Comparison of various calibration techniques for the direct spectroscopical analysis of SiC powders

Techniques for the direct analysis of powdered advanced ceramics provide an advantageous alternative to methods using wet digestion in sample preparation. The direct spectrochemical methods based on electrothermal vaporization (ETV-ICP-OES, solid-ETV-AAS, etc.) show a great similarity to the classical method of d. c. arc excitation. The calibration procedure is the major difficulty of all techniques applied for direct solid sample analysis, as there is a lack of suitable reference materials of ceramics. Consequently, it was necessary to verify various possibilities of preparation and application of model calibration samples. The results of such a calibration are compared with those using within-laboratory standards.     

Comparison of various calibration techniques for the direct spectroscopical analysis of SiC powders

Techniques for the direct analysis of powdered advanced ceramics provide an advantageous alternative to methods using wet digestion in sample preparation. The direct spectrochemical methods based on electrothermal vaporization (ETV-ICP-OES, solid-ETV-AAS, etc.) show a great similarity to the classical method of d. c. arc excitation. The calibration procedure is the major difficulty of all techniques applied for direct solid sample analysis, as there is a lack of suitable reference materials of ceramics. Consequently, it was necessary to verify various possibilities of preparation and application of model calibration samples. The results of such a calibration are compared with those using within-laboratory standards.     

Direct solid sample analysis of SiC-powders by DC glow discharge and DC-ARC emission spectroscopy

Glow discharge atomic emission spectroscopy (GD-OES) and the classical spectrographic method with a dc arc source (DC-ARC OES) have been applied to the direct analysis of SiC powders. The homogeneity of pellets prepared from mixtures of SiC with copper powder and used for the GD experiments was investigated in detail. Various methods have been tested for the analytical calibration. These have been applied to the direct solid sample analysis of technical SiC powders. The experimental data were evaluated by chemometrical procedures. The results of the two methods have been compared.     

Determination of trace impurities in boron nitride by graphite furnace atomic absorption spectrometry and electrothermal vaporization inductively coupled plasma optical emission spectrometry using solid sampling

Two digestion-free methods for trace analysis of boron nitride based on graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma spectrometry optical emission (ETV-ICP-OES) using direct solid sampling have been developed and applied to the determination of Al, Ca, Cr, Cu, Fe, Mg, Mn, Si, Ti and Zr in four boron nitride materials in concentration intervals of 1–23, 54–735, 0.05–21, 0.005–1.3, 1.6–112, 4.5–20, 0.03–1.8, 6–46, 38–170 and 0.4–2.3 μg g^− 1, respectively. At optimized experimental conditions, with both methods, effective in-situ analyte/matrix separation was achieved and calibration could be performed using calibration curves measured with aqueous standard solutions. In solid sampling GFAAS, before sampling, the platform was covered with graphite powder and, for determination of Si, also the Pd/Mg(NO₃)₂ modifier was used. In the determination of all analyte elements by solid sampling ETV-ICP-OES, Freon R12 was added to argon carrier gas. For solid sampling GFAAS and ETV-ICP-OES, the achievable limits of detection were within 5 (Cu)–130 (Si) ng g^− 1 and 8 (Cu)–200 (Si) ng g^− 1, respectively. The results obtained by these two methods for four boron nitride materials of different purity grades are compared each with the other and with those obtained in analysis of digests by ICP-OES. The performance of the two solid sampling methods is compared and discussed.     

A long-term validation of the modernised DC-ARC-OES solid-sample method

The validation procedure based on ISO 17025 standard has been used to study and illustrate both the longterm stability of the calibration process of the DC-ARC solid sample spectrometric method and the main validation criteria of the method. In the calculation of the validation characteristics depending on the linearity(calibration), also the fulfilment of predetermining criteria such as normality and homoscedasticity was checked. In order to decide whether there are any trends in the time-variation of the analytical signal or not, also the Neumann test of trend was applied and evaluated. Finally, a comparison with similar validation data of the ETV-ICP-OES method was carried out.     

Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods

In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and – for the first time – by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3σ-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly threefold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.     

Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods

In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and--for the first time--by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3sigma-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly three-fold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.     

