Study of the occupation site for the ancient iron smelters at Samaru-west, Nigeria, using neutron activation analysis

Summary Instrumental neutron activation analysis (INAA) has been employed to investigate the relationship between three ancient occupation sites — Samaru-west, Pantaki and Tsauni in Kaduna State, Nigeria, based on the analysis of cultural deposits at the sites. Samaru-west was found to be related with Pantaki site but not so with the Tsauni site. Elemental profiles for the pottery excavated from each site have been established.     

The interpretation of multielemental INAA data using pattern recognition methods

Three hundred ancient Turkish potsherds were analyzed by instrumental neutron activation analysis, and the resulting data analyzed by several techniques of multivariate statistical analysis, some only recently developed. The programs AGCLUS, MASLOC, and SIMCA were sequentially employed to characterize and group the samples by type of pottery and by site of excavation or collection. Comparison of the statistical analyses by each method provided archaeological insight into the site/type relationships of the samples and ultimately evidence relevant to commercial relations between the ancient communities and to specialization of pottery production over time. The techniques used for statistical analysis were found to be of significant potential utility in the future analysis of other archaeometric data sets.     

Comparative analysis of ancient ceramics by neutron activation analysis,inductively coupled plasma-optical-emission spectrometry,inductively coupled plasma-mass spectrometry,and X-ray fluorescence

The accurate measurement of the maximum possible number of elements in ancient ceramic samples is the main requirement in provenance studies. For this reason neutron activation analysis (NAA) and X-ray fluorescence (XRF) have been successfully used for most of the studies. In this work the analytical performance of inductively coupled plasma-optical-emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) has been compared with that of XRF and NAA for the chemical characterization of archaeological pottery. Correlation coefficients between ICP techniques and XRF or NAA data were generally better than 0.90. The reproducibility of data calculated on a sample prepared and analysed independently ten times was approximately 5% for most of the elements. Results from the ICP techniques were finally evaluated for their capacity to identify the same compositional pottery groups as results from XRF and NAA analysis, by use of multivariate statistics.     

Microwave-assisted versus conventional decomposition procedures applied to a ceramic potsherd standard reference material by inductively coupled plasma atomic emission spectrometry

Inductively coupled plasma atomic emission spectrometry (ICP-AES) is a powerful, sensitive analytical technique with numerous applications in chemical characterization including that of ancient pottery, mainly due to its multi-element character, and the relatively short time required for the analysis. A critical step in characterization studies of ancient pottery is the selection of a suitable decomposition procedure for the ceramic matrix. The current work presents the results of a comparative study of six decomposition procedures applied on a standard ceramic potsherd reference material, SARM 69. The investigated decomposition procedures included three microwave-assisted decomposition procedures, one wet decomposition (WD) procedure by conventional heating, one combined microwave-assisted and conventional heating WD procedure, and one fusion procedure. Chemical analysis was carried out by ICP-AES. Five major (Si, Al, Fe, Ca, Mg), three minor (Mn, Ba, Ti) and two trace (Cu, Co) elements were determined and compared with their certified values. Quantitation was performed at two different spectral lines for each element and multi-element matrix-matched calibration standards were used. The recovery values for the six decomposition procedures ranged between 75 and 110% with a few notable exceptions. Data were processed statistically in order to evaluate the investigated decomposition procedures in terms of recovery, accuracy and precision, and eventually select the most appropriate one for ancient pottery analysis.     

Photon and proton activation analysis of iron and steel standards using the internal standard method coupled with the standard addition method

The internal standard method coupled with the standard addition method has been applied to photon activation analysis and proton activation analysis of minor elements and trace impurities in various types of iron and steel samples issued by the Iron and Steel Institute of Japan (ISIJ). Samples and standard addition samples were once dissolved to mix homogeneously, an internal standard and elements to be determined and solidified as a silica-gel to make a similar matrix composition and geometry. Cerium and yttrium were used as an internal standard in photon and proton activation, respectively. In photon activation, 20 MeV electron beam was used for bremsstrahlung irradiation to reduce matrix activity and nuclear interference reactions, and the results were compared with those of 30 MeV irradiation. In proton activation, iron was removed by the MIBK extraction method after dissolving samples to reduce the radioactivity of⁵⁶Co from iron via⁵⁶Fe(p,n)⁵⁶Co reaction. The results of proton and photon activation analysis were in good agreement with the standard values of ISIJ.     

