to the experimental database published in Spectrochim. Acta 44B, 31 (1989). Accordingly, the data are for an inductively coupled plasma (ICP). The program enables the user to simulate spectra with the spectral bandwidth as an optional variable. The user may then generate spectra of both single REEs, without or with analyte, and mixtures of REEs of any composition, also without or with analyte, whereby for spectra with analyte the display includes the blank spectrum. Displays are accompanied by legends providing a set of essential numerical data. In addition, particular program options allow the generation of numerical data only, one of them being the calculation of true detection limits. This option permits it to perform, within the limited scope of the database, line selection for complex REE samples in a rational way.

The program operates, in principle, with the default values of the ICP Doppler temperature (6800 K) and “average” ICP a-parameter of the Voigt profile (0.5), but these values may be optionally modified. Similarly, the user may add new data files to the base and thus also apply the program for other purposes and outside the REE environment, such as model studies in general, and for learning or teaching, as explained in the manual on the diskette. The tutorial part of this manual provides the user not only with elementary instructions for using the program as a practical tool, but also incorporates a variety of instructive examples, including a brief “course” on spectral line profiles and spectral interferences.     

Investigation of matrix-induced interferences in mixed-gas helium-argon inductively coupled plasma mass spectrometry

The effects of various matrix constituents, Cd, Co, Pb, and synthetic ocean water, on analyte ion signal were investigated in He-Ar plasma source mass spectrometry. Analyte ion signal suppressions and enhancements were observed in the presence of varying concomitants. The method used for optimizing analyte ion lens signal determined whether suppression or enhancement was encountered. Tuning on a nitric acid standard solution results in a suppressed signal, whereas tuning on the analyte in the presence of the matrix results in signal enhancement, relative to that obtained with no concomitant present. The heavier mass lead concomitant had the greatest effect on the ion signal. Additionally, lighter analyte elements were affected to a greater extent than heavier analytes in the presence of high concomitant concentrations.     

Direct determination of 226Ra in environmental matrices using collision cell inductively coupled plasma mass-spectrometry

Direct determination of ²²⁶Ra in complex environmental matrices (biological and uranium ore samples) by collision-cell inductively coupled plasma mass-spectrometry was investigated. Possible polyatomic interferences were studied and their effects on ²²⁶Ra measurements were determined. The instrumental conditions for optimal signal-to-noise ratio for ²²⁶Ra were found. Concentrations of ²²⁶Ra in certified reference samples were measured using both external calibration and standard addition approaches. The best precision was obtained by applying standard additions. The absolute detection limit for ²²⁶Ra was 1 fg with optimal gas flow rates for the collision cell of 7 ml^.min^-1 for helium and 4 ml^.min^-1 for hydrogen.     

Non-linear spectral interferences in an inductively coupled plasma optimized for simultaneous multi-element analysis of plant and soil samples by atomic emission spectrometry

Summary The spectral interferences by Al, Ca, Fe, K, Mg and Na in the direct simultaneous determination of As, Cd, Co, Cu, Hg, Pb and Se in plant and soil samples by ICP-AES are investigated, and a non-linear relationship between the apparent analyte concentration for As, Cd, Co, Hg and Se is observed. A correction method for non-linear spectral interferences is discussed and non-linear spectral correction coefficients are calculated.     

Removal of spectral interferences and accuracy monitoring of trace cadmium in feeds by dynamic reaction cell inductively coupled plasma mass spectrometry

In the direct ICP-MS determination of Cd in feed samples, significant spectral interferences caused by high concentrations of Mo can play an important role. In the present study, Mo based oxide or hydroxide polyatomic interferences were eliminated by dynamic reaction cell (DRC) with O₂ as reaction gas. Some other oxide or hydroxide interferences (i.e. Zr and Ru) were simultaneously reduced by this technology. These potentially interfering polyatomic ions ⁹⁵Mo¹⁶O⁺, ⁹⁴Mo¹⁶OH⁺, ⁹⁴Zr¹⁶OH⁺, ⁹⁸Mo¹⁶O⁺, ⁹⁸Ru¹⁶O⁺ and ⁹⁷Mo¹⁶OH⁺ on ¹¹¹Cd⁺ and ¹¹⁴Cd⁺ were oxidized to higher oxides MoO₂⁺, MoO₃⁺, MoO₄⁺, RuO₃⁺, RuO₄⁺, MoO₂H⁺, MoO₃H⁺, ZrO₂H⁺ and ZrO₃H⁺. The rejection parameter q (RPq) of DRC and the flow rate of O₂ were optimized and set at 0.75 and 2.0 ml min^{− 1}, respectively. In addition, the residual isobaric interference of ¹¹⁴Sn on ¹¹⁴Cd was corrected using a mathematical correction equation. The limit of quantitation (LOQ) for ¹¹¹Cd or ¹¹⁴Cd was 0.8 or 1.0 ng g^{− 1} and the analysis results of NIST 1567a wheat flour and 1568a rice flour standard reference materials were in good agreement with the certified values. As the routine cadmium monitoring method in our laboratory, the proposed method was applied to the accuracy determination of 562 pig feed samples for the Monitoring of Central Meat Reserves (CMR) of China.     

