On the effect of catalyst status in the quantitative determination of platinum in Pt-Sn/MgO materials

The development of an analytical method for the determination of platinum in MgO based Pt/Sn catalysts is described. Electrothermal atomic absorption spectroscopy (ETAAS) was chosen because of its high sensitivity and robustness against spectral interferences. All the sources of chemical interferences were statistically analyzed and corrections were adopted for the presence of magnesium oxide support. The effectiveness of different mineralization procedures was critically evaluated as a function of the chemical of the solid catalyst. Microwave digestion allowed recovery of metal of 100% for all the catalysts analyzed and exhibited significant better precision values than other digestion methods, which could nevertheless be utilized under proper conditions in selected cases. Received: 31 July 2000 / Revised: 17 October 2000 / Accepted: 24 October 2000     

Analysis of Borosilicate Catalysts by Inductively Coupled Plasma Atomic Emission Spectroscopy

Abstract

A method was developed for the analysis of borosilicate catalysts. Samples were prepared by fusion technique with potassium hydroxide and analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The method was applied to a borosilicate NIST SRM 93 which was analyzed for major and minor elements (aluminum, sodium, silicon and boron). Despite the presence of relatively high concentration of the potassium, no matrix interferences were observed. This method provides precision and accuracy better than ±4% and ±6%, respectively.     

Microwave-assisted extraction of rare earth elements from petroleum refining catalysts and ambient fine aerosols prior to inductively coupled plasma-mass spectrometry

A robust microwave-assisted acid digestion procedure followed by inductively coupled plasma-mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM_2.5). High temperature (200 °C), high pressure (200 psig), acid digestion (HNO₃, HF and H₃BO₃) with 20 min dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst and PM_2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using ¹¹⁵In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu and Dy in ambient PM_2.5 in an industrial area of Houston, TX.     

电感耦合等离子体发射光谱法测定植物油中的磷

用电感耦合等离子体发射光谱法(ICP-AES)测定了植物油中的磷.采用多谱线拟合技术(MSF)校正了铜对P213.617 nm和P214.914 nm光谱干扰.比较了活性炭炭化灰化法和微波消解法两种样品前处理方法对分析结果的影响.结果表明这两种前处理方法所得结果都能与国标磷钼蓝分光光度法的分析结果吻合,其中活性炭炭化灰化法的方法检出限(0.053 mg/kg)较微波消解法的方法检出限(0.42 mg/kg)更低,所以对低含量的磷的检测结果其相对误差及精密度更好.该法应用于植物油中磷的测定.     

用ICP-AES同时测定脑瘤中17种元索

本文用ICP-AES技术,同时测定了30例脑瘤中17种元素的含量。研究了脑瘤试样的化学处理方法,并对共存元索干扰和回收率等项作了探讨     

ICP-AES测定铀污染土壤植物中铀的研究

采用电感耦合等离子体发射光谱(ICP-AES)对铀污染土壤植物中铀的测定方法进行了研究.在λU385.958 nm处,选择了仪器的最佳工作条件,考察了酸度和常见共存元素对测定的干扰情况,并且对比了干灰化消解和湿式消解对测定的影响.研究发现2%硝酸溶液为最佳介质,干扰离子对测定没有显著影响,干灰化消解比湿式消解得彻底.在选定条件下,方法检出限为0.18 mg·L-1,测定下限为0.61 mg·L-1,5.0000 mg·L-1的铀标准溶液的相对标准偏差RSD(n=10)为0.81%,方法回收率为96.2%～106.2%.该方法操作简单,快速.结果表明,用ICP-AES测定铀污染土壤植物样品中的铀是可行的.     

微波消解-ICP-MS测定塑料原料中14种催化剂残留元素

采用微波消解法预处理聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚对苯二甲酸乙二醇酯(PET)常用塑料原料,使用压力控制装置对消解过程进行监控并对消解条件进行摸索,考察了消解量、消解体系、消解温度和保持时间对消解结果的影响,优化选择了电感耦合等离子体-质谱法(ICP-MS)的测定参数和内标元素。建立了微波消解-电感耦合等离子体-质谱法测定塑料原料中Li、Ca、Mg、Al、Si、Ti、V、Cr、Co、Zn、Ga、Zr、Sb、Hf 14种元素的催化剂残留的检测方法。方法检出限在0.001～10.60μg/L,回收率在82%～120%之间,相对标准偏差小于20%。     

