Spatial characterization of analyte emission and excitation temperature in an inductively coupled plasma

Vertical, lateral and radial profiles of analyte emission in an inductively coupled plasma have been measured using photodiode array spatial profiling spectrometers. These profiles have been measured for both neutral atom and ionic lines of several elements. Neutral atom lines can be sub-divided into two basic groups on the basis of their vertical spatial emission characteristics. One group in which the peak vertical position of emission correlates positively with normal temperature and a second group in which the peak vertical position of emission correlates negatively with normal temperature. Utilizing radially resolved emission intensities and vertical and radial profiles of neutral atom excitation temperature, the caracteristic emission patterns of both groups of neutral atom lines can be explained. Analyte ionic line spatial emission characteristics, both vertically and radially, are shown to be relatively species independent and radial emission intensity ratio maps of ionic and neutral atom lines of the same element are presented that indicate the potential importance of plasma boundary regions as regions of major non-LTE behavior.     

Interference from easily ionizable element matrices in inductively coupled plasma emission spectrometry—a spatial study

Utilizing a photodiode array based spatial profiling spectrometer an extensive spatial characterization of the effect of an excess of an easily ionizabie element (EIE) on analyte emission in the inductively coupled plasma has been carried out. Significant spatial shifts, enhancements and depressions are induced on analyte emission by the presence of an EIE and it is shown that limited fixed height measurements may be seriously misleading with respect to interpretation of the effects of ElEs. In general, the addition of excess EIE enhances emission in the lower regions of the analyte channel for both atom and ion lines and in the upper regions of the analyte channel, emission intensity is depressed for both atom and ion species. Radial emission maps (for CaI and CaII) reveal that the enhancements low in the discharge occur along the off axis boundary of the analyte channel and the plasma discharge. Higher in the discharge CaI emission is generally depressed but CaII emission undergoes a central axis depression coupled with an off axis enhancement. Overall the data suggests that low in the discharge enhancement appears to be the result of increased collisional excitation and that higher in the discharge ambipolar diffusion may exert an influence on the spatial distribution of analyte species.     

电感耦合等离子体原子发射光谱法同时测定高强度玻璃纤维粉体中9种金属元素

建立电感耦合等离子体原子发射光谱法测定高强度玻璃纤维粉体中铝、镁、钙、铁、钛、锂、铈、钠、钾9种金属元素含量的方法。采用氢氟酸、高氯酸和盐酸分两段溶解样品,分别在选定的各元素分析谱线下,采用电感耦合等离子体原子发射光谱仪测定各元素含量。9种金属元素在各自的质量浓度范围内与光谱强度成良好的线性关系,相关系数均大于0.999,检出限为8.0~17.4 μg/g。测定结果的相对标准偏差小于1.8%(n=6),加标回收率为97.6%~103.7%。该方法准确,简便,快速,适用于高强度玻璃纤维中多金属元素的同时测定。     

端视等离子体原子发射光谱法中内标法校正钠基体干扰

端视电感耦合等离子体原子发射光谱在分析过程中易电离元素引起的非光谱干扰 ,常常使分析结果产生偏差。就不同浓度Na基体对分析谱线产生的干扰进行了实验和研究 ,并用Y作为内标元素来补偿钠基体的干扰。得出在Robust条件 ,即高功率和低载气流速条件下 ,选择合适的离子线 ,并且离子线的总能量大于 10eV下 ,用内标Y 4 37.4 94nm可以很好的补偿不同Na含量的干扰。     

Temporal characterization of femtosecond laser pulses induced plasma for spectrochemical analysis of aluminum alloys

This paper reports studies on time-resolved space-integrated laser induced breakdown spectroscopy (LIBS) of plasmas produced by ultrashort laser pulses at atmospheric pressure, on aluminum alloy targets. The temporal behavior of specific ion and neutral emission lines of Al, Mg and Fe has been characterized. The results show a faster decay of continuum and spectral lines, and a shorter plasma lifetime than in the case of longer laser pulses. Spectroscopic diagnostics were used to determine the time-resolved electron density, as well as the excitation and ionization temperatures. In comparison with plasmas produced by ns laser pulses, the plasma generated by ultrashort pulses exhibits a faster thermalization. Analytical performances of fs-LIBS were also evaluated. Linear calibration curves for minor elements (Mg, Fe, Si, Mn, Cu) presented in aluminum alloys were obtained. The limits of detection are in the parts per million (ppm) range and are element-dependent.     

