Screening of Iberian Coinage in the 2th‐1th BCE Period Using the Voltammetry of Immobilized Particles

The voltammetry of immobilized particles (VIMP) was applied for grouping a series of 86 Iberian coins nominally minted in the cities of Iltirta, Cástulo and Obulco in the 2^th‐1^th BCE period for which there are no chronological data. Using characteristic signatures for the reduction of cuprite, tenorite and lead corrosion products in the patina of the coins, voltammetric grouping of coins was proposed. Voltammetric data were found to be consistent with textural and compositional properties of the surface and subsurface of selected coins using FIB‐FESEM‐EDX. The obtained data confirmed a clear separation between the productions of Iltirta on one side, and those of Cástulo and Obulco on the other side, indicating the possibility to establish a rough chronology for these productions.     

Modeling Corrosion of Archaeological Silver‐Copper Coins Using the Voltammetry of Immobilized Particles

Two complementary models to describe the long‐term corrosion of silver‐copper coins, based on potential rate laws for smooth corrosion and those combined with diffusive law, for gross corrosion, are proposed. Theoretical kinetics can be tested using signatures of copper and silver corrosion products using the voltammetry of immobilized particles technique. The method is applied to silver coins minted during the 13^th–14^th centuries from the Libertad street hoard in Valencia (Spain) using non‐invasive one‐touch graphite pencil sampling. Voltammetric features yield functional dependences in agreement with the proposed model potentially useful for distinguishing between different mints.     

Potential Application of Voltammetry of Microparticles for Dating Porcine Blood‐based Binding Media used in Taiwanese Architectural Polychromies

A method for dating Hemoglobine‐containing archaeological samples using the voltammetry of microparticles is described. This is based on the record of the voltammetric response of such materials attached to paraffin‐impregnated graphite electrodes in contact with aqueous acetate buffer. Signals attributable to the Fe^III/Fe^II iron couple and their catalytic enhancement in the presence of H₂O₂ can be correlated, via first‐order reaction kinetics, with the time of aging of the samples. The method has been applied to the study and dating of the polychromed architectural decoration of different parts of the architectural complex of the Longshan Temple in Lukang (18^th century, Taiwan).     

Composition of 12–18th century window glass in Belgium: Non-figurative windows in secular buildings and stained-glass windows in religious buildings

A set of ca. 500 window glass fragments originating from different historical sites in Belgium and covering the period 12^th–18^th century was analyzed by means of electron probe microanalysis. Most samples are archaeological finds deriving from non-figurative windows in secular buildings. However, the analyzed set also contains glass sampled from still existing non-figurative windows in secular buildings and stained-glass windows in religious buildings. A sudden compositional change at the end of the 14^th century can be noticed among the series of glass compositions that were obtained. These changes could be related to the use of different glassmaker recipes and to the introduction of new raw materials for glass making.     

On the possibilities of ICP-AES for analysis of archaeological bones

The possibility of using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the elemental composition of archaeological bones elements was evaluated and discussed. The interferences of the major elements (Ca, P, K, Na, Al and Fe) on the microelements (Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) were investigated and the appropriate analytical lines were selected. The role of different nebulizers (cross-flow, Babington and Meinhard) on detection limits were investigated. The applicability of the proposed procedure was demonstrated analyzing IAEA-SRM-H-5 (Animal bone); and authentic bone sample dating back to the 4^th century BC. These results were compared to ETAAS and ICP-MS.     

Ancient coins: cluster analysis applied to find a correlation between corrosion process and burial soil characteristics

Although it is well known that any material degrades faster when exposed to an aggressive environment as well as that "aggressive" cannot be univocally defined as depending also on the chemical-physical characteristics of material, few researches on the identification of the most significant parameters influencing the corrosion of metallic object are available.A series of ancient coins, coming from the archaeological excavation of Palazzo Valentini (Rome) were collected together with soils, both near and far from them, and then analysed using different analytical techniques looking for a correlation between the corrosion products covering the coins and the chemical-physical soil characteristics. The content of soluble salts in the water-bearing stratum and surfacing in the archaeological site, was also measured.The obtained results stress the influence of alkaline soils on formation of patina. Cerussite, probably due to the circulation of water in layers rich in marble and plaster fragments, was the main corrosion product identified by X-ray Diffraction (XRD). Copper, lead and vanadium were found in soil surrounding coins. By measuring conductivity, pH and soluble salts content of the washing solutions from both coins and soils, we could easily separate coins coming from different stratigraphic units of the site.Data were treated by cluster and multivariate analysis, revealing a correlation between part of the coins and the nearby soil samples.     

