Trace elements in ancient human bone and associated soil using NAA

The elemental composition of 44 human bone samples and 56 soil samples from the Pre-Colombian Tutu site, St. Thomas, Virgin Islands were determined by neutron activation analysis and atomic absorption spectroscopy. Soils from the site were analyzed for the purpose of assessing diagenetic change in the bone samples after deposition. Twenty two elements were observed in the Tutu bones. The compositional data will be considered for use, along with other archaeological information, to aid in dietary reconstruction at the Tutu site.     

Distribution patterns of Mimbres ceramics using INAA and multivariate statistical methods

The distribution patterns of Classic Mimbres black-on-white bowls and jars were determined by instrumental neutron activation analysis to identify vessel movement between geographically defined regions and between villages within individual regions of southwestern New Mexico. The data set produced and utilized by the various multivariate statistical treatments included multielement neutron activation analysis results for 288 ceramic and clay samples from 15 sites in the Gila, Mimbres and Rio Grande valleys of southwest New Mexico. The results indicate that bowls were more frequently exchanged than jars and distribution frequencies between regions were lower than between villages. Two statistical approaches to the data were compared. In one, cluster analysis of the compositional data was used to form homogeneous groups and the distribution of those groups across sites and regions was examined. In the second, discriminant analysis was used to look for significant differences in composition between regions and sites. The significance of predetermining groups based on collection location as opposed to blind group formation from hierarchical cluster analysis was evaluated in terms of its potential to lead to different interpretations of the data.     

X-ray fluorescence analysis for the study of fragments pottery excavated at Tell Jendares site, Syria, employing multivariate statistical analysis

X-ray fluorescence analysis study of 44 archaeological pottery samples collected from Tell Jendares site north-west of Syria has been carried out. Four samples of the total previous investigated samples were obtained from the kiln found on Tell Jendares site. Seventeen different chemical elements were determined. The XRF results have been processed using two multivariate statistical cluster and factor analysis methods in order to determine the similarities and correlation between the selected samples based on their elemental composition. The methodology successfully separates the samples where three distinct chemical groups were discerned.     

Application of instrumental neutron activation analysis to study ceramic fragments from Damascus Castle site,Syria

Summary Thirty-three archaeological ceramic fragment samples from Damascus Castle archaeological site, Damascus city, Syria, were analyzed using instrumental neutron activation analysis (INAA). 36 elements were determined. These elemental concentrations have been processed using two multivariate statistical methods, cluster and factor analysis in order to determine similarities and correlation between the various samples. Factor analysis confirms that 84.8% of the ceramics samples classified by cluster analysis are correctly classified by cluster analysis. The results provided persuasive evidence that Castle pottery used at least four different clay sources. Moreover, by means of systematic local analysis it will be clear whether these sources are local or not.     

Investigations by various analytical techniques to the correct classification of archaeological finds and delineation of technological features: Late Roman lamps from Egnatia: From imports to local production

Late Roman oil lamps from the archaeological site of Egnatia (Fasano, Brindisi, Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Atomic Spectroscopy, Scanning Electron Microscopy and X-Ray Diffraction analyses were carried out on ceramic body and coatings with the aim of identifying the provenance of lamps, in order to arrive at a correct archaeological classification of finds and to outline their technological features.The analytical results show that the finds differ in raw materials and in production technology. The statistical multivariate treatment of compositional data of ceramic bodies groups the objects into two macro clusters and, according to a study of their different petrographic features and by a comparison with coeval pottery whose provenance is already known, suggests one group to have been imported from North Africa and the other to have been locally produced. Moreover, chemical results and in-depth archaeological analyses allow us to split the imported lamps into two subgroups, hypothesizing the first group to originate from central Tunisia and the second from the north of the same country.The analytical characterisation of finds, by different complementary techniques, has allowed us to identify the raw materials and the technological solutions used by the ancient potters from Egnatia to produce lamps. The potters made lamps which had an external appearance very similar to that of African prototypes, but which were nevertheless different as they employed the locally available materials.     

