Multielemental analysis of metallurgical samples by thermal neutron activation

Instrumental neutron activation analysis (INAA) was applied to investigated a total of 16 samples of raw materials, intermediate and final products involved in metallurgical processes in Romanian Iron and Stell works Sidex Galatzy: iron ores and pellets from different regions of the world, cast iron, slag and steels. A series of chemical elements was determined in the analyzed samples: Al, As, Ce, Co, Cr, Fe, La, Mn, Na, Sc, Sm, V, W. A qualitative discussion regarding the passing of from elements with different chemical affinity for oxygen compared to that of iron, from the raw materials to slag or to finite products is presented.     

Multielemental Analysis of Human Serum by Dynamic Reaction Cell–Inductively Coupled Plasma Mass Spectrometry

The selection of the most suitable dilution methods for determination of trace elements in human serum using inductively coupled plasma mass spectrometry is reported. The trace elements were Al, V, Cr, Fe, Mn, Co, Cu, Zn, As, Cd, Sn, Tl, and Pb. The performance of various dilution methods was assessed by precision, linearity, detection limits, quantification limits, fortified recoveries, and the analysis of reference materials. The results demonstrate that diluted solution containing only nitric acid is most suitable for As, Cr, Mn, and Co in serum. Dilute solutions containing nitric acid and Triton X-100 were most appropriate for Cu, Zn, Cd, and Tl. The optimum conditions for Al, V, Mn, Fe, Cr, Co, Sn, and Pb used tetra-n-butylammonium hydroxide, Triton X-100, and ethylenediamine tetraacetic acid.     

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 24 elements in four algae reference materials by neutron activation analysis and inductively coupled plasma mass spectrometry

Four algae reference materials, IAEA-391, 392, 393 and IAEA-140, prepared by the International Atomic Energy Agency for intercomparison under different preparation conditions were analyzed for 24 elements. Conventional neutron activation analysis (NAA) was used to determine Al, Ca, Cl, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Sb, V and Zn and epithermal NAA using BN and Cd as shielding material for I, Br, As, Ni, Mo and Cd. Inductively coupled plasma mass spectrometry (ICP-MS) as a complementary and comparative method was applied to determine Pb, Sn, Ni, Sr, Rb, As, Co, Cr, Cu, Mn, V, Mo and Zn. Two analytical quality control standard reference materials IAEA-V-10 (hay powder) and IAEA-331 (spinach) were analyzed simultaneously with real samples. The results agree quite well with each other and with the certified values.     

Determination of impurities in nuclear fuel element components by neutron activation analysis

Neutron activation analysis methods for the determination of impurities in zirconium cladding material and uranium oxide are described. Detection limits for the elements Al, Cd, Cr, Co, Cu, Hf, Fe, Mn, Ni, W and U in zirconium are below that required by the ASTM B 352-79 standard. The method has been tested on the NIST SRM 360a Zircaloy-2 from which the elements Na, Mg, Al, Ca, V, Cr, Fe, Co, Ni, Cu, Eu and U have been detected. The values for Cr, Fe, Ni and Cu are compared with the certified values. A method for the pre-irradiation separation of the elements Mg, Na, Al, K, Sc, Ca, V, Mn, Cr, Fe, Co, Cu, Zn, Rb, Zr, Cd, Cs, REE and Hf from uranium has been developed. A neutron activation analysis method for the determination of those elements in uranium is described. The method is tested by the analysis of the IAEA reference sample SR-54/64. The elements Al, Mn, V, Cu, Cr, Co, Ni and Fe have been detected and the results compared with the certified values.     

Instrumental neutron activation analysis of the hair of metallurgical workers

Hair samples were collected from 20 metallurgical workers (10 males and 10 females) and from 59 control subjects (32 males and 27 females), whose jobs do not indicate a specific occupational exposure. The concentrations of ten minor and trace elements (Al, Co, Cu, Fe, Mg, Mn, Sb, Se, V and Zn) were determined by instrumental neutron activation analysis (INAA). The statistical data distributions, the sex and age influences in these elemental concentrations and the average values obtained for the control group were compared with published data. The effect of occupational exposure to the metallic elements was reflected in elemental composition of hair by significant higher concentration levels of Al, Co, Cu, Fe, Mg, Mn, Sb, V and Zn in the hair of the exposed group, when compared with the control group.     