Characterisation of five coins from the archaeological heritage of Portugal

This paper reports a study carried out on three Roman and two Portuguese coins found in the archaeological site of São Pedro, in Fronteira (Alentejo, Portugal). The three Roman coins have been identified as a Follis, an AE 2 and an AE 3 (bronze alloys), while the Portuguese coins have been identified as a Ceitil (copper) and the “6 vinténs” (Ag–Cu alloy). Scanning electron microscopy (SEM) coupled to energy dispersive spectroscopy (EDS) has allowed the semi-quantitative determination of the elemental composition of both the corrosion products and the alloy used in the manufacture of the coins. The crystalline corrosion products constituents of the patinas were identified by X-ray powder diffraction spectroscopy (XRD). The more deteriorated coin, the AE 3, was submitted to electrochemical studies in Na₂SO₄ aqueous solution and the corresponding data analysed. After 3 weeks, the E _OCP was still quite stable, ranging between ?0.050 and ?0.070 V vs. SCE; the corrosion resistance, R _p, was of the order of 5 to 3?×?10³ Ω. Chemical treatment of the sample by 1-h immersion in 0.1 M NaOH produced a more active surface, with R _p showing a decrease of a factor of about ten. On the other hand, it was concluded from voltammetric data that polarisations of E _a?≥?0.050 V vs. SCE led to copper oxidation, with no reduction of the other corrosion products.     

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.     

On the AMS and EPR Studies of Chinese Cultural Objects

Accelerator mass spectrometry (AMS) is a versatile tool in carbon‐14 dating. In the studies of Chinese paintings and calligraphic works on paper substrates, it is necessary to assess the period of preparation. The precision of AMS measurements has been proven to be reliable for estimation, In conformity with historical background of the art works, AMS can be adapted to assess the age, authenticity, artistic information and conservation requirements. The AMS measurement of Chinese ink rubbing on paper, after OxCal data treatment, gave a result of 1105 ± 30BP. During the course of artistic preparations the paper received extensive impact force which induced the formation of entrapped free radicals. Thus, EPR spectrometry was used to investigate the sample, as well as for a print with an age of 345 ± 40BP by AMS dating and a piece of blank paper from 17^th century to find out the differences in free radical phenomena.     

Chemical Characterization of Iberian Amphorae and Tannin Determination as Indicative of Amphora Contents

 A chemical characterization of samples corresponding to three amphorae, dated from the 5^th century BC, and a fourth amphora dated prior to the 5^th century BC, has been made by X-ray diffraction spectrometry analysis. Major mineral constituents of the ceramic samples provided useful information about the origin area and the nature of the raw materials, as well as technological aspects related to amphora manufacture. Several conclusions have been drawn: three of the pieces analysed were probably made of raw materials from the surrounding areas of the archaeological site, while the other one was probably imported. A second conclusion was that all of them were baked below 700 °C. In order to find out the substances transported or stored in the amphorae, chemical analyses of the organic residues possibly absorbed or retained in the ceramic paste were carried out. The modified Folin-Denis method was used for the determination of tannins. As a result, their presence was only detected in one of the pieces. This evidence is indicative of the fact that these compounds, probably coming from wine, have withstood the passing of time protected into the amphora from the external degradation conditions. These analytical results lead to establish the nature and origin of raw materials, as well as to demonstrate or corroborate early technological practices of the ancient Iberians in Spain and to contribute to know better Iberian habits and economy. Received December 5, 2001; accepted July 25, 2002     

Examination and analysis of Indian silver punch‐marked coins employing WD‐XRF and other noninvasive techniques

The archaeometallurgical analysis of ancient silver coins provides useful information regarding fabrication methodology, provenance, and trade route and explains large diversification in elementary composition, weight, and physical features. The present investigation deals with the chemical analysis and examination of the processing history of Indian punch‐marked silver coins dating to 400–200 bc . The chemical analysis was carried out by wavelength dispersive X‐ray fluorescence and X‐ray Diffraction (XRD). The microstructural examination was performed using field emission scanning electron microscope (FE‐SEM) and different phases were identified by Scanning Electron Microscopy coupled with Energy Dispersive X‐ray (SEM‐EDX) Spectroscopy. It was observed that all eight coins were manufactured with silver‐copper alloy. The ore used for obtaining silver was argentiferous galena, and cupellation was carried with perfection. The absence of slag inclusions as revealed by SEM examination indicated that coins (numbers 2, 4, 5, and 7) were cast from a molten state. The presence of Cu₂O, CuO, and Ag₂O on the surfaces of the coins was confirmed by XRD. The formed oxide layers provided protection and saved the coins from bulky corrosion products. The data reveal great divergence of coin surface from the composition of the core with the far better metallurgical process for refining of silver for this hoard.     