Determining the local coordination of aluminium in cement using electron energy loss near-edge structure

The local site symmetry of aluminium in Al-substituted calcium silicate hydrate phases, similar to those found in hardened Portland cement pastes, has been determined by experimental measurement and theoretical modelling of the electron energy loss near-edge structure associated with the aluminium K-edge measured using parallel electron energy loss spectroscopy in the transmission electron microscope. Changes in the local aluminium environment were observed between different regions of the microstructure which are explained in terms of aluminium substitution into both tetrahedral silicon and octahedral magnesium sites. This spatially-resolved information is in excellent agreement with²⁷Al and²⁹Si magic angle spinning nuclear magnetic resonance data on bulk samples as well as the predictions based upon compositional trends derived from the results of energy dispersive X-ray and electron energy loss elemental microanalysis. In a wider context we wish to stress the complementarity of both spatially-resolved and bulk spectroscopic techniques, which possess differing degrees of sensitivity, in the analysis of materials science samples.     

Chemical compositional studies of archaeological artifacts: Comparison of LA-ICP-MS to INAA measurements

Summary Multielement analysis of archaeological artifacts for the purpose of correlating chemical composition in an effort to determine provenience has become a well-known and accepted procedure. In this study, inductively coupled plasma-mass spectrometry with laser ablation probe (LA-ICP-MS) for the direct study of solids was used to generate elemental data for comparison with existing instrumental neutron activation analysis (INAA) data. Matrix element Al was used as an internal standard in the ICP work to normalize for variations in sample density and sample mass ablated. While absolute accuracy and precision for the ICP data are inferior to INAA, multivariate statistical analysis of data resulting from the two methods demonstrates a high degree of comparability. Sample cluster assignments differed in only 4.7% (4 out of 86) of the cases. Results show a clear usefulness for LA-ICP-MS in archaeological compositional analysis.     

Snapshots of lignin oxidation and depolymerization in archaeological wood: an EGA‐MS study

Evolved gas analysis‐mass spectrometry (EGA‐MS) was used for the first time to study archaeological wood, in order to investigate its chemical degradation. The archaeological wood was from an oak pile from a stilt house found in the Neolithic ‘La Marmotta’ village (Lake Bracciano, Rome, Italy). The sampling was performed from the external to the internal part of the pile, following the annual growth rings in groups of five. In addition, sound oak wood and isolated wood components (holocellulose and cellulose) were also analyzed, and the results were used to highlight differences because of degradation. Our study demonstrated that EGA‐MS provides information on the thermo‐chemistry of archaeological wood along with in‐depth compositional data thanks to the use of MS. Our investigations not only highlighted wood degradation in terms of differences between carbohydrates and lignin content, but also showed that lignin oxidation and depolymerization took place in the archaeological wood. Mass spectral data revealed differences among the archaeological samples from the internal to the external part of the pile. An increase in the formation of wood pyrolysis products bearing a carbonyl group at the benzylic position and a decrease in the amount of lignin dimers were observed. These were related to oxidation and depolymerization reactions, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

On-site analysis of archaeological artifacts excavated from the site on the outcrop at Northwest Saqqara,Egypt, by using a newly developed portable fluorescence spectrometer and diffractometer

Blue-painted pottery was produced in the New Kingdom, Egypt, and decorated with blue, red, and black pigment. In this study, two newly developed portable instruments, a portable X-ray fluorescence spectrometer and a portable X-ray powder diffractometer, were brought to the site on the outcrop at Northwest Saqqara, an archaeological site in Egypt, to verify their performance in on-site analysis of excavated artifacts at the site. Pigments used for the blue-painted pottery and plasters in the New Kingdom were analyzed by these instruments on the basis of both their chemical compositions and crystal-structural information. The blue pigments were identified as two different pigments, Egyptian blue and cobalt blue. The diffraction pattern of the blue pigment of the painted pottery exhibited that of spinel structure. The XRF spectrum of the blue pigment obtained by the same instrument from the same position indicates the presence of Mn, Co, Fe, Ni, and Zn. The possibility of compositional transitions of the cobalt blue pigment with time was revealed on by detailed analysis of the XRF data. The reason for the transitions is considered together with the archaeological background of the New Kingdom, Egypt.     

