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.     

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.     

Analysis of pottery samples from Bourewa, the earliest known Lapita site in Fiji

We have carried out a thorough mineralogical analysis of 16 pottery samples from the Lapita site of Bourwera in Fiji, using micromorphological techniques with optical and polarising microscopes. While the overall mineralogy of all of the samples is similar the samples clearly divide into two groups, namely those with or without the mineral calcite. Our findings are backed up by chemical analysis using SEM-EDX and FTIR. SEM-EDX shows the clear presence of inclusions of calcite in some of the samples; FTIR shows bands arising from calcite in these samples. The study suggests that it is likely that more than one clay source was used for production of this pottery, but that most of the pottery comes from a single source. This finding is in line with previous studies which suggest some trading of pottery between the Fijian islands but a single source of clay for most of the pottery found at Bouwera. We found no evidence for the destruction of CaCO(3) by heating upon production of the pottery in line with the known technology of the Lapita people who produced earthenware pottery but not high temperature ceramics.     

Indoor radon concentration levels in Mexican caves, using nuclear track methodology, and the relationship with living habits of the bats

This work presents the results of a study of the radon levels in four caves in Mexico: Los Riscos Cave and El Judío Cave in the State of Querétaro, and Coyozochico Cave and Karmidas Cave in the State of Puebla. The measurements were made using the passive closed-end cup system, with CR-39 (Lantrack^®) as detection material, and following protocols established for the measurement of indoor radon, developed at the Dosimetry Applications Project of the Physics Institute of the Universidad Nacional Autónoma de México. The radon concentration at one location with Karmidas Cave reached more than 60,000 Bq/m³, while concentrations in the other three caves varied from 83.1–1216.0 Bq/m³, was found. During the study was observed an interesting coincidence between the radon concentration distribution inside the caves, and the bat colonies location. In general, the bat colonies are located at the medium or low radon concentration levels zones.     

Dating and classification of Syrian excavated pottery from Tell Saka Site,by means of thermoluminescence analysis,and multivariate statistical methods,based on PIXE analysis

Thermoluminescence (TL) dating and Proton Induced X-ray Emission (PIXE) techniques have been utilized for the study of archaeological pottery fragment samples from Tell Saka Site, which is located at 25 km south east of Damascus city, Syria. Four samples were chosen randomly from the site, two from third level and two from fourth level for dating using TL technique and the results were in good agreement with the date assigned by archaeologists. Twenty-eight sherds were analyzed using PIXE technique in order to identify and characterize the elemental composition of pottery excavated from third and fourth levels, using 3 MV tandem accelerator in Damascus. The analysis provided almost 20 elements (Na, Mg, Al, Si, P, S, K, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb). However, only 14 elements as follows: K, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb were chosen for statistical analysis and have been processed using two multivariate statistical methods, Cluster and Factor analysis. The studied pottery were classify into two well defined groups.     

Gross alpha and gross beta radioactivity in drinking water from Zacatecas and Guadalupe cities, Mexico

The conditions to measure the gross alpha and gross beta radioactivity in water samples from Zacatecas and Guadalupe cities in the State of Zacatecas, Mexico were established. The gross alpha and beta radioactivity of water samples were measured using a liquid scintillation detector. The results show that the gross beta radioactivity in all cases is lower than the maximum contaminant level and the gross alpha radioactivity is higher in the samples collected from Guadalupe City and in the samples collected from the Southwest of Zacatecas City.     

Analytical characterization of paintings on pre-Roman pottery by means of spectroscopic techniques. Part II: Red, brown and black colored shards

As a part of a systematic study aimed at assessing the chemical composition of ancient pigments as well as at collecting information useful for the understanding of the technical aspects related to pottery preservation and decoration, the results of analysis performed on red, brown and black pigments decorating pre-Roman pottery excavated in thirteen different tombs unearthed in the archaeological zone of Canosa (Puglia, Italy) are presented. Both surface (XPS) and bulk (FT-IR) spectroscopies were used which gave complementary information and XRD was used in some cases to further support the spectral assignments. Results suggested that the shards characterized by “nominally” the same color could be differentiated by the chemical composition of the pigmented layers; in particular, the shards exhibiting the red pigment could be divided into three groups containing, respectively, either hematite or ochre plus other substances not related to the color but of great concern for the understanding of ancient techniques used for color preparation. Manganese oxides were found to be the basis of the brown pigments, which could be divided into three groups on the basis of Mn and Fe contents. Either magnetite or carbon of vegetable origin was found in the black-pigmented layers. Furthermore, an attempt was made to find a possible correlation between this classification and the results of a provenance study carried out on the same pool of shards analyzed in the present investigation. Received: 28 May 1999 / Revised: 6 August 1999 / Accepted: 21 August 1999     