The vertical spatial characteristics of analyte emission in the inductively coupled plasma

Utilizing a photodiode array based spatial profiling spectrometer vertical spatial profiles of analyte emission have been measured for a large number of neutral atom and ion lines in the inductively coupled plasma. The lines can be subdivided into two basic categories. One group (called “ soft ” lines after Boumans) have spatial emission behaviour that is very dependent on power, aerosol flow and analyte excitation and ionization characteristics. The second group (called “ hard ” lines after Boumans) have spatial emission behaviour that is relatively insensitive to all of the above parameters. In all cases ion lines have hard line behaviour as do the more energetic atom lines. Under fixed ICP conditions all hard lines have their peak emission at essentially the same position in the discharge which is always higher in the discharge than that for soft lines. It is also shown that the spatial behaviour of soft lines can be directly correlated with normal temperature.     

Conversion of “Tables of Spectral-Line Intensities” for NBS copper arc into table for inductively coupled argon plasmas

This paper describes an approach used to convert the Tables of Spectral-Line Intensities for the copper arc explored by Meggers, Corliss and Scribner at the National Bureau of Standards (NBS Tables) into a table appropriate for inductively coupled plasmas (ICP). Previous work of this author was extended to determine “definitive” factors for converting the intensities listed in the NBS Tables into ICP sensitivities using the ICP detection limits of more than 800 prominent lines published by Winge, Peterson and Fassel. A computer iteration procedure was devised to find simultaneously the desired conversion factors and the true relative intensity distribution in the background spectrum of the argon ICP explored by Winge et al. This approach proved to be viable and resulted in a complete translation of the tables for the NBS copper arc into a table of ICP sensitivities, which, together with a previously described approach by this author to quantify line coincidences in terms of critical concentration ratios, formed the basis of new Line Coincidence Tables for Inductively Coupled Plasma Atomic Emission Spectrometry involving 896 prominent lines of 67 elements. The Appendix of the present work produces a list of these prominent lines arranged according to element and wavelength, along with sensitivities, detection limits, and ratios of the detection limits to the best detection limit of the element. A second list of some 200 supplementary computer predicted prominent lines is also appended.     

Qualitative and semi-quantitative analysis in ICP-AES using multivariate calibration

This paper describes a two step algorithm for qualitative and semiquantitative analysis in inductively coupled plasma—atomic emission spectroscopy (ICP-AES) including the preceding data acquisition. Sample and calibration spectra were recorded in 0.05 nm spectral windows centered about the most prominent lines of the 49 covered elements. In the first step of the analysis of an unknown sample spectrum it is decided which of these elements can be excluded from further operations because of the absence of their most prominent lines applying a multivariate criterion for peak detection. For the remaining elements quantitative analysis is performed via multivariate calibration taking into consideration the most prominent line of each element and possibly interfering lines of those elements which were not found absent during the first step. After the estimation of the element concentrations multivariate detection limits are used as criterion for the presence of an element. Results for six synthetic samples of increasing complexity prepared from standard solutions and three standard reference materials are given.     

Emission spectral characteristics of Cu,Ag, Zn,and Cd neutral atoms in a glow discharge

Detailed spectra highlighting the neutral atom emission characteristics (i.e. I lines) for Cu, Zn, Ag and Cd in a glow discharge device are presented in this study. A particular focus is the presentation of spectra that document the many high excitation energy neutral atom lines that are observed in these spectra. For Cu, several spectral lines originating from levels close to the ionization potential of copper are observed including lines from the so-called autoionizing levels which are actually just above the ionization potential for copper. Generally similar results are seen for Ag, Zn and Cd, including the observation of many high excitation energy neutral atom lines of Zn originating from the upper levels on the triplet side of the energy level diagram. The spectral data point to ion–electron recombination processes followed by stepwise de-excitation and radiative decay as a key mechanism in setting the spectral character of neutral atom emission in a glow discharge device. Unambiguous identification of spectral lines for specific transitions was facilitated by the acquisition of all spectral data utilizing a UV–visible Fourier transform spectrometer. This spectrometer provided complete and continuous coverage of the spectral region from 200 to 650 nm and allowed spectral lines to be identified with an accuracy of 1–2 pm.     

Line selection and interference correction for the analysis of tungsten alloy by inductively coupled plasma atomic emission spectrometry

A method for the analysis of tungsten alloy to determine selected elements using inductively coupled plasma atomic emission spectroscopy is described, with emphasis on line selection and spectral interference. The spectral interference coefficients were calculated for the spectral lines of selected major and trace elements. These values were used to select analytical lines and to calibrate concentrtions of the analytes. The detection limits of the elements for this method were determined and compared with those obtained by flame atomic absorption spectrometry and direct current carbon are emission spectrometry. The results indicated that the detection limits for all of the elements determined by the proposed method are significantly better than those obtained by other techniques. In this study, the analytical reliability of the proposed method was estimated by comparison of the analytical data for the two types of tungsten alloys produced by the Korean Tungsten Company with those obtained by the matrix matching method and the results indicated that the accuracy of multi-element analysis is satisfactory.     