Multielement trace determination in SiC powders: assessment of interlaboratory comparisons aimed at the validation and standardization of analytical procedures with direct solid sampling based on ETV ICP OES and DC arc OES

The members of the committee NMP 264 “Chemical analysis of non-oxidic raw and basic materials” of the German Standards Institute (DIN) have organized two interlaboratory comparisons for multielement determination of trace elements in silicon carbide (SiC) powders via direct solid sampling methods. One of the interlaboratory comparisons was based on the application of inductively coupled plasma optical emission spectrometry with electrothermal vaporization (ETV ICP OES), and the other on the application of optical emission spectrometry with direct current arc (DC arc OES). The interlaboratory comparisons were organized and performed in the framework of the development of two standards related to “the determination of mass fractions of metallic impurities in powders and grain sizes of ceramic raw and basic materials” by both methods. SiC powders were used as typical examples of this category of material. The aim of the interlaboratory comparisons was to determine the repeatability and reproducibility of both analytical methods to be standardized. This was an important contribution to the practical applicability of both draft standards. Eight laboratories participated in the interlaboratory comparison with ETV ICP OES and nine in the interlaboratory comparison with DC arc OES. Ten analytes were investigated by ETV ICP OES and eleven by DC arc OES. Six different SiC powders were used for the calibration. The mass fractions of their relevant trace elements were determined after wet chemical digestion. All participants followed the analytical requirements described in the draft standards. In the calculation process, three of the calibration materials were used successively as analytical samples. This was managed in the following manner: the material that had just been used as the analytical sample was excluded from the calibration, so the five other materials were used to establish the calibration plot. The results from the interlaboratory comparisons were summarized and used to determine the repeatability and the reproducibility (expressed as standard deviations) of both methods. The calculation was carried out according to the related standard. The results are specified and discussed in this paper, as are the optimized analytical conditions determined and used by the authors of this paper. For both methods, the repeatability relative standard deviations were <25%, usually ~10%, and the reproducibility relative standard deviations were <35%, usually ~15%. These results were regarded as satifactory for both methods intended for rapid analysis of materials for which decomposition is difficult and time-consuming. Also described are some results from an interlaboratory comparison used to certify one of the materials that had been previously used for validation in both interlaboratory comparisons. Thirty laboratories (from eight countries) participated in this interlaboratory comparison for certification. As examples, accepted results are shown from laboratories that used ETV ICP OES or DC arc OES and had performed calibrations by using solutions or oxides, respectively. The certified mass fractions of the certified reference materials were also compared with the mass fractions determined in the interlaboratory comparisons performed within the framework of method standardization. Good agreement was found for most of the analytes.     

Feasibility of ETV-ICP-OES for Characterization of Archaeological Glasses

In the present study the possibilities of electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) for characterization of archaeological glasses were investigated. The objects of our research were fragments of a colorless late antique Roman flat window glass (fifth century A.D.) and colored medieval glass bracelets (eleventh–twelfth century A.D.) excavated in the region of Pernik (West Bulgaria).

The finely ground glass samples were analyzed directly and CHF₃ was used as evaporation and transport modifier. Dried aqueous standard solutions and certified reference materials with different matrix (glass, fly ash, and stream sediment) were used as calibration standards. No matrix effects were observed by the optimized conditions. Measurements were performed using common calibration curves obtained with all appropriate calibration standards and major, minor, and trace element concentrations were determined. ETV-ICP-OES analytical data were used to establish the type of glass, the fluxing agents, the typical coloring and decoloring elements, and the recipe norm.     

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.     

Geoanalysis using plasma spectrochemistry – milestones and future prospects

Highlights of plasma spectrochemistry in geoanalysis are reviewed. The techniques are evaluated in terms of recent instrumental developments, calibration strategies, spectral and matrix interferences and analytical performance. While acid decomposition results in solutions containing low salt contents, this decomposition strategy is inappropriate for numerous sample types due to poor recoveries. On the other hand, alkali fusions result in total decomposition, but solutions containing high salt contents constrain the accuracy due to interference effects in the inductively coupled plasma (ICP), the sample introduction system, and in the quadrupole mass spectrometer interface. Therefore, practical limits of determination are evaluated in terms of salt tolerances. It is concluded that ICP-atomic emission spectrometry (AES) is employed mainly for the accurate determination of the major and minor elements and the more abundant trace elements. On the other hand, ICP-mass spectrometry (MS) is used mainly for the determination of trace elements and together with the possibility of obtaining some isotopic information, it profoundly enhances the capability for solving geochemical problems. Several methods of direct solid sample introduction are described. These include direct current (DC) arc emission spectroscopy (DC-AES), slurry nebulization (SN), spark ablation (SA), laser ablation (LA) and glow discharges (GD). These devices allow direct solid analysis of bulk samples, single minerals and inclusions.     