Micro-Raman study of copper hydroxychlorides and other corrosion products of bronze samples mimicking archaeological coins

Three bronze samples created by CNR-ISMN (National Research Council—Institute of Nanostructured Materials) to be similar to Punic and Roman coins found in Tharros (OR, Sardinia, Italy) were studied to identify the corrosion products on their surfaces and to evaluate the reliability of the reproduction process. Micro-Raman spectroscopy was chosen to investigate the corroded surfaces because it is a non-destructive technique, it has high spatial resolution, and it gives the opportunity to discriminate between polymorphs and to correlate colour and chemical composition. A significant amount of green copper hydroxychlorides (Cu₂(OH)₃Cl) was detected on all the coins. Their discrimination by Raman spectroscopy was challenging because the literature on the topic is currently confusing. Thus, it was necessary to determine the characteristic peaks of atacamite, clinoatacamite, and the recently discovered anatacamite by acquiring Raman spectra of comparable natural mineral samples. Clinoatacamite, with different degrees of order in its structure, was the major component identified on the three coins. The most widespread corrosion product, besides hydroxychlorides, was the red copper oxide cuprite (Cu₂O). Other corrosion products of the elements of the alloy (laurionite, plumbonacrite, zinc carbonate) and those resulting from burial in the soil (anatase, calcite, hematite) were also found. This study shows that identification of corrosion products, including discrimination of copper hydroxychlorides, could be accomplished by micro-Raman on valuable objects, for example archaeological findings or works of art, avoiding any damage because of extraction of samples or the use of a destructive analytical technique.     

Characterization of Phoenician pottery from Mothia by neutron activation analysis

The concentration of 7 elements (Na, Al, Mg, Ti, Ca, V, Mn) was determined by Neutron Activation Analysis in 35 samples of pottery and 14 samples of clay. The samples were collected in Mothia (a Phoenician stronghold in Sicily during 5^th–4^th century B. C.) and in its neighbourhoods. Cluster analysis of the data showed that most of the samples are homogeneous and confirmed the archaeological evidence that they are mostly local ware. The detailed results of the analyses are reported and the technique used for cluster analysis is described.     

Thermal and mineralogical contribution to the ancient ceramics and natural clays characterization

In the present work 39 ancient ceramic sherds from the archaeological excavation of Abdera, North-Eastern Greece, dating to 7^th century B.C., and 11 local raw clay bricks, fired at temperatures ranging from 500 to 1000°C, were characterized by ICP-AES, powder X-ray diffraction (PXRD) and thermal analysis (TG-DTA) techniques. It has been found that the mineralogical composition of the most studied sherds is quartz, feldspars and micas, which is in agreement with the composition of the local bricks. Chlorite is also present in a few samples, while there is one completely different sherd, which belongs to the Ca-rich clays. From the simultaneous TG/DTG and DTA data, under nitrogen atmosphere in the temperature ranges ambient to 1000°C, we comment on the possible firing temperature and distinguish between samples of different origin. The existence of muscovite or illite in most of the samples denotes that the firing temperature was lower than 950°C, while the existence of chlorite means that the firing process in these samples stopped before 700°C. A very different thermogram gave the Ca-rich ceramic sherd, due to the existence of calcite, denoting that the firing temperature was about 700°C.     

Archaeometrical studies of Greek and Roman silver coins

Quantitative analyses of various silver coins from the first century BC, found on current Romanian territory (Thasian tetradrachmae, Apollonia and Dyrrachium drachmae, Roman republican denarii) were performed using PIXE (3 MeV external proton beam) and XRF (1.1 GBq²⁴¹Am source). The elemental analysis provided evidence of a great variety of monetary alloys and helped Romanian archaeologists to classify the coins, in terms of their provenance, as originals, copies or imitations minted in different areas of the Balkan-Carpathian region.     

Optically stimulated luminescence dating of pottery from Turkey

In this study, the potential of optically stimulated luminescence (OSL) dating for archaeological potteries was investigated. Firstly, recently purchased OSL and alpha counter systems were calibrated. Then, archaeological sherds taken from Dat?a-Burgaz (Mu?la, Turkey) archaeological site of archaic and classical period (700-400 BC) were dated. Samples were prepared by the fine grain technique and paleodose was found by using the additive dose technique. The annual doses of uranium and thorium were determined by using the alpha counter. The potassium, which has no alpha activity, was determined by atomic absorption spectrometry. The age of the sherds was found to be 2340+/-190 years which is in good agreement with the archaeological evidence involving figurines and coins obtained in the same level.     