Analytical characterization of paintings on pre-Roman pottery by means of spectroscopic techniques. Part II: Red, brown and black colored shards

As a part of a systematic study aimed at assessing the chemical composition of ancient pigments as well as at collecting information useful for the understanding of the technical aspects related to pottery preservation and decoration, the results of analysis performed on red, brown and black pigments decorating pre-Roman pottery excavated in thirteen different tombs unearthed in the archaeological zone of Canosa (Puglia, Italy) are presented. Both surface (XPS) and bulk (FT-IR) spectroscopies were used which gave complementary information and XRD was used in some cases to further support the spectral assignments. Results suggested that the shards characterized by “nominally” the same color could be differentiated by the chemical composition of the pigmented layers; in particular, the shards exhibiting the red pigment could be divided into three groups containing, respectively, either hematite or ochre plus other substances not related to the color but of great concern for the understanding of ancient techniques used for color preparation. Manganese oxides were found to be the basis of the brown pigments, which could be divided into three groups on the basis of Mn and Fe contents. Either magnetite or carbon of vegetable origin was found in the black-pigmented layers. Furthermore, an attempt was made to find a possible correlation between this classification and the results of a provenance study carried out on the same pool of shards analyzed in the present investigation.     

Microscopy, porosimetry and chemical analysis to estimate the firing temperature of some archaeological pottery shreds from India

In recent times, science and technology have been applied to the world of cultural heritage, preservation and conservation. In the present study, the pottery samples belonging to 4th century were collected from Tandikkudi in Dindugul district of Tamilnadu, India and were subjected to chemical analysis to outline the information about the raw materials and technological–productive aspect such as firing temperature. Investigations such as Scanning Electron Microscope and Energy Dispersive Spectrometer (SEM/EDS) are also done for the accurate observation of the morphology and the qualitative and Semi-quantitative determination of the chemical elements present in the sample. The firing temperature of the samples at the time of manufacturing is also estimated from apparent porosity of the samples which agrees well with the SEM analysis. The results obtained from different analytical techniques on pottery shreds provide information of the firing temperature of the pottery which lies in the range of 800 °C–1000 °C in the oxidizing atmosphere. Moreover it was observed that the samples collected from this site are low refractory in nature and the artisans of Tandikkudi have used both calcareous and non-calcareous clays for their household utilities, but were unaware of firing their artifacts at reduced atmosphere or closed kiln. Hence this paper is a useful analytical tool for predicting the firing atmosphere, type of clay (calcareous, non calcareous) and its nature (fine and coarse). Hence this paper is suitable for estimating the firing temperature of ancient potteries.     

Archaeometric characterization of ancient glazed pottery sherds from Khirbet Faris, Jordan by inductively coupled plasma mass spectrometry (ICP-MS)

Multielement analysis of sixteen Ayyubid–Mamluk glazed pottery sherds was done for determination of chemical composition in order to study their provenance. The sherds tested in the present research come from the historical site of Khirbet Faris on the Karak Plateau in Jordan. The chemical analysis was carried out by inductively coupled plasma mass spectroscopy (ICP-MS). Mg, Al, Ti, V, Cr, Mn, Ni, Cu, Mo, Bi and U have been determined in the studied samples. The data were analyzed by using principal component analysis PCA and hierarchical cluster analysis with Bray-Curtis in order to define grouping of different glazed potteries by obtaining information about their similarity and clustering. The results of chemical analysis provided persuasive evidence that the Khirbet Faris pottery sherds have at least three different sources of provenance.     

A digital coding combination analysis for mutational genotyping using pyrosequencing

In the present study, we developed a novel digital coding combination analysis (DCCA) to analyze the gene mutation based on the sample combination principle. The principle is that any numerically named sample is divided into two groups, any two samples are not grouped in the same two groups, and any sample can be tested within the detection limit. Therefore, we proposed a specific combination that N samples were divided into M groups. Then N samples were analyzed, which could obtain the mutation results of M mixed groups. If only two groups showed positive (mutant type) signals, the same sample number from two positive signal groups would be the positive sample, and the remaining samples were negative (wild type). If three groups or more exhibited positive results, the same sample number from three positive signal groups would be the positive sample. If some samples remained uncertain, individual samples could be analyzed on a small scale. In the present study, we used the two genotypes of a mutation site (A5301G) to verify whether it was a useful and promising method. The results showed that we could quantitatively detect mutations and demonstrate 100% consistent results against a panel of defined mixtures with the detection limit using pyrosequencing. This method was suitable, sensitive, and reproducible for screening and analyzing low-frequency mutation samples, which could reduce reagent consumption and cost by approximately 70–80% compared with conventional clinical methods.     

