Provenance studies of ancient Etruscan marble monuments and Sardinian pottery by neutron activation analysis and data reduction

The development of a trace element fingerprint as obtained by trace element determination and data reduction has been successfully applied to clear out correlations and similarities among objects of archaeological interest. In the present paper instrumental neutron activation analysis and statistical data treatment were used to solve two archaeological question: (1) the search of white marble quarries which Etruscans were used to exploit to manufacture monuments and sculptures; (2) the search of similarity, and possibly of provenence, among pottery fragemets excavated in Sardinia and belonging to the eneolithic period. Trace element matrices are presented and discussed. Data treament, such as rare-earth element pattern and pattern recognition procedures, is reported and discussed.     

Provenance studies of the white marble of the cathedral of Como by neutron activation analysis and data reduction

Marble samples from major Italian quarries and from the Como Cathedral were analyzed for their trace element content, which is indicative of their provenance. Ca, Sc, Cr, Mn, Fe, Co, Rb, Sb, Cs, Ba, La, Ce, Sm, Eu, Gd, Ho, Tm, Yb, Lu, Hf, Th and U elements were determined by neutron activation analysis. Results as well as their precision and accuracy are presented and discussed. Data treatment has allowed to characterize the marble quarries on the basis of their trace element content, to identify the provenance of the marble used in the Como Cathedral and to show differences in the element distribution of new and weathered marble samples from the same quarry.     

Trace elements analysis in rice

Various rice species, marketed in Austria, were analyzed for their Se, Cr, Ni, Rb, Fe, Co, Cs, Ag and Hg contents by neutron activation analysis. The concentration values found for Se ranged between 0.023 and 0.265 ppm, for Cr 0.540–1.875 ppm, for Ni 0.359–0.965 ppm, for Rb 1.604–6.400 ppm, for Fe 24.3–139.8 ppm, for Co 0.026–0.055 ppm, for Cs 0.016–0.032 ppm, for Ag 0.0006–0.0034 ppm, for Hg 0.003–0.023 ppm. Statistical analysis showed in the majority of cases that there is a significant difference in Se, Cr, Ni, Rb, Fe, Co, Hg contents but not in Cs. Highest values of Se and Fe were found in rice from Belgium /long seed, super patna/, whereas the Cr concentration was the highest in rice from Thailand /siam patna/. Ni was highest in rice from Uncle Ben's, Rb in Kresto from USA.     

Provenance and use wears of Pre-Hispanic obsidian scrapers from Metztitlan, Hidalgo, Mexico

The research was performed with archaeological obsidian scrapers, collected at the Metztitlan area, Hidalgo, Mexico. The provenance of the raw material was determined by NAA. SEM technique was applied to identify use wears on pre-Hispanic tools and experimental replicas. The Metztitlan scrapers made of the obsidian of Zacualtipan, Hidalgo, Mexico, were probably used for Agave juice extraction in the Late Postclassical period.     

Neutron activation analysis for provenance studies of archaeological artifacts

Differences in composition of archaeological artifacts may only in distinct cases be interpreted in terms of provenance differences. This point is discussed with examples: the large number of elements analyzed with precision and the relative lack of sensitivity of many of them to the presence of crystalline inclusions, made of NAA the method most commonly used for provenance studies of ceramics.     

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.     

Neutron activation analysis in forensic investigations: Trace elements characterization of cigarettes

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO₂-P, was prepared by impregnating a crown ether derivative, 4,4￠,(5￠)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO₂-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO₃ This revised version was published online in July 2006 with corrections to the Cover Date.     

Trace element abundances in stone artifacts and related materials from Japan by neutron activation analysis. An approach to archaeological provenience studies

Instrumental neutron activation analysis was carried out for trace elements in green tuff cylindrical beads (KUDATAMA) and obsidians unearthed from the sites with special reference to their archaeological provenience studies. An approach based on the characteristic index elements, the correlation diagrams of some of the elements interested, and the abundance patterns of some of rare earth elements is valid for clarifying the different source regions.     

Trace elements in coloured opals using neutron activation analysis

Neutron activation analysis was used to determine the concentration of trace elements in 50 samples of orange, yellow, honey, green, blue and pink opals as well as 18 samples of colourless opals taken from a number of recognised fields in Australia, Peru, Mexico and USA. The results were evaluated to determine the relationship between trace element content and opal colour.     

Trace elements in Australian opals using neutron activation analysis

Neutron activation analysis was used to determine the concentration of trace elements in 42 samples of black, grey and white opals taken from a number of recognised Australian field. The results were evaluated to determine if a relationship existed between trace element content and opal colour.     