A practical approach to non-spectral interferences elimination in inductively coupled plasma optical emission spectrometry

Matrix effects and practical possibilities of reducing accompanying non-spectral interferences in inductively coupled plasma optical emission spectrometry (ICP-OES) were studied for microconcentric Micromist, concentric and V-groove nebulizers (VGN) coupled with two cyclonic spray chambers of different sizes. The effect of a wide scale of interferents and mixtures thereof in the concentration range of up to 2 mass % (Na, Ca, Ba, La, urea) or up to 20 vol. % (nitric acid) on the analysis of Cd, Cu, K, Mg, Mn, Pb and Zn was investigated in terms of their analytical recovery and Mg(II) 280.27 nm/Mg(I) 285.29 nm line intensity ratio. Recoveries of ionic lines were lower than those of atomic lines (37–102 %) depending on the matrix concentration. The Mg(II)/Mg(I) ratios were found to be 12–15 and they slightly decreased as the matrix load increased. Exceptional behavior of pure La matrix, steeply lowering the recoveries and Mg(II)/Mg(I) ratios was observed. A Micromist nebulizer coupled with a small inner volume spray chamber provided the highest recoveries (94–102 %), lowest matrix effects across the matrix loads and, compared to others, the least significant dependence without worsening of the analytical characteristics (recoveries, signal background ratios and the Mg(II)/Mg(I) ratios) across the studied matrices.     

Alleviation of polyatomic ion interferences for determination of chlorine isotope ratios by inductively coupled plasma mass spectrometry

A simple variation in sample preparation and introduction allows the measurement of chlorine isotope ratios by inductively coupled plasma mass spectrometry (ICP/MS). Dissolution of the sample in D₂O rather than H₂O attenuates the major polyatomic ion ³⁶ArH⁺ and frees m/z 37 for determination of ³⁷Cl⁺. The isotope ratio ³⁵Cl/³⁷Cl in a 50 mg/L solution of Cl as LiCl is determined with a relative standard deviation of 0.21%. Sample memory is low, as the ³⁵Cl signal decays to less than 1% of its original value after ～2 min of cleanout with D_2O . The detection limit for Cl using this procedure is approximately 20 μg/L.     

Absolute spectral radiance of 27 MHz inductively coupled argon plasma background emission

The spectral radiance of the plasma continuum of a 27 MHz argon ICP has been measured for two sets of operating conditions in the wavelength range from 192 to 600 nm. At an rf forward power of 1250 W and a viewing height of 15 mm above the load coil, a maximum spectral radiance of (1.5±0.3) × 10¹² photons s⁻¹ mm⁻² sr⁻¹ nm⁻¹ was observed, at a wavelength of approximately 450 nm. At 200 nm, the spectral radiance is 60 times lower. For wavelengths below 400 nm, the absolute plasma emission spectrum is well represented by a graybody function with a temperature of 5480 K and an emissivity of 4 × 10⁻⁵.     

Interferometric measurements of spectral line widths emitted by an inductively coupled plasma

Line widths of fifteen spectral lines of ten elements introduced into an inductively coupled plasma (ICP) have been measured with a Fabry-Pcrot interferometer. Instrumental broadening is estimated by measuring the line widths emitted by hollow-cathode lamps and assuming their actual profiles as purely Gaussian with Doppler widths at 400 K. For correction of the experimental widths of lines emitted by the ICP, actual profiles of the lines are assumed to be purely Gaussian as a first approximation. The calculated actual widths range from 0.0015 to 0.0051 nm. Values of the a-paramctcr of the Voigt profile are estimated by assuming the Doppler temperature of the plasma to be 5000 K. Most of the lines emitted by the ICP have a-values in a range between 0.2 and 0.7. The fact reported previously that ICP lines suffer from less collisional broadening than lines excited in flames is supported.     

Mutual spectral interferences of rare earth elements in inductively coupled plasma atomic emission spectrometry: I. Rational line selection and correction procedure

This paper is the first part of a series of three papers dealing with mutual spectral interferences of rare earth elements (REE). The present paper reports the measurement of the partial sensitivities of all REEs at the peak wavelengths of 30 prominent lines of Ce, La, Nd, Pr, Sm, and Yb, the most abundant REEs in geological samples. These sensitivities are split into line and wing contributions and are ratioed with respect to the analyte sensitivities. The “Q-values” thus obtained, along with the numerical values of the background equivalent concentrations for the pure solvent and the relative standard deviation of the background, permit a rational selection of analysis lines for REE mixtures of whatever composition using as a criterion the “true detection limit” as proposed by Boumans and Vrakking [Spectrochim. Acta42B, 819 (1987)]. The effectiveness of this approach is illustrated with examples. The data listed are likely to be also appropriate for other spectrometers having a spectral bandwidth of approximately the same magnitude as that used in the experiments, i.e. 17 pm. Therefore the paper includes brief instructions for applying the data. The article finally demonstrates the use of the same data for multielement interference corrections.     

Inelastic collisional deactivation in plasma-related non-spectroscopic matrix interferences in inductively coupled plasma atomic emission spectrometry

Inelastic collisional deactivation of the analyte excited state is demonstrated as a dominant cause for non-spectroscopic matrix interference in inductively coupled plasma atomic emission spectrometry (ICP-AES) for commonly used plasma operating conditions in routine analysis. A mathematical simulation of the inelastic collisional model was examined. Comparison between the theoretical model and experimental results using atomic and ionic lines of the analytes Zn, Ba, Mg, Mn and Sr validates the inelastic collisional deactivation model as a dominant cause for non-spectroscopic matrix effect. Matrices evaluated were NH₄Cl, NH₄SCN, (NH₄)₂SO₄, and H₂SO₄ to represent difficult-to-ionize matrices (DIE) and NaCl and CaCl₂ to represent easy-to-ionize element matrices (EIE).