Studies of archaeological problems by Mössbauer spectroscopy

The recent developments and achievements of the application of Mössbauer spectroscopy to archaeological problems are reviewed. The relevances of Mössbauer spectroscopy in studies of provenance, manufacturing technology and age dating of ancient pottery, as well as the ancient bronzes are discussed.     

Application of various spectroscopic techniques to characterize the archaeological pottery excavated from Manaveli,Puducherry, India

This paper is focused on a spectroscopic study of some ancient pottery shreds from an archaeological site Manaveli village, Puducherry, India. Analytical characterization using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and differential scanning colorimetric coupled with thermo gravimetric analysis were carried out on red and black ware and red ware recently excavated from the above site. The experimental results of FT-IR and XRD are similar and allowed us to identify the mineralogical composition of pottery samples. In addition, TGA was applied in order to study the dehydration of hydroscopic water and decomposition of carboxyl group in the powdered pottery samples during heating. Moreover, this paper proves that all the above spectroscopic techniques are very useful analytical tool for the examination of ancient pottery, which is also suitable for the identification of its firing temperature and firing atmosphere.     

Archaeological Ceramics Studied by Scanning Electron Microscopy

The use of scanning electron microscopy combined with energy dispersive X-ray fluorescence analysis in studies of archaeological pottery is discussed. The methods are described and results of their application to studies of Precolumbian glossy black pottery from northern Peru are reported in some detail.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

An integrated accelerator mass spectrometry radiocarbon dating and ion beam analysis approach for the study of archaeological contexts

The integration in the accelerator-based facility at CEDAD (Centro di Datazione e Diagnostica), University of Lecce, of a state-of-the art AMS (accelerator mass spectrometry) ¹⁴C dating system, and three different beam lines for IBA (ion beam analysis) compositional investigations, has given the possibility of developing an integrated IBA-AMS approach to the study of a wide range of archaeological problems. Here we present three cases where in air IBA methods were involved for the elemental characterisation of objects found in archaeological contexts, chronologically defined on the basis of high resolution AMS¹⁴C measurements.In particular we report on the identification of cinnabar (HgS) on Neolithic bones, the compositional analysis of a set of golden artefacts dated at the final Bronze age, and the analysis of red decorations on Neolithic pottery. PACS 32.30.Rj; 34.50.Dy; 82.80.Ms     

Portable X-ray powder diffractometer for the analysis of art and archaeological materials

Phase identification based on nondestructive analytical techniques using portable equipment is ideal for the analysis of art and archaeological objects. Portable(p)-XRF and p-Raman are very widely used for this purpose, yet p-XRD is relatively rare despite its importance for the analysis of crystalline materials. This paper overviews 6 types of p-XRD systems developed for analysis of art and archaeological materials. The characteristics of each system are compared. One of the p-XRD systems developed by the authors was brought to many museums as well as many archeological sites in Egypt and Syria to characterize the cultural heritage artifacts, e.g., amulet made of Egyptian blue, blue painted pottery, and Islamic pottery from Egypt, jade from China, variscite from Syria, a Japanese classic painting drawn by Korin Ogata, and oil paintings drawn by Taro Okamoto. Practical application data are shown to demonstrate the potential ability of the method for analysis of various art and archaeological materials.     

Application of X-ray fluorescence spectroscopy to provenance studies of Algerian archaeological pottery

The North African regions boast a multimillenary tradition of pottery production that represents a decisive progress in all societies. In this paper, we present the analysis of several fragments of pottery dating from the Middle Ages and collected in the archaeological site of Gouraya in Béjaïa (Algeria). Energy-dispersive X-ray fluorescence measurements were performed to obtain the elemental composition of the clays and to attempt a classification of the samples through multivariate analysis methods, connecting them to the archaeological information about the sites. Hierarchical clusters analysis (HCA) identified two possible different groups, related to different production sites, even if only one source of clay seem to be used, consistently with the geological contest. Based on the results, a tentative provenance interpretation could be proposed on historical bases. We put in place a strategy that made it possible to perform provenance studies respecting sample integrity as we aim to extend our research also to integer and well-preserved object from museum, to create a database for Algerian production of in the Middle Ages.     