High-Resolution continuum-source atomic absorption spectrometry in an inductively coupled plasma with photodiode array detection

Atomic absorption spectrometry (AAS) is a well established technique using flames and graphite furnaces. An inductively coupled plasma (ICP), however, is an attractive alternative atom/ion reservoir. A high-resolution continuum-source atomic absorption spectrometer with a photodiode array detector and an ICP as the atomization/ionization reservoir is described. Multi-wavelength capability permits the simultaneous determination of several elements by their atomic and/or ionic transitions. Each acquired spectrum is averaged for 10 s to improve the signal-to-noise ratios. Detection limits are calculated for 14 elements and compared with literature values.     

Inductively coupled plasma-ionic absorption spectrometry using a xenon arc lamp and an echelle monochromator

Ionic absorption spectrometry using the inductively coupled plasma (ICP) as an ionization source and a 150 W stable xenon arc lamp as a light source has been investigated. A high-resolution echelle spectrometer was used for the absorption measurement. Ionic absorption lines in the wavelength region above 320 nm showed high sensitivity and detection limits of Y, Ti, Zr, Sc, Ce and La were of the same order of magnitude as those attained by ICP atomic emission spectrometry. Linear dynamic ranges of three orders of magnitude were observed for most elements tested. Effects of the measurement conditions such as rf power, outer gas flow rate, inner gas flow rate and observation height on the transmittance of the beam through the plasma and the absorbed radiation power of the analytes are also given.     

Investigation of matrix effects in inductively coupled plasma-atomic emission spectroscopy using laser ablation and solution nebulization — effect of second ionization potential

Plasma-related non-spectroscopic matrix effects of 31 elements in inductively coupled plasma (ICP)-atomic emission spectrometry were investigated using both laser ablation and solution nebulization as sample introduction techniques. Matrix effects were studied by monitoring the excitation conditions of the plasma using the ionic to atomic spectral line intensity ratios of zinc and magnesium. A new kind of matrix interference was found in the ICP that appears to be related to matrices with elements of low second ionization potential. The matrix effects do not correlate with the first ionization potential of the element. Only those matrix elements with low second ionization potential showed severe matrix effects. Increasing the forward power of the ICP or replacing the carrier gas with a 50%/50% argon–helium mixture did not significantly reduce this matrix effect. However, using 100% helium as the carrier gas greatly reduced the extent of this matrix effect, suggesting that argon is involved in the interference mechanism. The interference mechanism may involve interactions between doubly-charged matrix ions and argon species.     

电感耦合等离子体原子发射光谱法高纯三甲基镓中的痕量杂质

对电感耦合等离子体原子发射光谱（ＩＣＰ－ＡＥＳ）法测定高纯三甲基镓（９９．９９９９Ｔ,相对于金属镓的含量）中Ｃu、Ｆe、Ｓi、Ｚn等３１种痕量杂质元素的含量进行了研究,考察了基体元素镓对杂质元素的光谱和非光谱干扰以及基体浓度对杂质元素谱线信噪比和检出限的影响在优化的实验条件下,获得了满意的结果。     

Practical implementation of survey analysis in inductively coupled plasma optical emission spectrometry

The combination of an echelle/charge coupled device detector based spectrometer with software for multicomponent analysis (MCA) allows practical implementation of survey analysis in inductively coupled plasma-optical emission spectrometry (ICP-OES). MCA requires models for the pure components. A procedure is described for how to obtain the models for 67 pure elements detectable in ICP-OES. In fact, each element is represented by two model vectors. Measurements at low analyte concentration provide the sensitivities for the prominent lines used in trace analysis, whereas weak lines and continuum emission are modelled with high concentration measurements. This modelling allows proper calibration for trace and major levels, and strongly reduces noise contributions. The model library is prepared once and a monitor solution, containing seven specific elements, is used to achieve a daily link with this once-only calibration (wavelength axis and sensitivity). To control the efficiency of atomization and ionization the Cr ii 267 nm to Cr i 357 nm ratio is used. The MCA calculations are repeated at different intensity levels in order to cover the dynamic range in intensity and, hence, concentration for all the elements present in the sample solution. Matrix-matching of the monitor solution was studied in order to overcome matrix effects owing to high acid or salt contents. Some certified reference materials were analysed. The results for most elements are found within 20% of the certified values.     