Application of chemical and chemometric analytical techniques to the study of ancient ceramics from Dougga (Tunisia)

In the present paper chemical characterization has been carried out on 67 shards of archaeological pottery from Dougga (North Tunisia). The analysed shards, dated to the Byzantine period (VI–VII century A.D.), belong to the three ceramic classes African Red Slip Ware, Dougga Ware and African cooking Ware. Fourteen elements have been determined by both atomic emission spectroscopy with flame as source (AES) and by using an inductively coupled plasma source (ICP-OES). The data acquired have been treated by statistical techniques in order to define grouping for the examined shards. Both unsupervised and supervised methods have been employed in order to define groups of different pottery shards. As a comparison, some samples (control group) coming from Southern Tunisia have been examined. All the statistical methods employed have evidenced how the control group, as concerns the chemical composition, is clearly distinguishable from Ain Wassel samples which are highly homogeneous. In fact because of the compositional homogeneity of the Northern Tunisia productions, it is quite difficult to establish a good classification and distribution of the samples in well defined cluster. Nevertheless supervised analysis has evidenced how, among the three classes, the African cooking Ware is the more distinguishable one confirming the archaeologists' hypothesis that Dougga Ware is an imitation of African Red Slip Ware.     

Chemical characterization of ancient potteries from Himera and Pestavecchia necropolis (Sicily, Italy) by Inductively Coupled Plasma–Optical Emission Spectrometry (ICP–OES)

Thirty-eight samples of pottery were analyzed for determining chemical composition in order to establish their provenance. The potteries tested in the present research come from Himera and Pestavecchia archaeological sites. After digestion in microwave oven, the samples have been analyzed for fourteen minor elements (Ba, Cd, Co, Cr, Cu, Ga, Li, Mn, Ni, Pb, Sr, Ti, Tl, and Zn) and six major elements (Al, Ca, Fe, K, Mg, and Na). Chemical analysis was carried out by Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP–OES). The most abundant minor elements are Cr, Ba and Ni. Cr concentration ranged from 66 to 3635 mg kg^{− 1}, Ba concentration ranged from 388 to 2677 mg kg^{− 1} and Ni concentration ranged from 35 to 1758 mg kg^{− 1}. The relative standard deviation (RSD) of the replicates on the concentrations of analyzed metals ranged from 0.07% to 14%.The aim of this study is to assign the local or non-local provenance of the examined potteries, in particular validating and clarifying archaeological hypothesis based on the simple visual examination and stylistic characterization of ceramic objects. Principal component analysis performed on the dataset, together with the application of cluster technique and non statistical analysis, allowed the identification of three main groups of samples and a lonely one (R 97). In particular, sample R 97 shows high Cr concentration (3635 mg kg^{− 1}) and high Ni concentration (1758 mg kg^{− 1}), typical of Corinthian pottery. The results of chemical analysis show that the stylistic features are not always sufficient to correctly identify the origin of a ceramic object.     

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.     

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.     

PIXE analysis of Tillandsia usneoides for air pollution studies at an industrial zone in Central Mexico

In order to find out if there is a relation between atmospheric particulate matter composition and human health effects, metals and other elements measurement are performed. Analysis of atmospheric aerosols collected in filters is the usual method to achieve this task. Biological monitors provide an advantageous alternative way of sampling, since there is no need of special sampling devices, and accumulation time can be as long as desired. In this study, Tillandsia usneoides a reliable air pollution biological monitor that occurs naturally throughout Mexico was used to monitor air quality of Tula–Tepeji corridor at central Mexico. This area is considered critical zone because of atmosphere contaminants high concentration. Some biomonitors were transplanted from a clean environment to four sites at the Tula corridor. Plants samples were collected every two weeks from February to April 2008. PM₁₀ sampling in filters was also performed simultaneously at three locations where T. usneoides was transplanted, for a comparison. Chemical composition was determined by PIXE. Results showed that T. usneoides incorporates anthropogenic elements reaching maximal levels after 6 to 10 weeks approximately. Since results obtained with biomonitors agree with those obtained with aerosol filters, T. usneoides could be employed as a first approximation to provide insights of the atmospheric pollution level previous to a detailed study using filters.     