Instrumental Neutron Activation Analysis and Multivariate Statistics for Pottery Provenance

The application of instrumental neutron activation analysis and multivariate statistics to archaeological studies of ceramics and clays is described. A small pottery data set from the Nasca culture in southern Peru is presented for illustration.     

基于X射线谱学和操作链分析的煤山遗址出土陶器综合研究

采用能量色散X射线荧光光谱（ED-XRF）技术结合考古学常用的陶器操作链研究模式, 对河南汝州煤山遗址出土的陶器遗存开展制作工艺和文化传承关系的综合研究。煤山遗址位于河南省汝州市（原为临汝县）北刘庄村,是研究中原地区新石器时代向文明国家转变的代表性遗址,出土了龙山时代的王湾三期文化（BC2300-BC1900）和具备早期国家形态的二里头文化（BC1750-BC1500）两个重要阶段大量具有典型考古学文化特点的陶器遗存,可以据此较为深入理解距今4000年前后社会复杂化进程和国家起源等重大问题。因此,对该遗址出土陶器的多学科综合研究具有极高的学术价值和文化意义。对煤山遗址出土具有不同文化类型的陶器样本进行化学组成与物理性能分析,将分析结果与陶器操作链分析相结合,进行比对分析。针对煤山遗址陶器遗存,谱学分析结果显示,不同时期考古学文化在制陶原料的选择上差异不大,具有同源性,暗示虽然文化类型不同,但其对粘土的认识和选择具有高度一致性。陶器操作链分析结果显示,虽然新石器时代的王湾三期文化年代较早,但其陶器制作工艺却较晚期的二里头文化更先进,体现了中原地区文化演进过程中既连续又摇摆的发展特点。陶器操作链分析可以反映文化内容的特征性和继承性,在使用谱学分析排除了原料与烧制影响后,对其所提取的信息具有更强的说服力和可比性。综合研究表明,将谱学分析和陶器操作链分析相结合,开展多学科对比和综合研究,可以更好的排除干扰,获取更为扎实且客观的认识,并为考古学文化演进研究提供重要的科学依据。     

Classification of ancient Etruscan ceramics using statistical multivariate analysis of data

About one hundred Etruscan ceramic shards dating from the VIII to the IV century BC and coming from the archaeological excavation at Pian di Civita in Tarquinia (central Italy) have been analyzed by inductively coupled plasma optical emission spectrometry and flame atomic emission spectrometry in order to settle their provenance and to acquire knowledge about the ceramic production technology. The examined shards belong to the class of the depurata pottery, a fine ware produced in Tarquinia over a long period, and are representative of different sub-classes. The samples have been analyzed for fifteen elements (Ca, Al, Mg, Fe, Ti, Cr, Cu, Ni, Zn, Mn, Zr, Sr, Na, K and Rb). The data acquired have been treated by multivariate analysis techniques such as principal component analysis and Kohonen artificial neural networks. Most of the analyzed shards have been locally produced as belonging to a unique large group. A continuity in usage of both choice of materials and technology has been recognized. PACS 02.50.Sk; 81.05.Mh; 82.80.-d     

Luminescence dating: laboratory procedures and protocols

In the last 30 years, from 1967 to 1997, the use of luminescence signals from naturally occurring minerals has gone though a major metamorphosis, from thermoluminescence (TL) dating of pottery to optically stimulated luminescence (OSL) dating of sediments. Laboratory procedures for dating sediments have been adapted from those for pottery and new procedures have been developed as the need arises.

The majority of sediment dating applications are carried out on quartz and potassium-rich feldspars and the general characteristics of the TL and OSL signals from these minerals are reviewed. For sediments some new problems were encountered, with some grains perhaps not being completely bleached at deposition. For OSL signals there is no simple procedure for the selection of a thermally stable signal, as there had been in the case of pottery.

Many different laboratory protocols have been developed as our understanding of the fundamental behaviour of luminescence signals from quartz and feldspar has improved. These protocols are explained and discussed, giving the advantages and disadvantages of each procedure as applied to different types of sediment.

This review is presented as a guide to the selection of the most appropriate procedure for a particular dating application.     