Critical review of the atomic spectrometric analysis of arsenic in foods

The literature on the determination of arsenic in foods by atomic spectroscopy involving hydride generation, platform furnace Zeeman and inductively coupled plasma has been critically reviewed. Hydride generation has been largely displaced as a powerful tool by platform furnace Zeeman, using the STPF (stabilized temperature platform furnace) concept for the control of interferences. Inductively coupled plasma with conventional pneumatic nebulization has been little used. An alternative is to employ hydride generation-ICP with extraction of the arsenic in an organic phase. This technique permits proper control of interferences together with an increase in sensitivity. Depending on the contents present in the foodstuff and the technique available, the sample can be solubilized by either wet or dry digestion.     

微波消解-电感耦合等离子体质谱法同时测定化妆品中的汞、铅、砷、锑

采用HNO_3-H_2O_2微波消解样品,电感耦合等离子体质谱法(ICP-MS)同时测定化妆品中的汞、铅、砷、锑.实验中探讨了最佳的消解程序,选择适当的同位素,并用铋、铟、锗做内标元素,有效地抑制了分析信号的漂移.结果表明,各元素的检出限在0.089～0.37μg/kg,相对标准偏差(RSD)在0.709%～2.10%,回收率为80.10%～102.67%.该方法具有简便、快速、准确、灵敏度高的优点,适用于化妆品中的汞、铅、砷、锑元素的同时测定.     

Comparison of Microwave-Assisted Digestion Methods and Selection of Internal Standards for the Determination of Rh, Pd and Pt in Dust Samples by ICP-MS

Different temperature-pressure controlled microwave-assisted digestion methods were compared for the digestion of dust samples prior to the determination of rhodium and platinum by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for platinum and rhodium in the digested reference material (BCR-723, road dust) were generally in good agreement with the certified values. However, the determination of matrix elements (Zn, Rb, Sr, Y, Hf and Pb) showed clear differences between the digestion methods. In addition, different internal standards were compared in the determination rhodium, palladium and platinum by ICP-MS. According to the results, even serious non-spectral interferences can be corrected by choosing a suitable internal standard or combination of internal standards.     

Use of an in vitro digestion method to evaluate the bioaccessibility of arsenic in edible seaweed by inductively coupled plasma-mass spectrometry

Different types of edible seaweeds (Kombu, Wakame, Nori and Sea Lettuce) harvested in the Galician coast (Northwestern Spain) were analyzed for total arsenic quantification before and after being cooked following manufacturer's instructions. Furthermore, the total arsenic in the bioaccessible fraction obtained after simulating a human digestion by an in vitro process was determined in those raw and cooked seaweeds. The detection of the target element was performed by inductively coupled plasma-mass spectrometry (ICP-MS) which was equipped with a collision cell to avoid polyatomic interferences. Piperazine-NN-bis (2-ethane-sulfonic acid) disodium (PIPES) buffer solution at a pH of 7.0 and dialysis membranes of 10 kDa molecular weight cut-off (MWCO) were used for intestinal digestion. Accuracy of the method was assessed by analyzing a BCR-279 certified reference material. The accuracy of the in vitro procedures was established by a mass balance study for Nori and Sea Lettuce which led to good accuracy of the whole in vitro process, after statistical evaluation (95% confidence interval). Results showed that the effect of cooking seaweed causes the removal of the element into the cooking water. Dialyzability percentages found in raw seaweed samples were comparable to those found in cooked seaweed, except in the case of Sea Lettuce sample for which a lower dialyzability percentage was found when it was cooked.     

Boron analysis in biological material: microwave digestion procedure and determination by different methods

Investigations were made on the determination of boron in biological material. A procedure using the microwave digestion technique was optimised. The analyses were performed by photometry with azomethine-H, fluorimetry with carminic acid, inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. The matrix interferences, the interferences caused by iron and the detection limits were investigated for these methods. Determinations were performed for plant material, wheat, milk, meat and blood plasma. Recoveries and precision of all methods were studied. To test accuracy and precision, four NBS reference materials were analysed and the results compared with the values in literature. Good recoveries were found with all methods, except the fluorimetric technique. The boron content found in the NBS standard reference materials agreed well with data reported before. Best precision was obtained for the two ICP methods. The azomethine-H method gave good results when material of high boron content was analysed. With the carminic acid method no reliable results were achieved.     