Matrix sensitivity of solid sampling AAS. Determination of zinc in geological samples

Direct solid sampling techniques in AAS have several advantages over wet digestion methods such as small sample size requirements and simple calibration procedures. But some disadvantages also exist such as the sample in homogeneity and the matrix sensitivity of calibration. The calibration is commonly carried out by varying the sample mass and evaluating the peak intensity versus absolute analyte amount. It is shown here that this procedure must be considered doubtful when matrix effects are expected. In the case of zinc determination in geological samples it has been shown that calibration functions obtained by different reference materials differ significantly from each other. As an alternative a three-dimensional calibration technique can be applied that evaluates the peak intensity versus both analyte content and sample weight. The resulting calibration planes are expected to be hyperbolically curved. This three-dimensional calibration has been applied to the determination of Zn in geological samples and compared with classical solid sampling AAS calibration procedures.     

Determination of minor elements in steelmaking flue dusts using laser ablation inductively coupled plasma mass spectrometry

Element determination in solid waste products from the steel industry usually involves the time-consuming step of preparing a solution of the solid. Laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the analysis of Cr, Ni, Cu, As, Cd and Sn, elements of importance from the point of view of their impact on the environment, in electric arc furnace flue dust (EAFD). A simple method of sample preparation as pressed pellets using a mixture of cellulose and paraffin as binder material was applied. Calibration standards were prepared spiking multielement solution standards to a 1:1 ZnO + Fe₂O₃ synthetic matrix. The wet powder was dried and mechanically homogenised. Quantitative analysis were based on external calibration using a set of matrix matched calibration standards with Rh as a internal standard. Results obtained using only one-point for calibration without matrix matched, needing less time for standardization and data processing, are also presented. Data are calculated for flue dust reference materials: CRM 876-1 (EAFD), AG-6203 (EAFD), AG-6201 (cupola dust) and AG-SX3705 (coke ashes), and for two representative electrical arc furnace flue dusts samples from Spanish steelmaking companies: MS-1 and MS-2. For the reference materials, an acceptable agreement with certificate values was achieved, and the results for the MS samples matched with those obtained from conventional nebulization solutions (CN). The analytical precision was found to be better than 7% R.S.D. both within a single pellet and between several pellets of the same sample for all the elements.     

Comparative Studies on Chemical Modification by Diethyldithiocarbamate for ETV-ICP-OES and ETAAS Determination of Chromium and Nickel

The chemical modification of diethyldithiocarbamate (DDTC) in electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) and in electrothermal atomic absorption spectrometry (ETAAS) was comparatively investigated. The experimental results indicated that the formation of Cr- and Ni-DDTC chelates enhanced significantly the emission signals of Cr and Ni in ETV-ICP-OES, but decreased the absorption signal of Cr and Ni in ETAAS. The different role of DDTC in ETV-ICP-OES and ETAAS was attributed to the different functions of the graphite furnace in the two techniques. The graphite furnace was used as both a vaporizer and an atom-vessel for analytes in ETAAS, but only used as a vaporizer for the sample in ETV-ICP-OES. Thermal gravimetric analysis of Cr- and Ni-DDTC chelates and UV-Vis analysis of the sample vapor collected in CHCl₃ after vaporization of their chelates from the graphite furnace indicated that the analytes were vaporized and transported into ICP as their chelates. In addition, the vaporization mechanism of Cr and Ni was also briefly discussed.     

电热原子吸收分析中的固体进样技术

本文综述了电热原子吸收分析中固体进样技术的进展,详细讨论了固体直接进样和悬浮体进样和样品制备方法、进样工具、校正曲线、基体改进技术、分析性能及其最新应用。     

Evaluation of different sample introduction approaches for the determination of boron in unalloyed steels by inductively coupled plasma mass spectrometry

