The luminescence properties of Fe3+ defects in feldspar are well know, but the role played by Fe2+ centres remains ambiguous, with tentative previous evidence suggesting it could act as a luminescence activator, luminescence quencher, or neither one nor the other: the outcome of these arguments would be of direct and topical relevance to consideration of using Fe3+ luminescence for the in situ dating of Martian sediments in future probe missions to the planet. Therefore, to elucidate the relative roles of Fe2+ and Fe3+, a synchrotron radiation study of Fe2+/Fe3+ defects in feldspar has been undertaken by probing the L-edges of the ion. Partial electron yield results allow a measure of the relative proportion of the ion states to be made, but of itself provides no indication of the defect's optical activity: in order to determine the latter, optical detection of x-ray absorption spectroscopy has been deployed. Although minor differences in the Fe2+/Fe3+ ratios are established using the two measurement methods, the results of the survey indicate that Fe2+ is unlikely to be an efficient luminescence quenching centre, and that competition for charge between the ion in its 2+/3+ states is not radically different. Equally, no evidence was found to suggest that it efficiently contributes to the visible emission in the range 380–750 nm.

A wooden shovel, dating from the Early Bronze Age, has survived in a remarkable state of preservation in the copper mines of Alderley Edge, Cheshire UK. Other historic timbers recovered from the mines, whilst still intact, have fared less well. An X-ray investigation into the distribution of minerals through the shovel using portable X-ray Fluorescence (PXRF) along with the use of synchrotron-based X-ray Absorption Spectroscopy (XAS) measurements of the copper and arsenic chemical speciations has provided clues to the methods by which metals from the mining environment have entered the wood of the shovel and ensured its survival. The distribution and nature of the minerals so determined suggest that the copper and arsenic, along with a significant lead content, entered the shovel during its original use in working mineral-rich deposits, rather than through the burial environment. The insights gained are expected to be applicable to other wooden artefacts recovered from ancient copper mines in other places.

Two analytical methods-Am-241-based X-Ray Fluorescence (XRF) and Synchrotron Radiation X-ray Diffraction (SR-XRD) - were used to investigate the elemental and mineralogical composition of pigments which decorate some Cucuteni Neolithic ceramics sherds. Taking into account the finding of the performed experiments, several conclusions regarding the employed manufacturing procedures and the potential trade routes during the Neolithic age were drawn.

The object of this study is a battle helmet of Corinthian type, now in the collections of The Manchester Museum. The Corinthian helmet has been called "one of the great independent achievements of early Greek technology". It was manufactured out of it single piece of bronze, probably on a rod-anvil, and like all body-armour it was made to measure. This required exceptional skill on the pan of the smith, but once discovered the design wits so efficient that it was still being used in fifteenth-century Italy, more than 2000 years after its invention around 700 BC. However, by the seventeenth century the art had been lost and had to be re-invented for modern replicas.Victorious Greek cities often set up trophies of armour front the defeated as thank-offerings at temples. Like animals being sacrificed, weapons were "killed" to be offered to the other world: so helmets had their cheek-pieces and nose-guards bent back. When the sanctuary became too crowded the trophies were cleared away and buried. The Manchester helmet was most likely found at such a site, probably Olympia itself. In order to sell it, the finder - probably in the 19th century - Straightened out the cheek-pieces, which cracked at the edges. but the nose-guard was either missing or snapped off altogether: in its present form it is too short and too close to the face to be practical.X-ray fluorescence has shown that the main body of the helmet is a copper-tin alloy of varying composition at different places and containing iron and lead while the nose-guard contains zinc in high abundance. This key compositional difference indicates that the nose-guard is not the genuine broken-off piece retrieved from the finding place but is a modern substitute fabricated for restoration purposes. Synchrotron XRD at glancing angle and variable wavelength oil several spots oil the head and the nose-guard itself shows a shift of the copper Bragg reflections which can be related to Cu-Sn or Cu-Zn percentage composition. In addition, several corrosion products are identified. Small samples of corrosion extracted from the inside of the helmet have been used to obtain powder XRD patterns. The same samples have been studied with synchrotron micro-FTIR. Neutron diffraction sampling the bronze volume at different areas has also been used to quantify the composition. Crystallographic texture data obtained oil a neutron diffractometer with large angular detector coverage was used to draw conclusions about the processes used to manufacture this precious example of archaic military technology. Some other interesting questions remain to be investigated in the near future.