Principal component analysis of the main factors of line intensity enhancements observed in oscillating direct current plasma

Enhancement of emission line intensities by induced oscillations of direct current (DC) arc plasma with continuous aerosol sample supply was investigated using multivariate statistics. Principal component analysis (PCA) was employed to evaluate enhancements of 34 atomic spectral lines belonging to 33 elements and 35 ionic spectral lines belonging to 23 elements. Correlation and classification of the elements were done not only by a single property such as the first ionization energy, but also by considering other relevant parameters. Special attention was paid to the influence of the oxide bond strength in an attempt to clarify/predict the enhancement effect. Energies of vaporization, atomization, and excitation were also considered in the analysis. In the case of atomic lines, the best correlation between the enhancements and first ionization energies was obtained as a negative correlation, with weak consistency in grouping of elements in score plots. Conversely, in the case of ionic lines, the best correlation of the enhancements with the sum of the first ionization energies and oxide bond energies was obtained as a positive correlation, with four distinctive groups of elements. The role of the gas-phase atom-oxide bond energy in the entire enhancement effect is underlined.     

Determination of trace elements in plant materials by inductively coupled plasma optical emission spectrometry

The use of inductively coupled plasmas as spectrometric emission sources for the determination of Fe, Mn, Cu, Al, B and Zn in orchard leaves is investigated. The plasma is shown to be sufficiently sensitive for the direct determination of all of the above elements in solutions of the plant materials after a dry ashing procedure. Comparative values for the trace element concentrations by other analytical methods are given.     

Effects of sample matrix on detection limits in analytical inductively coupled plasma-Fourier transform spectrometry

The feasibility of making analytical atomic spectrometry measurements by inductively coupled plasma-Fourier transform spectrometry (ICP-FTS) is demonstrated. Analytical working curves and detection limits are presented for Al, Ni, Fe and Ca. The effects of sample matrix composition on detection limits for analytical ICP-FTS are investigated. It is shown that a multiplex disadvantage may occur in the case of a spectral bandpass encompassing stroog emission lines of a matrix element. A “worse case” example of this problem is presented. Possible approaches to overcoming the multiplex disadvantage in analytical ICP-FTS and some ideal criteria for ICP-FTS instrumentation are presented.     

Investigation of plasma-related matrix effects in inductively coupled plasma-atomic emission spectrometry caused by matrices with low second ionization potentials—identification of the secondary factor

Plasma-related matrix effects induced by a comprehensive list of matrix elements (a total of fifty-one matrices) in inductively coupled plasma-atomic emission spectrometry were investigated and used to confirm that matrix effects caused by elements with a low second ionization potential are more severe than those from matrix elements having a low first ionization potential. Although the matrix effect is correlated unambiguously with the second ionization potential of a matrix, the correlation is not monotonic, which suggests that at least one other factor is operative. Through study of a large pool of matrix elements, it becomes possible to identify another critical parameter that defines the magnitude of the matrix effect; namely the presence of low-lying energy levels in the doubly charged matrix ion. Penning ionization by Ar excited states is proposed as the dominant mechanism for both analyte ionization/excitation and matrix effects; matrices with a low second ionization potential can effectively quench the population of Ar excited states through successive Penning ionization followed by ion-electron recombination and lead to more severe matrix effects.     

Analysis of superconductor oxides YBa2Cu3O8−x by inductively coupled plasma atomic emission spectrometry and complexometric titration

The elemental composition of superconductor oxides YBa₂Cu₃O_8−x were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and complexometric titration. Samples were dissolved in dilute HCl. A sequential PU 7000 Philips inductively coupled plasma atomic emission spectrometer was used for the measurements. A comparison of the different atom and ion emission lines of yttrium, barium and copper was carried out. The effect of changes of forward radio frequency (RF) power coupled into the plasma on emission intensity of various spectral lines was studied. The RF power was changed from 0.8 to 1.2 kW. The changes in the net intensities (%) of the emission lines of Cu(I) at 324.754 nm, Cu(II) at 224.700 nm, Ba(II) at 455.403, Ba(II) at 493.409 nm, Y(II) at 371.030 nm and Y(II) at 360.073 nm were calculated. The indicator 1-(2-Pyridylazo)-2-Naphthol (PAN) and different buffers were used for the complexometric titration of Cu, Y and Ba. No statistically significant differences were found between the results of ICP-AES and chemical methods of analysis.