Multielement analysis of aluminium by NAA and ICP/AES

The results of neutron activation analysis (NAA) and inductively coupled plasma atomic emission spectrometry (ICP/AES) are compared for aluminium samples in the purity range from 99.7 to 99.998%. The advantages of each method towards the determination of 25 elements is discussed.     

Laser microsampling and multivariate methods in provenance studies of obsidian artefacts

The provenance of obsidian artefacts and raw materials was studied by the multivariate statistical analysis of forty-five samples using elemental composition data obtained by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). One ICP-MS instrument equipped with a quadrupole mass filter and the other based on a time-of-flight analyser were coupled to the same type of laser ablation device (Nd:YAG 213 nm), thereby affording a comparison of the different mass spectrometers in terms of precision and verification of the consistency of the results. The influence of surface roughness (polished raw material vs artefact) and microinhomogeneity on the LA-ICP-MS signal was studied under the optimised working conditions of the laser ablation device. Principal component analysis, correspondence analysis, independent component analysis, multi-dimensional scaling, Sammon mapping and fuzzy cluster analysis were applied and compared in order to reveal statistically significant compositional differences between particular geological sites and to disclose the provenance of the raw materials used in manufacture of the artefacts. Twenty-seven artefacts and eighteen raw material samples from natural resources in the Czech Republic, Slovakia, Italy, Greece, Syria, Iraq, Turkey, Mexico and Nicaragua were examined with special attention focused on samples from Moravia (Czech Republic) and some Near East sites (Tell Arbid, Tell Asmar). The Carpathian origin of the obsidian artefacts was investigated in the Moravian samples using the Pb, Rb and U contents. The Near East samples were classified according to their Sr, Ba, Zr and REE contents as per-alkaline obsidians (Bingöl A/Nemrut Da?) originating from Southeast Anatolia.     

The provenance of archaeological obsidian artifacts from Northern Chile determined by source-induced X-ray fluorescence

A study of provenance of obsidian artifacts from "site 25-Las Estacas", Quebrada de Jorquera (Copiapó, Northern Chile) was carried out by means of X-ray fluorescence, using radioactive sources. Obsidian samples from different Chilean geological regions, located in South Central Chile (Laguna del Maule volcanic area, sources of La Coloradas and La Plata), "Radal Siete Tazas" and the North of Chile (Copiapó Volcano) were analyzed. The analysis was performed using ¹⁰⁹Cd and ²⁴¹Am annular excitation sources and X-ray fluorescence. This allowed the determination of Fe, Cu, Rb, Sr, Y, Zr, and Ba concentrations on samples of ground obsidian from the aforementioned sites. The measured Rb, Sr, and Zr concentrations were used to construct discriminant diagrams, which clearly showed clustering of the samples from the different sources, and the association of the archaeological obsidian sample to the Copiapó Volcano source, which is geographically close to the site.     

On-line preconcentration and ICP determination for trace metal analysis

The use of a closed-loop on-line enrichment procedure in combination with an ICP plasma emission spectrometer has been developed for the analysis of trace metal ions, such as Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The procedure utilizes a preconcentration column filled with an anion exchange resin and 8-hydroxy-7-iodoquinoline-5-sulphonic acid is added to the sample prior to preconcentration. Details on the optimization of pretreatment and instrumental conditions are described. Results obtained for the analysis of river water and antarctic seawater are reported.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Status of NAA facilities in the Advanced Neutron Source

The special features of the Advanced Neutron Source research reactor with planned beginning of construction in 1994 are listed. Pneumatic and beam irradiation facilities will be included and are described in the text of this paper.     

Diffusion of obsidian in the Mediterranean basin in the neolithic period: A trace element characterization of obsidian from Sardinia by instrumental neutron activation analysis

Obsidian samples from Monte Arci in Sardinia (Italy) have been characterized by their minor and trace element concentration in order to find discriminating parameters useful to provenance the prime matter of obsidian artifacts. Obsidian samples were collected both at the SA, SB and SC outcrops and far away from them. All samples were submitted to INAA. The trace element concentration appears to be very useful to discriminate the three flows. Multivariate statistical analysis confirms the satisfactory distinction between the three sources. The assignment of the samples collected far away from outcrops to a specific flow (SC) validates the hypothesis that obsidian blocks might have been washed out by alluvial events.     

X-ray fluorescence analysis of obsidian objects from Catamarca,Argentina

The concentrations of five trace elements (Rb, Zr, Sr, Ti and Mn) and one major (Fe) element have been determined in groups of obsidian samples by wavelength dispersive X-ray fluorescence spectrometry. Two methods were used for different elements on the basis of different excitation conditions and sample preparation procedures. Synthetic standards with compositions similar to those of the igneous stone were prepared into which the analytes were incorporated in solution. The method was used to establish the provenance of a number of prehistoric obsidian artifacts. The results ascertained in these analyses are discussed in this paper.     

