Calibration graphs for steels by IR laser ablation inductively coupled plasma atomic emission spectrometry

Infrared laser ablation (IRLA) was studied as a sample-introduction technique for the analysis of steels by inductively coupled plasma atomic emission spectrometry (ICP–AES). A comparison of two IRLA–ICP–AES systems based on Q-switched nanosecond Nd?:?YAG lasers was performed. The beam of the Lina-Spark atomizer (LSA Sarl, Cully, Switzerland) based on the Surelite I-20 laser (Continuum, USA) was moved along a circle. A Perkin–Elmer Optima 3000 DV ICP system was used both with lateral and axial viewing modes. A laboratory-made ablation system based on the Brilliant laser (Quantel) was coupled to a Jobin-Yvon 170 Ultrace ICP (lateral viewing, polychromator part employed). A sample was rotated along a circle during ablation. Linearity of calibration plots was verified at least up to 19% Cr and 12% Ni without internal standardization for both LA–ICP–AES systems. Other elements examined were Mo up to 3%, Mn up 1.5%, Si up to 1.7%, and Cu up to 0.15%. The reproducibility was in the range 5–1 %RSD for a mass percentage 0.5–20% of steel constituents. The relative uncertainty of the centroids of the calibration lines was in the range from ± 4% to ± 12% for Cr, Ni, Mn, Mo, and Si, and from ± 8% to ± 19% for Cu. The lowest determinable quantities were calculated for calibration dependencies. Performances of both the IR-LA–ICP–AES were comparable.     

Direct solid atomic emission spectrometric analysis of metal samples by an argon microwave plasma torch coupled to spark ablation

Spark ablation has been combined to microwave plasma torch atomic emission spectrometry for the direct analysis of compact metallic samples. The material is ablated by a medium voltage spark (450 V, 370 Hz) in a point-to-plane configuration and swept into a 100-W, 2.45-GHz argon microwave discharge. The microwave plasma is observed end-on and the radiation analysed with a polychromator. The detection limits for Fe, Ni, Pb and Sn in brass, Cr, Cu, Ni, Mn, Mo, Si and V in steel and Cu, Fe, Mg, Mn, Si and Zn in aluminium with the microwave plasma torch in the case of measurements with a polychromator are in the μg/g range and by a factor of up to 20 higher than those obtained with spark ablation coupled to inductively coupled plasma atomic emission spectrometry using a high resolution sequential spectrometer. The stability of the emission signal depends on the element studied and relative standard deviations usually are between 0.5 and 3.5%. In the case of low-alloy steels, the linearity and the precision of the calibration could be improved by internal standardisation. Several elements (Cr, Cu, Ni, Si and V) could be determined in a steel sample (BAS SS 410/1) with high accuracy and precision.     

Biomonitoring of essential and toxic metals in single hair using on-line solution-based calibration in laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful and sensitive surface analytical technique for the determination of concentration and distribution of trace metals within biological systems at micrometer spatial resolution. LA-ICP-MS allows easy quantification procedures if suitable standard references materials (SRM) are available. In this work a new SRM-free approach of solution-based calibration method in LA-ICP-MS for element quantification in hair is described. A dual argon flow of the carrier gas and nebulizer gas is used. A dry aerosol produced by laser ablation (LA) of biological sample and a desolvated aerosol generated by pneumatic nebulization (PN) of standard solutions are carried by two different flows of argon as carrier or nebulizer gas, respectively and introduced separately in the injector tube of a special ICP torch, through two separated apertures. Both argon flows are mixed directly in the ICP torch. External calibration via defined standard solutions before analysis of single hair was employed as calibration strategy. A correction factor, calculated using hair with known analyte concentration (measured by ICP-MS), is applied to correct the different elemental sensitivities of ICP-MS and LA-ICP-MS. Calibration curves are obtained by plotting the ratio of analyte ion M⁺/³⁴S⁺ ion intensities measured using LA-ICP-MS in dependence of analyte concentration in calibration solutions. Matrix-matched on-line calibration in LA-ICP-MS is carried out by ablating of human hair strands (mounted on a sticky tape in the LA chamber) using a focused laser beam in parallel with conventional nebulization of calibration solutions. Calibrations curves of Li, Na, Mg, Al, K, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Mo, Ag, Cd, I, Hg, Pb, Tl, Bi and U are presented. The linear correlation coefficients (R) of calibration curves for analytes were typically between 0.97 and 0.999. The limits of detection (LODs) of Li, V, Mn, Ni, Co, Cu, Sr, Mo, Ag, Ba, Cd, I, Hg, Pb, Bi and U in a single hair strand were in the range of 0.001-0.90 μg g⁻¹, whereas those of Cr and Zn were 3.4 and 5.1 μg g⁻¹, respectively. The proposed quantification strategy using on-line solution-based calibration in LA-ICP-MS was applied for biomonitoring (the spatial resolved distribution analysis) of essential and toxic metals and iodine in human hair and mouse hair.     