Geochemical studies of Guarani ethnic groups pottery with XRF

Artefacts of pottery belonging to the Guarani ethnic group were investigated by XRF techniques. The Tupi-Guarani, is one of the three main representatives of the Neolithic culture in the Amazonian scope. Such an ethnic group dispersed towards the South; in the Paraguayan area between the Paraguay and the Parana Rivers several Guarani ethnic movements by both rivers and their tributaries are perceived. The lithology and ceramics typology have contributed to support that perception. The archaeological findings help to clarify prehistoric cultural aspects and dispersal areas. In that context, the knowledge of the chemical composition of the found ceramic devices, in particular of the rare earth elements (REE) and other refractory ones provide information on this dispersion and its expansion. Selected trace elements (Rb, Sr, Y, Zr, Nb, Ba, La, Ce, and Nd) were determined in samples from thirteen archaeological sites with XRF using an Am-241 source. Their spidergrams have allowed identifying four different sets of samples according to their areas of provenance.     

A comparison of scanning electron microscopy energy dispersive X-ray (SEM/EDX) and inductively coupled plasma optical emission spectrometry (ICP-OES) for provenance inferences of grog-tempered Bronze Age pottery

Pottery tempered with former pottery fragments (named grogs) is very common during the Bronze Age in the Cantabrian Cornice (North Spain). Grog tempered pottery from two coeval archaeological sites Santa Maria de Estarrona and Peracho are studied in order to establishes pottery provenance. Chemical analyses of pottery are used to discriminate locally from imported pottery under the assumption that different geological regions exhibit a distinctive chemical fingerprint. However, the pottery-maker usually transforms the original clay by tempering and prepares the material suitable for firing modifying the raw material chemical fingerprint. The problem increases when grogs are used as tempering agent. In these cases the chemical input is clearly contaminated with foreign materials making impossible to assign a source area. SEM-EDX has been applied to both the matrix and the different types of grog tempers and the results have been compared to the whole potsherd analysis performed by ICP-OES. Chemometric analysis of matrices enable to discriminate different raw materials that can be attributed to locally produced pottery. This chemical characterization of the matrices by SEM-EDX is more effective than the chemical composition determined for the whole potsherd by ICP-OES. The occurrence of grogs within grog tempers and various types of grogs indicates modes of production based on intensive recycling. The presence of some pottery vessels at the Estarrona site with chemical features similar to those of Peracho is indicative of the transport of pieces during the migrations of semi-sedentary groups and/or the exchange of pieces between different groups of humans.     

Structure and some properties of small water clusters

The energies and structures of many small water clusters (H₂O)_n (n=8-26) are calculated using the atom-atom potential functions suggested earlier. For each n, several stable configurations were found that differ in the number of H-bonds and in the topology of the graphs formed by such bonds. The clusters in which the molecules lie at the vertices of convex polyhedra have the lowest-energy but other configurations may have close or even lower energies. For the most stable clusters, the energy dependence on n is close to linear. At 300 K, the mean energies of the clusters behave similarly. Monte-Carlo simulations showed that the clusters undergo pseudomelting at approximately 200 K. Puebla Autonomous University, Puebla, Mexico, Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences. Institute of Mathematical Problems of Biology, Russian Academy of Sciences. Institute of Physical Chemistry, Russian Academy of Sciences Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 6 pp. 113–121, November–December, 1994. Translated by L. Smolina     

Determination of trace elements in archaeological ceramics and application of Kernel Density Estimates: Implications for the definition of production locations

Summary Chemistry fingerprint of materials helps determine provenance and technological production techniques, and, therefore, is useful way to study interaction between prehistoric people. In this work 38 ceramic fragments from Justino and S?o José sites, in Brazilian northeast, were analyzed using instrumental neutron activation analysis (INAA). The recognition of the compositionally homogeneous group within of the database was performed by means of principal component (PC). The PC scores were calculated on the matrix covariance of the log base 10 transformed concentration values, and grouping was sought in the PC scores using Kernel Density Estimates (KDE). By using KDE from PC scores two chemically different groups were found. Discriminant analysis was performed to assess the groups' validity. Despite of the pottery from Justino and S?o José sites present same technical profile, different of the Tupiguarani and Aratu traditions, it was obtained that Justino and S?o José samples are constitute of distinct ceramic pastes. This result can be understood in terms of the cultural influences in the preparation of the ceramic past and that potteries analyzed are originate locally.