Determination of <Superscript>210</Superscript>Pb in human skeletal remains from Morocco: implications for time since death assessment

In forensic contexts, time since death assessment in human skeletal remains is crucial for identification, and both accuracy and reliability are required. In this paper, we present the possibilities and constraints of the use of ²¹⁰Pb in dating skeletonized human bones in Morocco. The method was tested on recent as well as archaeological bones of known dates of death. A calibration curve was obtained from the available data in the scientific literature. The ²¹⁰Pb initial activity was introduced as an increasing lineal function with time. The ²¹⁰Pb dating approach gives promising results only for recent bones. On the contrary, for archaeological bones, the technique has erroneously led to post-mortem intervals in the range of recent bones which constitute a serious limitation of the method. On the other hand, uranium isotopes content in bones is suggested in this work as a possible indicator in placing a studied bone within either a forensic or archaeological context.     

Lead(II) Formate in Rembrandt's Night Watch: Detection and Distribution from the Macro- to the Micro-scale

The Night Watch, painted in 1642 and on view in the Rijksmuseum in Amsterdam, is considered Rembrandt's most famous work. X-ray powder diffraction (XRPD) mapping at multiple length scales revealed the unusual presence of lead(II) formate, Pb(HCOO)₂, in several areas of the painting. Until now, this compound was never reported in historical oil paints. In order to get insights into this phenomenon, one possible chemical pathway was explored thanks to the preparation and micro-analysis of model oil paint media prepared by heating linseed oil and lead(II) oxide (PbO) drier as described in 17^th century recipes. Synchrotron radiation based micro-XRPD (SR-μ-XRPD) and infrared microscopy were combined to identify and map at the micro-scale various neo-formed lead-based compounds in these model samples. Both lead(II) formate and lead(II) formate hydroxide Pb(HCOO)(OH) were detected and mapped, providing new clues regarding the reactivity of lead driers in oil matrices in historical paintings.     

Laser ablation single-collector inductively coupled plasma mass spectrometry for lead isotopic analysis to investigate evolution of the Bilbilis mint

This work explores the performance of laser ablation—inductively coupled plasma mass spectrometry using different types of single-collector devices (sector field and time-of-flight instrumentation) for lead isotopic analysis of bronze coins, minted in the ancient city of Bilbilis. The aim of the study was achieving sufficient discrimination power to reveal similarities and differences for coins originating from different historical periods, and to obtain information on the possible source of the lead ores used in their production, while restricting the damage inflicted to the samples such that it is not visible to the naked eye.It was found that satisfactory results (RSD in the 0.15-0.30% range for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios) could be finally obtained, despite the noisy nature of signals generated upon ablation of the highly inhomogeneous coins, by means of a methodology based on: (a) selection of the line profiling ablation mode; (b) use of a dual pass spray chamber that permits the simultaneous introduction of a solution (containing thallium of known isotopic composition), thus resulting in a wet plasma that showed an increased robustness towards matrix effects and (c) detection using a TOF-ICPMS unit, which proved to be much better suited to deal with the transient signals obtained, while being also sufficiently sensitive to obtain good counting statistics, owing to the high lead level (average around 5%) present in the samples. Moreover, under these conditions, the simultaneous aspiration of the thallium spike permitted accurate correction for mass discrimination, such that it was not necessary to use external matrix-matched standards for calibration.     

Characterization of waterlogged wood by NMR and GPC techniques

Anaerobic erosion bacteria can slowly degrade waterlogged wood, causing a loss of cellulose and hemicellulose. During this process, lignin can also be altered. For this reason, the chemical characterization of waterlogged archaeological wood is crucial for both the elucidation of the degradation processes and also the development of consolidation and conservation procedures.The complex structure of wood makes it practically impossible to dissolve wood in its native form in conventional molecular solvents. Ionic liquids can provide a homogeneous reaction medium for wood-based lignocellulosic materials. Highly substituted lignocellulosic esters and phosphite esters can be obtained under mild conditions by reacting pulverized wood dissolved in ionic liquid with either acyl chlorides or dioxaphospholanes in the presence of pyridine. As a result, the functionalized wood develops an enhanced solubility in molecular solvents, allowing for a complete characterization by means of spectroscopic and chromatographic techniques.In this study, archaeological woods and reference sound woods of the same taxa (Quercus and Arbutus unedo), along with the corresponding extracted lignin, were fully characterized by means of phosphorus NMR spectroscopy, two dimensional NMR spectroscopy and GPC analysis. The samples were collected from the Site of the Ancient Ships of San Rossore (Pisa, Italy), where many shipwrecks dating from 2nd century BC to 5th century AD have been discovered.The results highlighted a deeper and faster depolymerization of the polysaccharide matrix against a limited degradation of the lignin fraction. The use of innovative solvent system as the ionic liquid [amim]Cl enables to highlight chemical and morphologic changes in wood composition avoiding further degradation.