Chemical characterization of Bronze Age pottery from Greek South Aegean islands by INAA

This paper presents the results on 20 minor and trace elements of a wide analytical programme — based on neutron activation and statistical analysis — which deals with the chemical characterization of pottery from the Cycladic islands and Crete, during the Bronze Age (Cycladic period), with particular reference to Akrotiri on Thera. Multivariate analysis of the neutron activation data showed that the majority of the pottery found in Akrotiri was locally made, by one type of clay. This in connection with the local style that Akrotiri had introduced, supports the idea of an autonomous development. Contacts with neighbouring islands were also confirmed.     

On the determination of silicon in pottery

To study the nature of ancient and modern pottery it is necessary to be able to determine the concentrations of the major constituent elements. For such studies, mass balances calculated from these elemental concentrations cluster around 100% for a silicate-silica matrix and around 80–90% in highly calcarious pottery which has a silicate-carbonate (silica) matrix. This work requires experimental measurements with coefficients of variation wihtin approximately ±5%. The high concentrations of silicon in pottery may reasonably be determined by neutron activation analysis using the nuclear reaction²⁹Si(n, p)²⁹ Al. Aluminium-29 has a half life of 6.56 minutes and a γ-ray energy of 1272 keV. Epithermal neutron irradiations of samples in cadmium foil are required to minimize the quantities of thermal neutron induced radionuclides. The method of analysis developed for the low flux SLOWPOKE reactor is described and the accuracy and precision of the technique is discussed by allusion to analyses of standard reference materials. The application of this technique to two different archaeological problems is addressed. The first is a case of carbonate dilution found in neolithic pottery from Iran and the second case is a problem of silica dilution in Roman pottery from Germany.     

Instrumental neutron activation analysis of “melian”potsherds

Instrumental neutron activation analysis has been applied for the determination of 20 minor and trace elements (As, Ce, Co, Cr, Cs, Eu, Fe, Hf, La, Lu, Na, Rb, Sb, Sc, Sm, Ta, Tb, Th, Yb and Zn) in two groups of potsherds which had been excavated at two different sites of Greece, the islands of Thasos (Group A) and Delos (Group B). A good agreement for all the elements examined between the pottery specimens of Groups A and B was found. The matching in chemical composition between the stylistically related potteries of Group A (Thasos) and Group B (Delos) provides strong support for the archaeologist's hypothesis that the two groups of potsherds belong to the same major group of “melian” pottery.     

An attempt to select suitable elements to characterize an ancient ceramic by neutron activation analysis

The classification of pottery into groups having the same provenience can be determined by several different methods: activation analysis allows dosing of a number of elements and seems to be a promising method of analysis. But the number of elements capable of characterising a group must be limited. To show the slight variation in the major and trace element concentrations present in the same ancient ceramic, special care was taken in the irradiation and the spectrometric analysis of the samples. The results of the analysis of the 12 samples surveyed are given. We attempted to represent the curves of isoconcentration. Activation analysis allows definition of a pottery group by analysis of easily dosed elements such as Hf, Sc, Co, Cr, Ti and V.     

Analysis of large and non-standard geometry samples of ancient potteries by internal monostandard neutron activation analysis using in situ detection efficiency

The k ₀-based internal monostandard neutron activation analysis (IM-NAA) method was used for the analysis of 30 large and non-standard geometry ancient pottery samples obtained from Buddhist sites of Andhra Pradesh, India. One freshly finished pottery and a sun-drenched pottery were also analyzed for comparison. Samples were irradiated in thermal column facility of Apsara reactor and also in graphite reflector position of critical facility of Bhabha Atomic Research Centre. Radioactive assay was carried out using a 40% relative efficiency HPGe detector coupled to MCA. Concentration ratios of 15 elements with respect to Sc were determined. The La/Ce values as well as statistical cluster analysis utilizing concentration ratios of elements were used for grouping/provenance of the potteries.     

Determination of trace and minor elements in coal: A comparison between instrumental photon and thermal neutron activation analysis

Instrumental photon and neutron activation techniques have been compared through the determination of sixteen major, minor and trace constituents in two British Columbian coals and a standard coal. Between the two techniques, the results generally agreed to within one standard deviation with replicate precision being maintained, for both techniques, below twenty percent at worst and down to five percent or better for several elements. Almost all of the elements having environmental, industrial or economic significance in fossil fuels can be determined with good sensitivity by either of these two methods, both of which share the advantages of being non-destructive and multi-element in nature and sufficiently accurate as demonstrated in this paper.     

Combined non-destructive XRF and SR-XAS study of archaeological artefacts

We report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as “proto-majolica” pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples’ speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent.     

Instrumental multielement activation analysis of soil samples

Soil samples from a waste water cleaning facility in Berlin, Germany, have been analyzed using several activation analysis methods. 43 elements have been determined by instrumental high energy photon activation analysis (PAA), instrumental thermal neutron activation analysis (NAA) and 14 MeV neutron activation analysis (fNAA). Conventional gamma ray spectroscopy and low energy photon spectroscopy (LEPS) have been applied for product activity measurement. It has turned out that these methods in combination offer a wide spectrum of analytical information.     