TG and DSC investigation of gallstone samples collected from patients submitted to cholecystectomy

In the present work are performed the TG and DSC study of gallstone samples collected from patients submitted to cholecystectomy at the Hospital Universitário Onofre Lopes of Universidade Federal do Rio Grande do Norte, in Natal, Rio Grande do Norte State, Brazil. The gallstone samples were characterized by elemental analysis and infrared spectroscopy. Standard cholesterol was used for all analysis as comparison with the gallstones. Is verified that cholesterol is the main chemical component of all studied gallstone samples. The thermoanalytical study was performed on air and nitrogen atmospheres. The presence of cholesterol as the main chemical component of all gallstone samples is confirmed by TG and DSC results.     

Laser-induced breakdown spectroscopy of archaeological findings with calibration-free inverse method: Comparison with classical laser-induced breakdown spectroscopy and conventional techniques

A modified version of the calibration-free (CF) method was applied to the analysis of a set of archaeological brooches made of various copper-based alloys and coming from the archaeological site of Egnatia (Apulia, Southern Italy). The developed methodology consists in determining the plasma temperature by reversing the set of equations employed in the usual CF algorithm, and it is thus referred to as “inverse method”. The plasma temperature is determined for one certified standard, by using its known elemental composition as an input data, and then applied to the set of unknown samples to evaluate their composition in a CF mode. The feasibility of such an approach is demonstrated by comparing the results obtained with classical LIBS (drawing calibration lines with a series of matrix-matched certified standards) and with independent measurements performed with a conventional technique (LA-ICP-MS).     

Discrimination and Provenances of Phoenician Red Slip Ware Using both the Solid State Electrochemistry and Petrographic Analyses

Solid state electrochemistry based on the voltammetry of immobilized microparticles (VIMP) methodology is applied to a series of 80 Phoenician Red Slip samples from the archaeological sites of Motya (Sicily, Italy), Mogador (Morocco), Ramat‐Rahel (Israel), Sulky (Sardinia, Italy), Tas Silg (Malta), Pantelleria (Italy), and Cádiz (Spain), dated from the 8^th to the 6^th century BC. Upon attachment of sub‐microsamples to graphite electrodes in contact with aqueous H₂SO₄ electrolyte, voltammetric features due to the reduction of Fe(III) minerals and the oxidation of Fe(II) ones, complemented with electrocatalytic effects on oxygen reduction and oxygen evolution reactions, provide characteristic electrochemical fingerprints for pottery samples. A consistent sample grouping discriminating between different potteries from different archaelogical sites, is obtained, all results being consistent with morphological, compositional and mineralogical data. Petrographic analysis supports the grouping, defining the manufacture and firing procedure for the different archaeological context.     

Radioisotope x-ray fluorescence analysis of ancient pottery from Tel Kouzama site in Damascus, Syria

The radioisotope X-ray fluorescence method has been utilized in the analysis of thirty nine archaeological pottery fragment samples from Tel Kouzama site, Damascus city, Syria. The samples were irradiated by a 109Cd radioisotope source (-9 10(8) Bq) for 1000 s. 17 chemical elements were determined. These elemental concentrations have been processed using two multivariate statistical methods, cluster and factor analysis in order to determine similarities and correlation between the various samples. Factor analysis confirms that samples were correctly classified by cluster analysis. These two methods suggest that samples can be considered to be manufactured using four different sources of raw material.     

Gas chromatography/mass spectrometry and pyrolysis-gas chromatography/mass spectrometry for the chemical characterisation of modern and archaeological figs (Ficus carica)

Gas chromatography/mass spectrometry (GC/MS) after alkaline hydrolysis, solvent extraction and trimethylsilylation, and analytical pyrolysis using hexamethyldisilazane (HMDS) for in situ derivatisation followed by gas chromatographic/mass spectrometric analysis (Pyrolysis-silylation-GC/MS) were used to investigate the hydrolysable and soluble constituents, and the polymerised macromolecules of an archaeological fig (Ficus carica) recovered in Zaragoza (Spain), as well as of modern figs. The main aim was to study the compositional alterations undergone by the fig tissues in a particular archaeological environment: the fig was in a vessel and covered by a layer of a mixture of orpiment and gypsum. A comparison between the GC/MS results from modern and archaeological figs revealed that degradative reactions took place, leading to the disappearance/depletion of reactive (unsaturated fatty acids) and sensitive compounds (phytosterols and triterpenes). Py-silylation-GC/MS data provided evidence of a significant degradation of the saccharide and lipid components of the fig tissue, which left a residue enriched in polyphenols and polyesters.     