Flow familiar were the pre-Homeric Greeks with Egyptian technology'? Accounts of apparent mythological nature and archaeological evidence indicate cultural contacts. To what extent did Greek craftsmen learn their ail from Egyptians? At excavations in Djoser's pyramid (3rd dynasty, ca. 2750 13C) sonic 36000 glazed tiles were found. most with a turqoise-blue glaze coating but also many with other colours. The glazing process has been interpreted as a self-glazing process involving alkali salts, copper oxide (CuO) and firing temperatures of around 850 degrees C. One investigation (Schiegel, 1988) indicated that this glaze was composed mainly of quartz, tenorite and water with a minor amount of alkalis, iron. phosphorus and chlorine. The interpretation of the data as indicative of the presence of chemically bound water is rather puzzling if such high temperatures were indeed used to produce the,laze oil these tiles, and in such large quantities.An alternative explanation has been proposed (Davidovits, 2005) according to which what is needed in order to replicate this self-glazing process is soluble silicate SiO2, K2O, Na2O + synthetic turquoise (inafkat), aluminium phosphate hydrate + copper phosphate hydrate and a firing temperature of 250'C. The resulting glaze call be described its it geopolynier-type material where the vitrified matfix is (K, Na)-Poly(Sialate-decaSiloxo), (Si-O-Al-O)-(Si-O-) 10. The process call be controlled to produce blue (K+) or green (Na+) at 250'C or black at 350'C in the presence of Cu-phosphate, Cu-silicate and tenorite, or beige in the presence of' Fe-salts (phosphate, arsenate). The process results in a vitreous matrix with the appearance of a fitience-type material and with a composition corresponding to the starting materials. We have used a number of techniques to characterise this turqUoise-blue --copolymer glaze" produced experimentally by Davidovits. Synchrotron-XRD of'sinall flakes front the outer blue surface layer and the white inner core was used to determine the %weight ofthe diffracting phases as well as the amorphous component which constitutes some 87% ofthe scattering mass. SEM/EDS was employed to study the vitreous matrix morphology as well as the local elemental composition. Raman spectroscopy was used to correlate the other observations with the Molecular composition of the areas examined. It is an appealing thought, that ancient craftsmen were as ingenious in matters of solid state chemistry and metallurgy as present-day industrial materials scientists. Could similar skills have been used for decorating metal obJects such its mentioned in the Homeric epics, particularly when referring to Hephaestian arts? Why not? Whitt else could the Greeks have learned from the wiseold Egyptians, a mature and technologically advanced civilisation well before Homeric times'?

In this work, the potentiality of two-dimensional X-ray diffraction (XRD(2)) to characterise aerosol particles collected on commercial glass filters is presented. Indeed, even if routine analysis usually requires only mass determination, and rarely chemical composition, phase determination is fundamental to recognize the primary or secondary origin of the particulate matter and thus to determine the main sources of the pollution and to model contamination events. The experiments were performed at Daresbury Synchrotron (UK) Laboratory on 14.1 Beamline. The analysis of filters collected in Tuscany (Italy) is discussed with particular attention to the presence of arsenic sulfide. The first results of these experiments are very promising, showing the presence of unexpected compounds in the particulate matter of the investigated area.

With the aim of contributing to the knowledge of north-Mesopotamian Bronze Age pottery production (3rd millennium BC, early Dynastic and early Akkadian period), the mineralogy of pottery excavated from the site of Tell Beydar (Syria) has been studied in order to make inferences concerning the clay preparation and firing techniques of that period. The fired pottery finds have been classified by archaeologists into three distinct groups on the basis of their aesthetic and visual appearance and their mechanical strength: standard, cooking and “metallic” ware. SR X-ray powder diffraction data have been collected from 100 individual shards as well as from local clays and one unbaked object, an inscribed tablet. The XRD data is supplemented by SEM-EDS, XRF and polarising microscopy studies of 200 polished thin sections. The synthesis of the results from this extensive study quantifies the basic physical characteristics of the ensemble: the standard ware required no specific clay preparation and firing procedures. The body of the cooking ware contains large inclusions which result in a body texture intended to make them resistant to repeated thermal cycles. Both standard and cooking ware are made of a calcareous clay, typical of pottery from the Middle East. The metallic ware, however, are of a much finer quality with a distinctly different mineralogy than the other two groups.