ICP–AES法测定铬镍不锈钢中锰、铬、镍、硅、磷、铜、钼的含量

建立电感耦合等离子体原子发射光谱(ICP–AES)法测定铬镍不锈钢中锰、铬、镍、硅、磷、铜、钼7种元素含量的方法。试样用盐酸与硝酸混合酸溶液溶解,采用溶解国家标准样品的方法制备校准曲线溶液,确定了元素最佳分析谱线。各元素的含量在其测试范围内与原子发射强度呈良好的线性关系,线性相关系数不小于0.999,7种元素的检出限在0.000 3%~0.003 0%之间。该方法应用于铬镍不锈钢标准样品的测定,测定值与认定值相符,测定值的相对标准偏差在0.12%~1.15%之间(n=8)。应用于铬镍不锈钢样品测定时,加标回收率在90%~110%之间。该方法操作简便、迅速,可满足日常铬镍不锈钢中多元素含量的检测需要。     

抗癌草药半边旗微量元素含量的分析

用等离子体发射光谱法测定了广州和化州两地区半边旗的２５种元素，在检出的２０种元素中，含有人体必需的微量元素Ｆｅ、Ｚｎ、Ｃｕ、Ｍｎ、Ｃｏ、Ｍｏ、Ｎｉ、Ｃｒ、Ｖ，以Ｚｎ、Ｍｎ、Ｆｅ、Ｃｕ等元素含量较高，这为研究微量元素对半边旗的生长和抗癌作用的影响提供了启示。     

Determination of impurity elements in high-purity solid precursors based on tantalum pentoxide by inductively coupled plasma mass spectrometry

Conditions for the inductively coupled plasma mass-spectrometric (ICP MS) analysis of high-purity tantalum pentoxide and tantalum pentoxide doped with rare-earth elements without the separation of a sample matrix from analytes (Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Sn, W, Gd, Dy, Er, and Pb) were determined. The metrological parameters of ICP MS analysis (accuracy, precision, and detection limits) were calculated. It was established that, in the analysis of test sample solutions with tantalum concentrations higher than 30 mg/L, a matrix effect appeared: the intensity of the measured ion current of analytes decreased against the background of a high concentration of sample matrix (tantalum) ions. This caused a proportional underestimation of the results of analysis. It was shown that it is reasonable to plot calibration functions against the background of a solution containing no more than 30 mg/L of tantalum ions. The results of the ICP MS analysis were compared with X-ray fluorescence (XRF) and optical emission spectrometry (OES) analysis data and calculation data on the amounts of admixtures introduced into tantalum pentoxide at the stage of the extraction preparation of a precursor.     

Quantitative analysis using remote laser-induced breakdown spectroscopy (LIBS)

A measurement system for quantitative, remote materials analysis has been realised. It is based on the method of laser-induced breakdown spectroscopy (LIBS), utilising an optical fibre system, both to deliver the laser radiation to the sample specimen and to collect the light emission from the luminous plasma plume. Distances of up to 100 m between the remote location and the apparatus have been demonstrated. All experiments were performed in situ, under standard conditions of air at atmospheric pressure. In particular, quantitative analysis of ferrous specimens has been achieved, detecting traces of the elements Cr, Cu, Mn, Mo, Ni, Si and V, down to relative concentrations of about 200 ppm. This remote analytical technique has been implemented successfully for measurements in the hostile environment of nuclear reactor buildings.     

The determination of minor elements in steel by proton-induced prompt gamma-ray spectrometry

Pure elemental targets of Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and W were irradiated with protons from 3.5 to 6.0 MeV, interference-free sensitivities were calculated for analysis by prompt gamma-ray spectrometry and sensitivity curves were plotted to show the variation of sensitivity with bombarding energy. Appropriate bombarding energies were selected for analysis and the extent of possible inter-element interferences and background effects were determined. Standard reference steels were used to evaluate this method for the determination of the minor elements Si, V, Cr, Mn and Co.     