Determination of platinum and rhodium in dust and plant samples using microwave-assisted sample digestion and ICP-MS

The platinum group elements (PGEs), particularly platinum, palladium and rhodium, are nowadays increasingly emitted into the environment from automotive catalytic converters. Thus, a method for the determination of PGEs (especially platinum and rhodium) in dust and plant samples was developed. The developed method was based on microwave-assisted sample digestion and inductively coupled plasma mass spectrometric (ICP-MS) determination. Spectral interferences in ICP-MS determination were corrected using mathematical correction equations based on signal ratio measurement. In addition, platinum and rhodium concentrations in the digested dust samples were also determined after Te coprecipitation without correction of the interferences. The results for platinum and rhodium in reference materials (NIST SRM 2557, recycled monolith autocatalyst and BCR-723, road dust) were in good agreement with the certified values. Preliminary results for the anthropogenic platinum and rhodium emissions in Oulu, northern Finland, based on dust and plant samples, indicated a common traffic-related source of these metals.     

Development of chiral HPLC for selenoamino acids with ICP-MS detection:application to selenium nutritional supplements

The enantiomeric separation of three underivatized seleno-amino acids, D,L-selenocystine, and D,L-selenomethionine, and D,L-selenomethionine, with UV and ICP-MS detection is described. An HPLC column with a chiral crown ether stationary phase and a mobile phase of 0.10 M HCIO4 was used. Absolute detection limits obtained with UV detection ranged from 34.5 to 47.1 ng whereas those obtained with the plasma detector were ca. 40-400 times better. The separations with either detector were good, with the little detector effect on the resolution. Ten commercially available dietary selenium supplements were analyzed using the chiral column to identify and quantify the selenium species present with both detection modes. Selenium species were easily identified using ICP-MS detection, whereas UV detection was not viable because of interferences from the sample matrix and inadequate sensitivity. Selenium species that were unretained using the chiral column were identified using anion exchange chromatography. Total amounts in the samples were also measured using a conventional digestion and enzymatic digestion with ICP-MS detection.     

Investigation of the completeness of digestion procedures prior to voltammetric trace metal analysis of olive leaves

Summary Wet decomposition of olive leaves in open and closed systems, low temperature ashing, UV-irradiation and combinations of these methods have been tested for their application in the determination of heavy metals by anodic stripping voltammetry. Completeness of the decompositon and interferences in the electrochemical determination have been evaluated. Wet decomposition with perchloric acid, low temperature ashing and a combination of pressurized digestion and UV-irradiation were found to be suitable for application in electrochemical measurements. The most serious interferences were observed with well but not fully decomposed samples, such as those obtained by wet decomposition with nitric acid in an open system.

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Untersuchung der Vollständigkeit von Aufschlußverfahren für die voltammetrische Spurenmetall-Analyse von Oliven-Blättern

     

Comparative study of pretreatment methods for the determination of metals in atmospheric aerosol by electrothermal atomic absorption spectrometry

A comparative study of pretreatment methods for the determination of 10 elements (As, Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) in atmospheric aerosols by electrothermal atomic absorption spectrometry (ETAAS) was conducted. For the digestion of the particulates collected in filters, six methods were compared using a mixture of HNO₃ and HF with or without the addition of various oxidative agents (HClO₄ or H₂O₂) or acids (HCl). The comparative study was performed using loaded cellulose filter samples, which were digested in Parr bombs and heated in a conventional oven at 170 °C for 5 h. The extraction efficiency and blanks were compared and it was proved that the digestion method using only HNO₃–HF extracted most of the metals and gave the lowest blanks. The HNO₃–HF mixture was selected for the development of an improved microwave digestion method specific for aerosol-loaded filters. The operating parameters were optimized, so that quantitative recovery of the reference materials NIST 1649a urban dust and NIST 1648 urban particulate matter was achieved. The blank of cellulose and teflon filters were also determined and compared. Teflon filters present the lowest blanks for all the elements. The obtained limits of detection for each type of filters were adequate for environmental monitoring purposes. ETAAS instrumental operation was also optimized for the compensation and the elimination of interferences. The temperature optimization was performed for each metal in every type of filter and optimized parameters are proposed for 10 elements.     