Trace elements in precious and common opals using neutron activation analysis

Neutron activation analysis (NAA) was used to determine the concentration of trace elements in 44 precious and 52 common opals sampled from a number of recognised fields within Australia. The purpose of this study was to determine if precious and common opals of the same colour and location have the same or a different trace element profile. Similar numbers of black, white and grey samples were studied in each case. In most cases common opals had a significantly higher concentrationof certain trace elements when compared with precious opals.     

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.     

Trace elements in human bone determined by neutron activation analysis

There is an evidence that some of the essential trace elements are crucial determinants of bone health. Excess or deficiency of these elements has a role in the development of bone diseases, therefore research on trace elements in bone is very important. Iliac crest bone biopsies were optioned from twelve persons undergoing orthopedic surgery due to any reason than osteoporosis. Cortical and trabecular parts were separated, and blood and fats were removed. Up to 30 minor and trace elements were determined in these samples by instrumental neutron activation analysis and other techniques and their relations were discussed.     

Trace elements distribution in Antarctic sediments by neutron activation analysis

In the present investigation iron and trace elements were determined by instrumental neutron activation analysis in a number of sea bottom sediment samples, collected in the Ross Sea and close to the Italian Station at Terra Nova Bay in Antarctica. Full listing of results is presented and discussed as well as the evaluation of precision and accuracy. In order to find correlations and similarities among the sediment samples, the analytical data were submitted to statistical treatment. In addition rare earth element patterns were obtained. Typical trends were observed with no evident Eu negative anomaly and a depletion of heavy rare earth elements.     

Trace elements in soil: Their determination and speciation

Summary The different types of soil analysis are reviewed in-outline and some recent developments and methodologies are discussed.For the determination of the total trace element content of soils, conventional, multi-element, solid sample methods including d.c. arc optical emission and spark source mass spectrometric procedures are briefly considered together with the potential of current X-ray fluorescence, solid sample graphite furnace atomic absorption and glow discharge mass spectrometry.The use of strong acid digestion, with for example aqua regia, for the determination of pseudo-total concentrations of heavy or toxic metal accumulations in soil is described.The limitations of solution methods for multi-element analysis of soils are outlined together with the prospects for the use of soil slurries to eliminate the sample preparation and dilution problems associated with the dissolution of soils. The difficulties in taking reproducible and representative samples of inhomogeneous materials such as soils are highlighted.Trace element speciation can be defined as the identification and quantification of the different forms or phases in which they occur in soils. Some examples of such procedures and extractants for both essential and toxic elements in soils are presented. The difficulties of trace element speciation in soils as distinct from soil extracts or soil solutions are illustrated briefly.     

Spectrophotometric data reduction by eigenvector analysis for equilibrium and kinetic studies and a new method of fitting exponentials

The investigation of multicomponent mixtures by spectrophotometry is described. A desk computer, APPLE II, is used to calculate the number of absorbing species in a series of measured spectra by matrix rank analysis. Representation of the observed spectra as linear combinations of eigenvectors leads to significant reduction of the data set, so that a nonlinear least-squares fit based on the Newton—Gauss—Marquardt algorithm is possible on a small computer. As an example, the complexation of copper(II) with 1,4,7-triazaheptane (dien) was studied by combined spectrophotometric and pH titration. The spectra of 62 mixtures at 26 wavelengths were analysed; the number of absorbing species, their spectra and the underlying equilibrium constants were determined. Representation of kinetic curves as linear combinations of eigenvectors is described. It is shown that instead of finding the minimum of the square sum in a multidimensional rate constant space, these minima can be found in a one-dimensional space. Two examples are given: the first is theoretical whereas the second is based on the kinetics of dissociation of the μ-peroxo complexes formed between cobalt(II), oxygen and 4,7,10-triazatridecanedioic acid in acidic solution.     

Provenance study of obsidian samples by using portable and conventional X ray fluorescence spectrometers. Performance comparison of both instrumentations

The potentiality of portable instrumentation lies on the possibility of the in situ determinations. Sampling, packaging and transport of samples from the site to the laboratory are avoided and the analysis becomes non destructive at all. However, detection limits for light elements are, in most cases, a limitation for quantification purposes. In this work a comparison between the results obtained with an X ray fluorescence spectrometer laboratory based and a portable instrument is performed. A set of 76 obsidian archaeological specimens from northwest Patagonia, Argentina was used to carry out the study. Samples were collected in the area of the middle and high basin of the Limay River. The analytical information obtained with both instrumentations was complemented with Principal Component Analysis in order to define groups and identify provenance sources. The information from both instruments allows arriving to the same conclusion about sample provenance and mobility of hunter-gatherer groups. Three groups of sources were identified in both cases matching with the geographical information. Also, same sets of outlier samples or not associated to these sources were found. Artifact samples were associated mainly to the closest sources, but some of them are related to sources located more than three hundred kilometers, evidencing the large mobility of the hunter-gatherers by the obsidian interchange. No significant differences between concentrations values obtained by laboratory based instrument and portable one were found.