Elektrolytische L?sungsherstellung zur Stahlanalyse mit der ICP-Spektrometrie

Zusammenfassung Die Lösungsherstellung für die Stahlanalyse mit der ICP-Spectrometrie erfolgt durch Elektrolyse in HCl. Zahlreiche Elemente (wie Al, Si, Mn, Cr, Ni, Co) können in unlegierten und niedriglegierten Stahlproben mit C-Gehalten unter 0.3% bestimmt werden.

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Electrolytic preparation of solution for steel analysis by ICP spectrometry

Summary The preparation of solutions for steel analysis by ICP spectrometry is performed by electrolysis in HCl. Numerous elements (as Al, Si, Mn, Cr, Ni, Co) can be determined in unalloyed and low-alloy steel with C-contents of less than 0.3%.

     

光电发射光谱法分析钛合金中的主要合金元素

依据光电发射光谱仪光源激发机理,结合钛合金的材料性能,选用火花放电激励光源和时间分解脉冲分布测光法,绘制钛合金中主要合金元素的工作曲线,对A l、V、Fe、S i、C、Mn、Cu、Mo、Sn、Zr、N i、Cr等元素进行光谱直接测定。测定结果与化学法测定结果基本一致,测定结果的相对标准偏差为0.72%~4.27%(n=11)。     

Determination of trace elements in quartz glass by use of LINA-Spark-ICP-MS as a new method for bulk analysis of solid samples

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g(-1) range with detection limits of less than 10 ng g(-1) for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120-220 ng g(-1) for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2-4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr+ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA-ICP-MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA-ICP-MS is less appropriate for bulk analysis in the ng g(-1) range.     

色谱分离ICP-AES法测定高纯度八氧化三铀中的13种微量杂质

采用磷酸三丁酯（TBP）萃淋树脂色层分离铀，用电感耦合等离子体-原子发射光谱法测定分离后的离纯度铀氧化物的杂质元素Al、Ca、Cr、Cu、Fu、Mn、Mo、Ni、P、Ti、V、Zn、Zr，除Al、Fe、Mo外的其余10种元素的测定结果符合标准物质定值的要求。     

Characterization and screening of metals,metalloids and biomarkers in crude oil by ICP–MS/OES,and GC–MS techniques after digestion by microwave‐induced combustion

A method for digestion of light and medium Iraqi crude oils (Basrah and Khanaken oils) using microwave‐induced combustion (MIC) in closed vessels is described for the determination of Hg, Au, Cu, Al, Ca, Co, K, Mg, Si and Sr by inductively coupled plasma optical emission spectrometry (ICP–OES) and Mo, Ti, Mn, Li, Se^?1, Rb, Ag, Ba, Pb, As, Cd, Cr, Fe, Ni, V and Zn by inductively coupled plasma mass spectrometry (ICP–MS). Upon using MIC it was possible to obtain lower limits of detection by ICP–MS and also by ICP–OES compared with those obtained by microwave‐assisted digestion. The MIC was the best choice with regard to the possibility of using dilute nitric acid as an absorbing solution, which is important to minimize the interference encountered by ICP–MS and ICP–OES.The physicochemical parameters and some contaminants of crude oil samples were analyzed to classify and assess the quality of the crude oils. This study determines the viability of the use of Fourier transform infrared spectroscopy as an alternativee to traditional petroleum geochemical methods for crude oil characterization. The infrared fingerprints agree with the results obtained from GC–MS analysis.     

Verfahren zur Spurenanalyse aus metallischen Proben

Zusammenfassung Ein neues lösungsspektrographisches Zerstäubungsverfahren wird beschrieben, bei dem die Lösung so zerstäubt wird, daß sie die Graphitelektroden nicht berührt. Mit diesem Verfahren könnten 10^–3 bis 10^–5 % Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V und Zr in Eisen und Stahl bestimmt werden.Zur Bestimmung von Verunreinigungen oder Einschlüssen in Stahl wird ein spektrographisches Verfahren mit Preßlingselektroden empfohlen, das nur 0,1–1 mg Rückstand benötigt. Oxide von Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn und Zr konnten bis herab zu etwa 10^–7 g erfaßt werden.

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Methods for the determination of trace elements from metallic samples

The principles of a new spectrographical atomizing-method of solution are described. The solution has to be atomized into a gap without contacting the surface of the graphite electrodes. In this way the exact determination of 10^–3 to 10^–5 % of Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V and Zr in iron and steel is possible.The microanalytical determination of impurities or inclusions in steel has been achieved by a spectrographical method with briquette electrodes. The necessary amount of isolation residue is only 0.1–1 mg. The oxides of Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn and Zr can be accurately determined by this procedure. The limit of determination is about 10^–7 g.