Determination of Trace Metals in Woodlice and their Skins with Particular Emphasis on Quality Control

AI, Fe, Mn and Zn were determined in two ditTerent species of woodlouse: Porcellio scaber and Porcellio dilalalus. Both species were cultivated under standardized conditions in a climatic chamber. Moreover, skins of the cultivated animals were collected and analyzed separately to examine a possible way of decontamination by moulting. To obtain enough sample material for each species, IS animals of the same age and size were pooled. For skin analysis, 10–12 skins were collected and pooled. The animals and their skins were dried, ground and digested in pure concentrated nitric acid using multiwave-assisted high-pressure digestion and. finally, analyzed by ICP-OES. Special emphasis was given to quality control: the reference materials Dorm-2, Dogfish Muscle (Squalus acanthias) and SRM 1577b Bovine Liver, were used to evaluate the whole analytical process including sample digestion. These reference materials of animal origin were selected to match the matrix of the samples as closely as possible. While concentrations of Fe. Mn and Zn were traced to both reference materials, the concentration of AI was checked by Dorm-2 only. Analyses of the elements in the reference materials were carried out using four ditTerent wavelengths for each element simultaneously. aiming at the determination of the best suited wavelength for each element. Analyses of woodlouse samples and their skins were finally carried out using the wavelengths with the highest sensitivities after absence of spectral interferences had been demonstrated.     

Determination of platinum and ruthenium in Pt and Pt-Ru catalysts with carbon support by direct and derivative spectrophotometry

Platinum and ruthenium in carbon supported Pt and Pt-Ru catalysts were determined by direct and derivative spectrophotometric methods. Complexes of platinum and ruthenium with SnCl(3)(-) ligands (tin(II) chloride in HCl) were used to determine both metals in solutions obtained after digestion of the samples of the catalysts. Platinum in the Pt/C catalyst can be determined in solutions obtained by digestion of the samples in aqua regia. Derivative spectrophotometry was used to determine both metals in the presence of each other in solutions obtained after digestion of samples of the Pt-Ru/C catalyst in the mixture of HCl+HNO(3) (6:1). The first derivative at 377 nm (;zero-crossing' point of ruthenium) and the second-derivative values at 495 nm (;zero-crossing' point of platinum) were used to estimate the concentration of platinum and ruthenium, respectively.     

Simultaneous determination of boron,phosphorus and sulphur in some biological and soil materials by inductively-coupled plasma emission spectrometry

Atomic emission lines at 249.678 nm, 214.911 nm and 180.735 nm are used simultaneously to determine total concentrations of boron, phosphorus and sulphur respectively, in plant and soil sample digests by means of inductively-coupled plasma emission spectrometry. The digestion procedures chosen enable these elements to be determined simultaneously on a single digest. Analytical data are compared after using various digestion procedures on standard reference materials. Actual and potential interelement interferences in the plasma are discussed together with attempts to overcome these interferences. Limitations for simultaneous determinations of boron, phosphorus and sulphur remain in the digestion and dissolution procedures.     

Comparison of four microwave digestion methods for the determination of selenium in fish tissue by using hydride generation atomic absorption spectrometry

Four microwave digestion methods of fish tissue for selenium determination by hydride generation atomic absorption spectrometry were compared, in which potassium hexacyanoferrate(III) was chosen as a masking agent for eliminating matrix interferences. The results showed that the methods employing HNO(3)/H(2)O(2), HNO(3)/K(2)S(2)O(8)/H(2)O(2) and HNO(3)/H(3)PO(4)/H(2)O(2) digestion media were unreliable. However, the decomposition using the digestion media of HNO(3)/H(2)SO(4)/H(2)O(2) enabled adequate digestion of fish tissue and retention of selenium in a state amenable for determination. Therefore, the digestion procedures with HNO(3)/H(2)SO(4)/H(2)O(2) media are proposed for the determination of selenium in fish tissue by hydride generation atomic absorption spectrometry. The recoveries of the spiked samples investigated ranged from 90 to 102%. The result obtained from analyzing the NIES CRM No. 6 mussel was in good agreement with the reference value (reference value: 1.5 mug/g; found: 1.45 +/- 0.05 mug/g). The limit of detection for selenium was 0.03 mug/g dry mass for a 100 mg sample. The contents of selenium in local fish species investigated ranged from 0.49 to 2.90 mug/g, and the relative standard deviation for the determination of selenium was less than 8%.