Determination of the provenance of majolica ceramics from Europe by thermoluminescence employing principal components

Thermoluminescence data, obtained from majolica pottery after irradiation in the laboratory with gamma rays, were studied using the principal components technique to determine if the places of manufacture of this ceramic are differentiated one from another. A total of ten provenances in Holland, Spain and Italy was established by principal components. Six variables were used for the statistical analysis: the three glow-peaks positions, the relative intensity of the second peak to the first peak, the relative intensity of the third peak to the first peak, and the area under the glow curve.The precision for these parameters was about ± 5%, but the precision of the variables for a suite of standards was much higher. In addition, two groups of sherds collected in Latin America, and previously assigned to the provenances of Cataluna and Sevilla (Spain) by artistic criteria, were investigated in this study. All six samples of Cataluna agreed well with their previous assignment of provenance, but several of the samples assigned previously to Sevilla were not related unambiguously to this provenance, although they were with certainty excluded from other provenances.     

Provenance studies of obsidian artifacts: Trace elements analysis and data reduction

Iron and trace elements, such as rare-earth elements, scandium, rubidium, cesium, tantalum, thorium and uranium were determined by instrumental neutron activation analysis in geological samples of obsidian rocks from the Mediterranean Area and in obsidian artifacts found in some prehistorical human settlements in Italy. REE patterns and discriminant analysis allow a firm identification of the source material of artifacts, thus confirming and implementing fission track data of the same artifacts and rocks on the origin of the obsidian rock used to mould the artifacts.     

Pre-irradiation separations for the ultratrace elemental characterisation of high purity materials by NAA

Ion-exchange and solvent extraction procedures that can enable the use of NAA for the determination of trace elements from gallium matrix, using pre-irradiation separations are discussed. Matrix separation coefficients of the order of 10³–10⁶ are obtained.     

Determination of the provenance of obsidian samples collected in the archaeological site of San Miguel Ixtapan, Mexico State, Mexico by means of neutron activation analysis

Obsidian samples from San Miguel Ixtapan Mexico State, Mexico were analyzed by means of neutron activation. Statistical treatments such as bivariate, cluster and principal-components analyses were applied to the data set. Obsidians were identified as coming from three important sources: Sierra of Pachuca in the state of Hidalgo, Zinapécuaro and Zináparo-Varal in the state of Michoacán. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fast determination of chromium by neutron activation analysis /NAA/ using reactor and epithermal neutrons

Fast determination of Cr by Instrumental Neutron Activation Analysis through the formation of⁵²V from⁵²Cr/n,p/⁵²V by using both reactor and epithermal neutron irradiation is described and evaluated.     

Reference values in blood from inhabitants of Brazil: Br,Cl, K and Na determination using NAA

In this study, bromine (Br), chlorine (Cl), potassium (K) and sodium (Na) were measured in the blood of Brazilian inhabitants from Southeast (S) and Northeast (N) regions. A reference range was established as a function of sex and considering lifestyle factors (non-smokers and non- drinkers). For both regions lower values of K were found in females when compared to males and lower values of Na were found in males compared to females. Increasing trends for Na and Br were observed in the Northeast region.     

Comparative instrumental multi-element analysis I: Comparison of ICP source mass spectrometry with ICP atomic emission spectrometry, ICP atomic fluorescence spectrometry and atomic absorption spectrometry for the analysis of natural waters from a granite region

Summary Multi-element analysis by ICP source mass spectrometry for practically matrix-free natural waters, coming from a granitic area and, therefore, rich in trace elements, has been compared with ICP-atomic emission, ICP atomic fluorescence and atomic absorption spectrometry. The following elements have been investigated and their concentrations are in the decreasing order: Ca, Si, Na, Mg, K, Al; Sr, Mn, Ba, Fe, Rb, Zn, B, U, Y, Li, La, Be, Cs, Co, Cr, V, Sb, Bi, Th, Cu, Cd, Ni, Se, Pb, As, Hg, Mo, Tl, Sn. The concentration ranges were between 10 ppm and <0.01 ppb.As a measure of agreement between the different methods under investigation, two criteria have been used (a) the relative variation coefficient VK (%) of the mean element concentration of an element, determined by different methods in all the 98 water samples and (b) the linear, logarithmic and Spearman rank correlation coefficients between ICP-MS and each of the other methods. Detection limits are given from literature for about 32 elements using different methods.The elements Ca, Na, Mg, K, Mn, Sr, Zn, Fe, Li, Cu have been determined with ICP-MS, ICP-AES and AAS; Al, Ba with ICP-MS and ICP-AES; Si only with ICP-AES, whereas B, Be, Bi, Co, Cr, Cs, Hg, La, Mo, Ni, Pb, Rb, Sb, Sn, Th, Tl, U, V, Y only with ICP-MS. In all 34 of the investigated 36 elements could be analysed by ICP-MS, 14 (from about 20 possible) by AAS, 13 by ICP-AES and 12 by ICP-AFS.The agreement between ICP-MS and ICP-AES as well as between ICP-MS and AAS in most cases is remarkably good according to (a). VK (%) for each element in 98 water samples is in the range from ±2.6 to 10% for Na, Mg, Ca, K, Fe, Sr, Ba, Cu, Li (increasing order). Cd and Zn have unexpectedly higher values (±17.3 and ±20.5%); Cd concentrations are, however, near the detection limit.Comparing the different methods on the basis of correlation coefficients according to (b), gives for the Spearman rank correlation coefficient over the whole range of concentrations, respectively for ICP-MS/ICP-AES, AAS, ICP-AFS in case of Ca: 0.998; 0.984; 0.899; Na: 0.993; 0.991; 0.978; Mg: 0.997; 0.993; 0.959; K: 0.986; 0.942; 0.677; Al: 0.987; -; -; Fe: 0.864; 0.974; 0.701; Mn: 0.989; 0.990; 0.198; Sr: 0.988; 0.992; -; Zn: 0.894; 0.819; 0.300; Cu: -; 0.977; 0.202; Li: -; 0.907; 0.586.It is evident from these trace element concentrations as well as the electrical conductivities, that only about three fourths of the investigated samples are typical granitic waters and the remaining ones are associated with different geological background. The samples have been mainly radon waters with more than 18 nCi/l of Rn-222.