前列舒通胶囊中26种无机元素的分析

目的：明确造成前列舒通胶囊不同批次间差异的标志性无机元素,并进行安全性评价。方法：采用ICP-MS测定制剂中Al、As、B、Ba、Ca、Cd、Co、Cr、Cu、Fe、K、Mg、Mn、Mo、Na、Ni、Pb、Sb、Se、Sn、Sr、Ti、Tl、V、Zn和Hg元素含量并进行数据分析。运用主成分及综合评分结合聚类分析手段,确定制剂的特征性元素;进行元素含量和相关性分析,明确不同批次各元素的差异及元素之间的关系;以多元素含量为指标,绘制无机元素谱图。结果：19批样品中均未检测出Se、Mo、Sn、Sb、Tl和Hg,且Pb、Cd、As、Cu、Hg均符合限量标准,无机元素含量谱图趋势一致。主成分分析提取了4个主成分,确定元素B、K、Al、V、Cr、Ca、Ti、Na、Co和Mn可作为特征元素。主成分得分图将19批样品分为两类,聚类分析及综合评分结果与其一致,两类样品中各元素含量存在差异性。相关性分析中,明确了B与K、Al、Cr正相关,K与Cr、Co正相关,V与Cr、Mn正相关,Mn与Co正相关,Ca、Ti、Na两两正相关。结论：通过分析前列舒通胶囊中无机元素含量,确定了特征元素,为前列舒通胶囊质量全面控制研究提供科学依据。     

Comparative PGAA and NAA results of geological samples and standards

Concentrations of major and trace elements in volcanic rock and soil samples, including geological standard reference materials, were determined by neutron activation analysis (NAA) and prompt gamma activation analysis (PGAA), both using the k ₀-standardization method. The paper highlights the different experimental procedures, such as sample preparation, data collection and spectrum evaluation. In geological samples, PGAA gives precise results for major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K and—as a unique method—for H), for some of the light trace elements as B and Cl, as well as for Sc, S, Cr, Co, Ni, Cd, Nd, Sm and Gd. NAA is sensitive for the rare earth elements, and for many major (Ti, Al, Fe, Mn, Mg, Ca, Na, K) and trace elements (e.g.: Sc, V, Cr, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Zr, As, Sb, Ce, Ba, Hf, Ta, W). For most major elements the results obtained by the two methods show good agreement. The comparison of the results obtained for trace elements is not always possible, since PGAA is less sensitive and concentrations are often below its detection limits. Nevertheless, the complementarity of NAA and PGAA allows nearly panoramic analysis of geological materials.     

Relative sensitivity coefficients for the analysis of steel by spark-source mass-spectrometry

Quantitative analysis by spark-source mass-spectrometry requires the knowledge of socalled sensitivity coefficients for the elements being determined. Five series of analyses have been carried out on five different steel standard reference materials (NBS-SRM 661-665), using photoplate detection. The relative sensitivity coefficients (S(R)) of Ti, V, Cr, Mn, Co, Ni, Cu, As, Zr, Nb, Mo, Sn, Sb, La, Ta and W were determined vs. iron as an internal standard. The S(R) values were independent of the elemental concentration. A relative standard deviation of about 15% was obtained. The accuracy as confirmed by comparing the results for a pure iron sample with those obtained by neutron-activation analysis was within the same limits.     

Internal standard activation analysis of silicon in steel

Non-destructive 14-MeV neutron activation analysis for silicon in steel has been applied with ⁵⁶Mn as internal standard.⁵⁶Mn is formed from the iron matrix via the ⁵⁶Fe(n,p)⁵⁶Mn reaction. Several methods of internal standardisation via⁵⁶Mn are discussed. The 0.84-MeV photopeak of ⁵⁶Mn is recommended if steel samples of about the same composition are to be analysed. Chemically analysed steel samples are used as silicon standards. A precision of 0.7% was obtained for an analysis plus standardisation time of 13 min. Special attention was paid to interferences produced by concentration changes of impurity elements. Several possible sources of errors were investigated.     

Collection efficiency of metallic contaminants on si wafer by vapor-phase decomposition-droplet collection.

The collection efficiency of metallic contaminants on four different types of silicon wafers was investigated. P, p+, n and n(+)-type polished silicon wafers were used for the substrate, and 14 metallic elements (Na, Mg, Al, K, Ca, Cr, Fe, Mn, Co, Ni, Cu, Zn, Mo and Ti) were contaminated on silicon wafer surface. Vapor-phase decomposition-droplet collection (VPD-DC) was employed as the sample preparation procedure. For the collecting solution, HNO3, HF and a mixture of HF and H2O2 were used, respectively. A liquid droplet collecting metallic contaminants during VPD-DC was analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). As a result, it was found that HNO3 and HF were not suitable for collecting Cu. Copper was not collected completely in HNO3 and HF. A mixture of HF and H2O2 is the most effective to collect all of the tested metallic elements, regardless of the dopant concentration and type of substrate.     

Study on the solid solubility of transition metals in high-purity silicon by instrumental neutron activation analysis and anticompton-spectrometry

The solid solubility of the 3d metals Cr, Mn, Fe, Co and Ni in high-purity silicon was studied by INAA and electron paramagnetic resonance techniques in the temperature range of ≊600°C–1250°C. The solubility increases with atomic number from Cr to Mn and more distinctly from Co to Ni. For Mn, Fe and Co the solubilities are nearly the same within the experimental errors. An enthalpy of formation (ΔH) of about 2.8 eV was determined for Cr, Mn, Fe and Co, whereas for Ni 1.7 eV was derived. Relatively large diffusion coefficients were estimated from the rather short times, in which saturation of the solid solution was reached. From these observations and from the results of the EPR measurements it is concluded that the 3d metals occupy predominantly interstitial sites in the silicon lattice in thermal equilibrium.     