Electron Paramagnetic Resonance and petrographic analysis for dating Mesolithic and Neolithic pottery from Al Khiday (Sudan)

Electron Paramagnetic Resonance (EPR) dating, like luminescence techniques, is based on the time-dependent accumulation of trapped charges at mineral defect centres. However, Fe(III) ions prevent the common Continuous Wave (CW-EPR) approach for dating pottery, which always contains iron. The Pulsed method (ED-EPR) allowed this limitation to be overcome, with recording of radiation-induced defect signals, as shown by increased signal intensity after artificial irradiation of samples. The method was applied to studying Mesolithic and Neolithic pottery from Al Khiday (Central Sudan), characterized by quartz-rich tempers and coming from dated contexts. As the occurrence of a natural ED-EPR signal was found to be related to the quartz grain size of the temper, a petrographic study was carried out. This first attempt at age determination of pottery by ED-EPR meant that experimental conditions and important parameters could be taken into account in developing a new dating procedure.     

Technological features of ‘gnathia’ pottery

‘Gnathia’ pottery samples, dating back to the mid‐fourth and third century BC, from the archaeological site of Egnazia (Fasano, Brindisi, Italy) have been characterised from the physical‐chemical, mineralogical and morphological points of view. Optical and scanning electron microscopy, X‐ray energy‐dispersive spectroscopy and X‐ray diffraction analyses have been carried out on the ceramic body, black gloss, white, yellow and red over‐paintings of fragments, with the aim of outlining technological features and defining the nature of coatings and decorations. Analytical results confirm from both a technological and morphological/decorative point of view the close relationship between ‘Gnathia’ pottery and red figured pottery, particularly with the Apulian red figured from which it takes its inspiration. At the same time the experimental results highlight shared characteristics and differences with both Attic and Apulian red figured productions. The biggest difference is in the utilisation of the ‘ingobbio rosso’ layer that covers the ceramic body. This does not seem to be based on aesthetic grounds, as in the case of Apulian red figured pottery, but on application of acquired production processes, since ‘Gnathia’ pottery was made in the same workshops as red figured pottery. Copyright © 2009 John Wiley & Sons, Ltd.     

Changes in luminescence properties induced by thermal treatments; a case study at Sipan and Trujillo Moche sites (Peru)

TL-dating studies were carried out on prehispanic pottery attributed to the Moche culture of Peru (from BC 200 to AD 800 according to the previously known chronology). A greater than expected scatter in ages was found for samples known, from archaeological considerations, to have been contemporaneous. This was related to applying a fixed, but inappropriate, annealing temperature to the grains prior to their irradiation to regenerate the TL growth curve. The dependence of growth of TL and equivalent dose evaluation on this annealing temperature was tested in the range 400–1000°C. A combined cathodoluminescence/TL study was used to select the appropriate thermal treatment for evaluation of the final equivalent dose. This procedure, which we suggest can be generally applied in pottery dating, resulted in a reduction of age dispersion when applied to groups of contemporaneous ceramics.     

Evaluating the use of laser radiation in cleaning of copper embroidery threads on archaeological Egyptian textiles

Cleaning of copper embroidery threads on archaeological textiles is still a complicated conservation process, as most textile conservators believe that the advantages of using traditional cleaning techniques are less than their disadvantages. In this study, the uses of laser cleaning method and two modified recipes of wet cleaning methods were evaluated for cleaning of the corroded archaeological Egyptian copper embroidery threads on an archaeological Egyptian textile fabric. Some corroded copper thread samples were cleaned using modified recipes of wet cleaning method; other corroded copper thread samples were cleaned with Q-switched Nd:YAG laser radiation of wavelength 532 nm. All tested metal thread samples before and after cleaning were investigated using a light microscope and a scanning electron microscope with an energy dispersive X-ray analysis unit. Also the laser-induced breakdown spectroscopy (LIBS) technique was used for the elemental analysis of laser-cleaned samples to follow up the laser cleaning procedure. The results show that laser cleaning is the most effective method among all tested methods in the cleaning of corroded copper threads. It can be used safely in removing the corrosion products without any damage to both metal strips and fibrous core. The tested laser cleaning technique has solved the problems caused by other traditional cleaning techniques that are commonly used in the cleaning of metal threads on museum textiles.     