The high analytical sensitivity and high spatial resolution of synchrotron radiation-based techniques, in particular SR-XRD and SR-FT-IR, allows the identification of complex micrometric mixtures of compounds that constitute the different layers of ancient paintings. The reliability of the measurements even with an extremely small amount of sampled material is very high, and this is particularly important when analyzing art works.

Luster is a golden metallic-like decoration produced on glazed ceramics since early Islamic times (Iraq, 9th AD). Luster is obtained by the reaction of a luster paint and the glaze surface over which it is applied. A temperature-resolved XRD experiment was designed to study the high temperature reactions in the luster paint while the luster layer is formed. The luster paint composition has been made based on the original luster paints found during the excavation of the 13th AD workshop site at Paterna (Valencia). The sulfo-reducing atmosphere created during the decomposition of cinnabar promotes the reduction of Cu 2+ containing compounds to Cu + and the presence of Hg vapours delays the precipitation of metal silver. Moreover, evidence of the formation of a melt in which the copper and silver-containing compounds dissolve has also been obtained. The thickness of the luster paint applied results in the formation of luster layers of different hues and colours. The use of a mixture of copper and silver paint results in the formation of dark-brown luster layer similar to the ones produced in early Islamic times in Iraq and showed also the characteristic blue iridescences.

The phase transformations as a function of the temperature of two natural illitic clays were investigated through XRD measurements, ex situ at room temperature with conventional set up and in situ with synchrotron radiation, in order to understand the origin of the corundum phase, which is one of the main characteristics of the red glaze (slip) of Terra Sigillata from south Gaul. These clays were chosen on the basis of their chemical composition and for the quality of vitrification in the firing temperature range of sigillata (1030–1080 °C). Results show that corundum can be formed above 1000 °C if the amount of Mg is not too high. The corundum formation does not result directly from the total decomposition of illite (<900 °C) but from the formation and disruption of an intermediate potassium aluminum silicate phase. On the other hand, if chlorite is present in the raw clay so that the amount of Mg>3–4 wt. %, this intermediate phase is not observed and only a spinel phase is formed.

From ancient times to today glasses, generally based on siliceous oxides cooled to a hard condition to avoid crystallization, have been extensively used, for their chemical-physical durability. Indeed, glass is one of the materials most frequently discovered during archaeological excavations. The degradation induces the loss of brightness and transparency, and the formation of pits, crystals and patinas. Sometimes peeling layers may appear, too. All these phenomena alter irreversibly the aesthetic appearance of the glassworks. The research in this field, initially focused on the knowledge of history, composition and technology of the manufacture of works of art is trying now to rationalize the problems connected with degradation processes through, both, very sensitive characterization techniques and model experiments simulating degradation phenomena. In this work we deepen the analyses of glass degradation regarding samples coming from the Roman ship Iulia Felix found on the seabed of Grado lagoon (Italy) and dated to the 11 century A.D. Their surfaces have been investigated through XPS (X-Ray Photoelectron Spectroscopy) and SIMS (Secondary Ion Mass Spectrometry) to understand water effects on glass degradation and interesting considerations oil the mobility of the present ionic species are proposed. We also report the results of micro-XRF and synchrotron-XRD analyses that will allow us to single out the various crystallization species present resulting from the degradation phenomena of these glasses.

Archaeological cellulose textile fibres (linen and cotton) from caves in the Dead Sea region were investigated using synchrotron X-ray microdiffraction. The degradation of the up to 2100 year old fibres was found to depend on the climatic conditions at the place of storage. The size and the lattice parameters of the cellulose nanocrystals (microfibrils) in the fibres change upon degradation; these parameters are shown to be strongly correlated, leading to a microscopic description of the degradation process in terms of molecular disorder. Artificial ageing does not seem to reproduce the effects observed here for the first time on archaeological cellulose fibres.