Investigation of ancient pottery from Lefkanti,Greece, by epithermal gamma spectroscopy using loss-free counting technology

For the analysis of pottery fragments from ancient Lefkanti, instrumental neutron activation analysis was used. To have a good throughput of samples, a detectable series of short-lived isotopes was selected for the investigation. The problem of the initial high radioactivity, which normally hinders a fast -spectroscopic analysis, was eluded by using loss-free counting technology. This technology allows the measurement of pottery samples of about 100 mg size 1 day after a 30 min epithermal irradiation. Up to 15 samples could be analyzed in one day under these working conditions, having the possibility to analyze the elements As, Eu, Ga, Gd, La, Mn, Sb, Sm, Th, U, W and Zn, which are enough to perform statistical characterizations of potteries.     

Mössbauer studies of Algerian ancient pottery

Mössbauer spectroscopy and a set of refiring experiments have been used to characterize ancient potsherds coming from the archaeological site of Gueldamane. Information about the original firing techniques and conditions has been deduced from the refiring experiments and a firing process has been proposed for Gueldamane pottery.     

Instrumental photon activation analysis of coal fly ashes using the internal standard method coupled with the standard addition method

Multielement determinations of coal fly ashes (NIST SRM-1633a and BCR CRM-38) have been carried out by instrumental photon activation analysis using 30 MeV bremsstrahlung and the internal standard method coupled with the standard addition method. In these determinations, some major and minor constituent elements in the samples were properly used as effective internal standards. As a result, it was demonstrated that concentrations of 18 elements were determined accurately and precisely. Furthermore, a similar multielement determination has also been examined using 20 MeV bremsstrahlung. In this case, it was proved that better results can be achieved, because all interfering reactions were eliminated completely.     

Classification of Korean old potteries by trace elements analysis

Instrumental neutron activation analysis (INAA), ICP/MS and XRF were applied for the characterization of relative locales of Korean old potteries, which had three different era and four regional characters. From the elemental analysis, two major elements such as Fe, Ti and some minor elements such as Cr, Sc, Zr were supposed to the main contributing factors for the regional classification. And the contents of rare earth elements, such as Eu and La were different in each pottery.     

Wet-chemical analysis and determination of trace elements by neutron activation in meteorites

As a contribution to the cosmochemical distribution of elements, 35 meteorites of the collections of the Museum of Natural History in Vienna, the Mineralogical-Petrographical Institute and the Analytical Institute of the University of Vienna were analyzed. In the meteorites main and minor constituents were determined by wet-chemical methods, whereas for the determination of about 16 trace elements neutron activation analysis was employed. This paper has been dedicated to Prof. Dr.J. W. Breitenbach on the occasion of his 60th birthday.     

Iron Forms Fe(II) and Fe(III) Determination in Pre-Roman Iron Age Archaeological Pottery as a New Tool in Archaeometry

This article presents studies on iron speciation in the pottery obtained from archaeological sites. The determination of iron forms Fe(II) and Fe(III) has been provided by a very simple test that is available for routine analysis involving the technique of molecular absorption spectrophotometry (UV–Vis) in the acid leachable fraction of pottery. The elemental composition of the acid leachable fraction has been determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Additionally, the total concentration of the selected elements has been determined by X-ray fluorescence spectrometry with energy dispersion (EDXRF). The results of the iron forms’ determinations in archaeological pottery samples have been applied in the archaeometric studies on the potential recognition of the pottery production technology, definitely going beyond the traditional analysis of the pottery colour.     

A standardless approach of INAA for grouping study of ancient potteries

The k ₀ based internal monostandard neutron activation analysis was used to analyze 41 ancient pottery samples from three major locations of Andhra Pradesh state, India, belonging to two different age groups namely Megalithic and Buddhist periods. Samples were irradiated with neutron flux obtained from CIRUS reactor and radioactive assay was carried out using a 40% relative efficiency HPGe detector coupled to 8?k MCA. Concentration ratios of 21 elements were calculated with respect to internal monostandard Sc. Absolute concentrations for six (three each from both Megalithic and Buddhist periods) representative samples along with a modern pottery were obtained for comparison. Elemental concentration ratios with respect to Sc were used for grouping of these archaeological samples. Preliminary grouping of these artifacts was done using La/Ce values, and the grouping was confirmed by statistical cluster analysis using eleven selected trace elements. The IAEA RM SL-3 sample was analysed for validation of the method, where in both concentration ratios and absolute concentrations were calculated.