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Vergleichende Instrumentelle Multielementanalyse I: Vergleich von ICP-Massenspektrometrie mit ICP-Atomemissionsspektrometrie, ICP-Atomfluorescenzspektrometrie und Atomabsorptionsspektrometrie zur Analyse natürlicher Wässer aus einem Granitgebiet

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6th Contribution to the principles of trace analysis of elements and radionuclides

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Dedicated to Professor Dr. H. Kelker, Frankfurt, on the occasion of his 65th birthday     

Radiochemical scheme for the determination of molybdenum and uranium in biological materials by NAA

A new universal radiochemical separation scheme for selective and quantitative isolation of molybdenum and neptunium (formed from uranium), from neutron irradiated biological materials has been elaborated. The procedure is based on ion exchange and extraction chromatography with final fixation of molybdenum on a column with -benzoinoxime supported on Bio-Beads SM2 and neptunium on Dowex 1-X8 [No ₃ ^– ]. The separated elements are quantified using gamma-spectrometric measurements. The new NAA method is able to overcome problems associated with high contents of phosphorous in some samples and assures detection limits better than 3 ppb for both elements. The validity of the proposed scheme has been demonstrated by the analysis of several CRM's.     

On the direct determination of metals in lubricating oils by ICP

New equipment and procedures are evaluated for the direct analysis of metals in lubricating oils without the need for sample pretreatment or dilution. A modified Babington principle nebulizer equipped with a sample heater is shown to be capable of producing aerosols from undiluted oils, which are suitable for introduction into an inductively coupled plasma atomic emission spectrophotometer. Heating the samples immediately prior to nebulization greatly increases the output of aerosol and reduces output variations in emission intensity due to differences in oil manufacture and viscosity. The type of organometallic complex used in the preparation of standards is shown to be unimportant if the plasma observation region is properly chosen. Performance of a conventional plasma geometry and an inverted torch geometry on analysis of field collected oil samples is presented.     

Chemical characterisations of Carpathian obsidian sources by instrumental and epithermal neutron activation analysis

Obsidian samples from the Tokaj Mountains (Hungary) and from the neighbouring Zemplin Hills (Slovakia) were analysed by instrumental and epithermal neutron activation analysis for obtaining a “fingerprint” for discrimination of potential natural sources of raw material that would permit tracing the origin of archaeological obsidian artefacts. These techniques fully discriminate the Zemplin Hills sources (Carpathian I, eastern Slovakia) and the Tokaj Mountain sources (Carpathian II, north-eastern Hungary) as well as these Central European sources from those already studied of the Mediterranean basin and adjacent regions.     

Comparison of NAA and ICP-MS for the determination of major and trace elements in environmental sample

Summary Major and trace elements in soil and plant samples, including standard reference materials were determined by means of neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS). The analytical procedure for NAA utilized dried powder samples. The concentration of iodine in soil samples was determined by radiochemical NAA. The irradiated samples were cooled and then counted with a Ge gamma-ray detector connected to a multi-channel analyzer. For ICP-MS analysis, the samples were decomposed by microwave digestion with an acid mixture. The concentration of I in the soil samples was measured by ICP-MS after separation by ignition. The analytical values for most elements in the environmental samples by both methods were in good agreement, whereas sample treatments were different. Measured value of Zr in the soil samples by ICP-MS was about 50% lower than that by NAA. It should be assumed that some minerals of Zr in soil particles were not entirely dissolved by the acid mixture. Analytical results of Cd for three different Cd levels in unpolished rice flour samples (NIES 10-a, b and c) determined by ICP-MS were in agreement with certified values. The concentration of Cd in the sample with the lowest Cd level, as determined by NAA with 57% counting error, was 3 times higher than the certified value.