Analysis of Roman-Hispanic Archaeological Ceramics using Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a useful tool for characterization of archaeological samples because it involves little or no sample preparation, and it allows on-site rapid and nondestructive analysis. In this study, ceramics from the archaeological site of Labitolosa (Huesca) were analyzed qualitatively and quantitatively. Furthermore, a protocol is described for the determination of iron in archaeological materials by interpolating calibration graphs and standard addition. Moreover, the potential of LIBS for direct quantitative analysis of iron in real archaeological materials was evaluated, and optimum analytical conditions were determined. The reproducibility of LIBS spectra from different archaeological samples was investigated as a function of the number of laser shots. The results were compared with those of a reference material.     

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.     

k0-INAA of Venezuelan ceramics and complete statistical analysis to establish their provenance

A group of 46 archaeological figurines samples (ad 1300 and 1500) from Venezuelan mainland and northern island were analyzed by k0-instrumental neutron activation analysis (k0-INAA) to obtain their elemental content and give a step ahead to establish the provenance of the island figurines. In total 37 elemental concentrations were measured with uncertainties between 3 and 20 %. To make the study of provenance, a complete statistical analysis was achieved; Fisher linear discriminant, principal component analysis, hierarchical clustering and the Hotelling T² test were used to this end. Furthermore, not only the 46 samples analyzed in this work by k0-INAA were used, but also 40 samples analyzed by PGNAA and reported by Sajo-Bohus et al. (JRNC 265(2):247–256, 2005) were included in the statistical analysis. It was done in order to increase the size of the data set, and then to obtain from the statistical techniques more reliable results. It was found that a very good differentiation exits between the figurines from the island and from the mainland supporting the idea that the raw materials of the figurines come from different places.     

An archaeometric approach about the study of medieval glass from Siponto (Foggia, Italy)

Medieval glasses, including feet and rims of chalices, fragments of lamps and globular bottles, coming from the archaeological site of Siponto (Foggia, Italy), were analyzed by Inductively Coupled Plasma Emission Spectroscopy and Graphite Furnace Atomic Absorption Spectroscopy for investigating and defining glass production technology in Apulia (Italy) in the Middle Ages, because of the poor understanding currently achieved on either compositional and technological features of medieval glass items. The examined finds, whether colourless or coloured blue, yellow-green, yellow, pink and red, revealed a typical silica-soda-lime-composition. The chemical analysis and the statistical treatment of data allowed to trace former, flux, modifier and, where it is present, the element responsible for colour, clarifying production technology issues. It has been possible to identify, moreover, objects obtained by recycling of cullets or finished items.Finally, this work evaluates the effectiveness of the statistical multivariate treatment by Principal Component Analysis (PCA), Clustering Analysis (CA) and Factor Analysis (FA) on compositional data to obtain technological information in opposition to the conventional binary oxides diagram, which represent the most common, widely assessed, archaeometrical practice to obtain technological information from compositional data.     

Study of prehispanic wall paintings from Xochicalco, Mexico, using PIXE, XRD, SEM and FTIR

The characterization of samples of painted plasters obtained from the archaeological site of Xochicalco, in Central Mexico, is presented. Elemental concentrations of the painted layers were obtained by using proton induced X-ray emission (PIXE). The main crystalline structures of the samples are identified with the help of X-ray diffraction (XRD), while the microstructure is studied by scanning electron microscopy (SEM). The information resulting from the application of these three techniques is used to achieve more accurate values for the elemental concentrations. Additional data regarding organic components of the paintings was obtained through Fourier transform infrared spectrometry (FTIR). Although the latter results only provided reliable data on inorganic components, they help to clarify the results from XRD and confirm those of SEM.