     

Quantitative determination of trace metals in high-purity silicon carbide powder by laser ablation inductively coupled plasma mass spectrometry without binders

We have developed a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method to directly determine the concentrations of trace metals in high-purity powdery silicon carbide (SiC) samples. The sample preparation procedure is simple and rapid. The sample was formed into pellets using no binders and heated at 1000 °C for 2 h. The operation parameters for LA and ICP-MS were optimized to achieve a table signal intensity and high sensitivity. National Institute of Standards and Technology Standard Reference Materials glasses were chosen as calibration standards, with ²⁹Si chosen as the internal standard. The relative sensitivity factor obtained from the glass matrix was used to calculate the concentrations of analytes in the SiC ceramic samples. The regression correlation coefficients of the calibration curves for elements with internal standard correction ranged from 0.9981 to 0.9999, which are better than those obtained with an external standard correction method only. The relative standard deviation of the measured trace element concentrations was less than 5%. The limits of detection were 0.02, 0.08, 0.04, 0.005, 0.01, 0.02, 0.004, 0.07, and 0.006 mg kg^− 1 for B, Ti, Cr, Mn, Fe, Ni, Co, Cu, and Sr, respectively. The method was applied to analyze SiC samples with two different particle sizes. The analysis showed good agreement with the results of inductively coupled plasma optical emission spectrometry. The reliability of the proposed method was confirmed by determining the contents of B, Ti, Cr, Mn, Fe, Ni, and Cu in BAM-S003.     

Development of multi-elemental method for quality control of parenteral component solutions using ICP-MS

An inductively coupled plasma mass spectrometry (ICP-MS) method for elemental impurities determination in components used for parenteral nutrition solutions is proposed. Solutions of amino acids (10% m/v), glucose (50% m/v) and lipids (20% m/v) were analyzed. Arsenic, Cd, Cu, Pb and Mo were determined by ICP-MS operated at standard mode, whilst pneumatic nebulization was used for introducing the sample solution into the ICP. Mercury was determined using cold vapor generation (CVG) coupled to ICP-MS. Chromium, Mn, Ni and V were determined by means of dynamic reaction cell-inductively coupled plasma mass spectrometry (DRC-ICP-MS), while ammonia was used as reaction gas. The operational conditions of each technique were optimized in order to achieve better sensitivity, precision and accuracy. The influence of the sample matrix, mainly carbon, on all investigated elements was evaluated. The use of DRC was effective to reduce interferences on Cr, Mn, Ni and V determination. The other investigated elements (As, Cd, Cu, Pb, Mo and Hg) were determined directly in the samples, which were properly diluted. Results obtained were in good agreement (between 96 and 103%) with certified values (certified reference materials of water were analyzed), at the same time as the relative standard deviation was lower than 5%. Sample throughput was relatively high (up to 30 samples of components used for parenteral nutrition solution could be analyzed per hour). In this way, the proposed method can be recommended for routine analysis.     

Determination of trace elements in quartz glass by use of LINA-Spark–ICP–MS as a new method for bulk analysis of solid samples

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g^–1 range with detection limits of less than 10 ng g^–1 for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120–220 ng g^–1 for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2–4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr⁺ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA–ICP–MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA–ICP–MS is less appropriate for bulk analysis in the ng g^–1 range.     

Effect of Metal Inclusions on the Porous Structure and Photocatalytic Activity of Titanium Dioxide

A study was carried out on the effect of the inclusion of a series of transition metals (V, Cr, Mn, Fe, Ni, Cu, Zr, Mo) and also Al, Si, Zn, and Sn into titanium dioxide on its porous structure, anatase formation, and photocatalytic activity in the generation of molecular hydrogen from aqueous ethanol. An increase in the content of these metals leads to a decrease in photocatalytic activity, while an increase in the anatase content in titanium dioxide leads to an increase in such activity.     

Multielement analysis of gypsiferous soils using a sequential inductively coupled plasma-atomic emission spectrometric method

The amount of major, minor, and trace elements (Ca, Mg, Fe, Na, Sr, Mn, Cu, Cr, V, Mo, B, Ni, Li, and Ba) in gypsiferous soils formed by evaporitic processes was determined. A sequential analysis method by atomic emission spectroscopy with an inductively coupled plasma was used, working with partial matrix matching between the reference standards and the real samples. Furthermore, a simplified method, based on two calibration graphs (Fe and Li), was developed for calibrating the analysis procedure.