Sampling pottery in luminescence dating studies

A programme of dating pottery from Later Prehistoric sites in Britain revealed that pottery sampled from large features such as enclosure ditches is likely to be residual, i.e. not contemporary with the infilling of the feature. This is important since in luminescence dating such features are often preferred due to the simplification of the dosimetry. Dates obtained for the pottery from smaller contexts, however, were clustered and in agreement with the expected date. In the light of these findings, it is recommended that in situations where the purpose of dating the pottery is to date the feature, pottery be sampled from smaller, shorter-lived contexts. This introduces some complications in the dosimetry, but a simple means of determining the gamma dose rate is presented.     

Composition analysis of medieval ceramics by laser-induced breakdown spectroscopy (LIBS)

Laser-induced breakdown spectroscopy (LIBS) technique is expected to be one of the most preferred techniques in archaeology research since it does not disrupt the structural and chemical form of archaeological samples, and it is considered virtually nondestructive analysis method. In this work, LIBS is used for analyses of glaze, paint, and clay of medieval ceramics collected from East Plain Cilicia, Osmaniye Province during archaeological survey. Transparent glazed and colour-painted ceramics of the Islam and Byzantine pottery traditions are analysed to detect distinctive and common features of the chemical compositions of their glazes. The spectral lines of Islamic and Byzantine glazes indicate that their structures are same. However, strontium (Sr) is determined in the transparent glaze of Islamic ceramics. Elemental composition and homogeneity of paint on one of the sample are determined by LIBS analysis. Colour changes are related with composition differences of the paint content in the archaeological ceramic. In addition, the clay classification of archaeological ceramics taken from the Yap?l?p?nar mounds, Ta?l?höyük mounds, and Ören?ehir ancient sites is done using PCA and PLS-DA chemometric techniques. According to the results of the classification, Yap?l?p?nar mounds terracotta ceramics differ from those of Ta?l?höyük and Ören?ehir ancient sites.     

TL and radiocarbon dating of neolithic sepultures from Sudan: Intercomparison of results

Thermoluminescence dating of a set of 29 pottery sherds excavated at the neolithic sites of El Kadada and El Ghaba (near Shendi, Central Sudan) was carried out at Bordeaux University. The archaeological dose was measured using the fine grain technique. The annual dose was determined by analytical techniques (neutron activation analysis, ICP spectrometry, XRF, low background gamma spectrometry) and by “on-site” measurements of the environmental radioactivity (gammametry). The crystalline inclusions of the samples were characterized by optical microscopy and cathodoluminescence: the TL minerals mainly consist of quartz and K-feldspar crystals. In some cases, radioactive inclusions of zircons and monazites are observed. The TL and the radiocarbon dates show a good agreement, verifying the validity of the radiocarbon ages which were suspected to be too old because of the nature of the dated material (shells). Taking into account all the chronological data, it is shown that El Ghaba and El Ghaba necropolis were used respectively within the 4800-3300 B.C. and 4200-3000 B.C. date-ranges for neolithic cultures, the occupation of El Kadada starting five or six centuries later than El Ghaba.     

Combined XRF‐SEM analysis of varnished pottery: the case of Syracuse and Adrano (Sicily) archaelogical finds

Micro‐destructive and non‐destructive X‐Ray fluorescence techniques and scanning electron microscopy coupled with energy‐dispersive spectrometry have been applied for the analysis of ten samples of Hellenistic black‐varnished pottery, coming from archaeological excavations in Syracuse and Adrano (South Italy, Sicily). Micro‐morphological and compositional investigations, together with statistical data processing, have shown several differences among the varnishes of the specimen found in the two sites. In particular, Syracuse varnishes are characterised by a more homogeneous composition and well‐defined raw materials, whereas Adrano samples show a higher variability, probably linked to the use of different raw materials and the poorer quality of the varnish as well. The obtained results attest that, as Syracuse black pottery is concerned, the production technique is at an advanced level, whereas Adrano manufacture seems to be less specialised. Copyright © 2012 John Wiley & Sons, Ltd.