Instrumental neutron activation analysis as a tool for assessing the solubility of soil mineral matter in strong acid

Fifty samples of natural surface soils with high but variable organic matter content were analyzed for 13 elements (Na, Al, K, Sc, V, Cr, Mn, Fe, Co, Zn, Sr, Ba, La) by INAA. The same samples were analyzed for the “total-recoverable” fraction of these elements by ICP-OES after decomposition with 7M HNO₃, and the results are compared. The data are discussed separately for two groups of samples with organic matter contents of respectively >80% and <70%. In the group with < 70 % organic matter the “total-recoverable” fractions show the following sequence (% of total): Co (83)>Mn (77)>La (60)>Fe=Zn (53)>V (33)>Cr (29)>Sc (25)>Al=Ba (17)>Sr (13)>K (5)>Na (2). The results are in good agreement with corresponding literature data for mineral soils in the case of Al, K, Sc, V, Cr, Fe, and La. In the case of Na, Mn, Co, Zn, Sr, and Ba the present surface soils showed significantly higher “total-recoverable” fractions than the previously studied subsoils. Possible reasons for these differences are discussed. INAA remains a convenient reference technique for determination of total concentrations with the rapidly increasing use of strong mineral acids in environmental studies of elements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sources of heavy metals in the Western Bay of Izmit surface sediments

The study aimed to examine source apportionment of heavy metals of the surface sediments in the <63?µm size fraction. The sediment samples collected from 34 sites at the Western Bay of Izmit were subjected to a total digestion technique and analysed for major (total organic carbon, Al, Fe, Mg, and S) and trace (As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, V, and Zn) elements by inductively coupled plasma-atomic emission spectrometry. The results were compared with the marine sediment quality standards, as well as literature values reported to assess the pollution status of the sediments. A factor analysis/multiple regression (FA/MR) multivariate receptor modelling technique was used for quantitative source apportionment to estimate the contributions from each source of contamination. Source fingerprints were obtained from the literature. A varimax rotated factor analysis was applied to the whole data set, and four probable source types were identified as the iron and steel industry, paint industry, crustal and sewage for heavy metals, explaining about 84% of the total variance. Source apportionment results derived from the FA and FA/MR methods agree well with each other.     

Multi-elemental analysis in biological samples by on-line preconcentration on 8-hydroxyquinoline-cellulose microcolumn coupled to simultaneous ICP-AES

Summary The analytical performance of an on-line oxine-cellulose microcolumn preconcentration system coupled to simultaneous ICP was investigated. Different factors including the pH of the sample solution, the flow rates of sample loading and eluation, the acidity of eluent and different eluents were investigated and optimized. In comparison with continuous aspiration, the signal enhancement factors of eleven elements (Zn, Cu, Ni, V, Cr, Fe, Mn, Co, Pb, Cd and Al) were in the range of 6.4 to 13.5 for peak height (0.5 s) and 3.7 to 5.8 for peak area (15 s), respectively. The influences of matrix ions, such as Ca, Mg, Fe, Cu and NaCl were studied. Performance was demonstrated by simultaneous determination of seven (Zn, Cu, Ni, V, Cr, Fe, Mn) elements in a number of CRMs. Most results were satisfactory, except for iron and chromium. The possible reasons were discussed. Co, Pb, Cd and Al were not available in the simultaneous instrument. Therefore, only the analytical performance was measured for these elements by the sequential instrument.On leave from Shanghai Institute of Metallurgy, Academia Sinica, Shanghai, China 200050     

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.     

Use of neutron-energy moderation for resolving interferences in fast-neutron activation analysis

Four elements, vanadium, chromium, manganese and iron, have been determined in nickel-base samples after measurement of the intensity of two gamma-lines; the 0.85-MeV gamma-ray emitted by (56)Mn (produced from both Mn and Fe), and the 1.44-MeV gamma-ray from (52)V (arising from V and Cr). The two elements contributing to each gamma-peak were assayed separately from data obtained by irradiating each sample twice with neutrons of different energy distributions.     

Quality Control in Element Analysis of Plant Materials

A worldwide laboratory intercomparison was organized by the International Atomic Energy Agency's Analytical Quality Control Services (AQCS) involving the determination of elements in plant materials used for human consumption. The main purpose of this work was to evaluate the performance of our analytical methods including sample preparation and to obtain new reference materials that can be used in our further work. Both materials (spinach and cabbage) were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES) and instrumental neutron activation analysis (INAA). Six subsamples of each material were subjected to our digestion procedure and the solutions were measured by ICP-AES. The dried samples were analyzed using INAA. Up to 26 elements were determined in plant materials. For easy review of our data a score has been calculated based on the reference value for each measured element. According to our results the ICP-AES technique was useful for determination of the following elements: Ba, Ca, Cr, Fe, K, Mn, Mo, P, S, Sr, Ti. The INAA method was reliable for measurement of Ce, Co, Mn, Na, Rb, Th, and V.