An extended study of different sampling introduction approaches using inductively coupled plasma mass spectrometry (ICP-MS) is presented for the determination of boron in steel samples. The following systems for sample introduction were applied: direct sample solution nebulization by continuous nebulization (CN) using a cross-flow nebulizer and with flow injection (FI), applied to 0.1% (m/v) and 0.5% (m/v) sample solutions, respectively; FI after iron matrix extraction, using acetylacetone–chloroform, and isotopic dilution (ID) analysis as the calibration method; FI with on-line electrolytic matrix separation; and spark ablation (SA) and laser ablation (LA) as solid sampling techniques. External calibration with matrix-matching samples was used with CN, SA, and LA, and only acid solutions (without matrix matching) with FI methods. When FI was directly applied to a sample solution, the detection limit was of 0.15 μg g⁻¹, improving by a factor of 4 that was obtained from the CN measurements. Isotopic dilution analysis, after matrix removal by solvent extraction, made it possible to analyse boron with a detection limit of 0.02 μg g⁻¹ and, with the on-line electrolytic process, the detection limit was of 0.05 μg g⁻¹. The precision for concentrations above 10 times the detection limit was better than 2% for CN, as well as for FI methods. Spark and laser ablation sampling systems, avoiding digestion and sample preparation procedures, provided detection limits at the μg g⁻¹ levels, with RSD values better than 6% in both cases. Certified Reference Materials with B contents in the range 0.5–118 μg g⁻¹ were used for validation, finding a good agreement between certified and calculated values.     

Uncertainty in analytical results from solid materials with electrothermal atomic absorption spectrometry: a comparison of methods

The combined uncertainty in the analytical results of solid materials for two methods (ET-AAS, analysis after prior sample digestion and direct solid sampling) are derived by applying the Guide to the Expression of Uncertainty in Measurement from the International Standards Organization. For the analysis of solid materials, generally, three uncertainty components must be considered: (i) those in the calibration, (ii) those in the unknown sample measurement and (iii) those in the analytical quality control (AQC) process. The expanded uncertainty limits for the content of cadmium and lead from analytical data of biological samples are calculated with the derived statistical estimates. For both methods the expanded uncertainty intervals are generally of similar width, if all sources of uncertainty are included. The relative uncertainty limits for the determination of cadmium range from 6% to 10%, and for the determination of lead they range from 8% to 16%. However, the different uncertainty components contribute to different degrees. Though with the calibration based on reference solutions (digestion method) the respective contribution may be negligible (precision < 3%), the uncertainty from a calibration based directly on a certified reference material (CRM) (solid sampling) may contribute significantly (precision about 10%). In contrast to that, the required AQC measurement (if the calibration is based on reference solutions) contributes an additional uncertainty component, though for the CRM calibration the AQC is “built-in”. For both methods, the uncertainty in the certified content of the CRM, which is used for AQC, must be considered. The estimation of the uncertainty components is shown to be a suitable tool for the experimental design in order to obtain a small uncertainty in the analytical result.     

Direct determination of lead in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after furnace-fusion in the sample cuvette-tungsten boat furnace

The newly conceived electrothermal vaporization (ETV) system using a tungsten boat furnace (TBF) sample cuvette was designed for the direct analysis of solid samples with detection by inductively coupled plasma mass spectrometry (ICP-MS). Into this small sample cuvette, a solid mixture of the biological samples and diammonium hydrogenphosphate powder as a fusion flux was placed and situated on a TBF. Tetramethylammonium hydroxide solution was added to the mixture. After the on-furnace digestion had been completed, the analyte in the cuvette was vaporized and introduced into the ICP mass spectrometer. The solid samples were analyzed by using a calibration curve prepared from the aqueous standard solutions. The detection limit was estimated to be 5.1 pg of lead, which corresponds to 10.2 ng g(-1) of lead in solid samples when a prepared sample amount of 1.0 mg was applied. The relative standard deviation for 8 replicate measurements obtained with 100 pg of lead was calculated to be 6.5%. The analytical results for various biological samples are described.     

多工作曲线-全谱交直流电弧发射光谱法测定地质样品中的铅含量

在分析仪器测定中,当元素含量变化较大时,部分低含量和高含量的样品很难得到理想的测定结果。通过使用多条工作曲线来扩大元素测定的动态范围,对地质样品中不同含量的铅进行了测定,结果表明,方法的相对标准偏差均小于10%,用多工作曲线法测得的铅含量与推荐值更接近。待测样品含量首先由第一条灵敏度高的曲线进行测定,若测定浓度大于该曲线的转换值,则由第二条灵敏度较低的工作曲线进行测定。转换值的设定要充分考虑工作曲线的衔接问题,设定的转换值浓度应该在衔接的两条工作曲线上都处于线性部分。使用多工作曲线法,设定合理的转换值,可以同时获得高、低含量样品的理想测定结果。