A new method of ion‐exchange between raw compounds containing copper oxide and alkali glasses has been used to grow copper nanoparticles within a glass matrix, forming a metal–glass nanocomposite that is the structure on which both ancient and modern lustre glazes are based. When excited by X‐rays at 300 K, two dominant emission bands appear in the material in the visible region, peaking at 2.60 eV and 1.98 eV. Synchrotron radiation methods are deployed that enables the luminescence and structural properties of the nanocomposite to be interlinked. Standard Extended X‐ray Absorption Fine Structure (EXAFS) shows that both metallic copper and copper oxide local sites structure are present in the glass matrix, and the detailed atomic arrangement of each are derived; however, the method provides no information as to whether either structures are actually involved in the luminescence processes. In order to provide this direct link, Optically Detected X‐ray Absorption Spectroscopy (OD‐XAS) has been deployed, and this provides strong evidence that copper metal nanoparticles are responsible for the red emission. The method also shows that the X‐ray absorption processes of the metal particles and silicate lattice (that result in the red and blue emissions respectively) are distinctly different. This is the first report of OD‐XAS involving metallic nanoparticles, and opens the possibility of using the method more generally for metal nanoparticle research. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

In the early 9th century AD ancient potters of Iraq discovered that after firing some copper oxides and silver salts with clay, iron oxides and some sulphur compounds applied on a ceramic glaze produced a beautiful layer with a wide range of colours, from reddish to yellowish or even greenish, and some with a characteristic metallic copper or purplish shine. Modern studies of these layers showed that they are formed by nanocrystals of copper and silver embedded in a glass matrix. Some attempts have been performed to understand ancient lustre coloration and characteristic gloss but have failed to give a clear correlation between chemical composition and colour, and generally make some assumptions on the shape and the size of the nanoparticles and the lustre nanostructure. The aim of this paper is to establish a basis for understanding lustre nanostructure linked to its optical properties from a sequence of lustre reproductions on traditional lead glazed tiles. These modern lustre decorations have been studied by means of optical microscopy, transmission electron microscopy and electron energy loss spectroscopy, UV–vis spectroscopy, low irradiation angle X-ray diffraction, synchrotron radiation X-ray diffraction and electron microprobe analysis. These results show that changes in the lustre nanostructure affect the glaze colour and shine during the lustre formation process. Lustre nanostructure showed crystal size range as a function of depth, that subsequently disappeared followed by an increase of nanoparticles mean diameter and reduction of the interparticle distances. Consequently, the dipole plasmon coupling between copper nanoparticles appeared, and seems to be responsible for the metallic shine and copper metal like coloration of the copper lustre. However, colour from the glaze surface differs when calculated for diffuse or reflected light. Diffuse coloration appears strongly affected by the copper nanocrystals, while specular coloration is not only affected by copper but also by the presence of an inhomogeneous distribution of silver nanocrystals which gives the lustre a characteristic purplish shine.

With the aim of shedding new light on the still poorly understood North Mesopotamian metallic ware, ceramic and soil samples from Tell Beydar (northeastern Syria, third millennium bc) were investigated using a range of analytical techniques, including optical microscopy, SR–XRD and SEM–EDX. The objective of this work was to differentiate calcareous metallic ware from non-calcareous ware without the aid of chemical analyses and to find further validation of the existing hypothesis that the former group is an imitation of the latter. A third group of metallic wares from Tell Beydar is believed to be of non-local, still regional origin.

Single 2000-year-old archaeological fibres from textile fragments excavated in the Cave of Letters in the Dead Sea region were investigated by a combined approach using microscopy (optical and SEM), X-ray microbeam diffraction and X-ray microbeam fluorescence. In comparison with modern reference samples, most of the fibres were identified as wool, some as plant bast fibres (flax). The molecular and supermolecular structure of both keratin (wool) and cellulose (flax) were found completely intact. In many fibres, mineral crystals were intimately connected with the fibres. The fluorescence analysis of the dyed wool textiles suggests the possible use of metal-containing mordants for the fixation of organic dyes.

The focus of this study consists of examining how corrosion potential measurements can contribute in providing information on the effectiveness of storage and stabilization treatments of copper alloys in aqueous solutions. We report on the electrochemical behavior of artificial copper alloy coupons (covered or not with corrosion layers), simulating the behavior of real artifacts, immersed in sodium sesquicarbonate solutions. Particular attention is given to the transformation of the corrosion layer as a function of time. In addition, synchrotron radiation X-ray diffraction measurements are performed before and after the treatment in order to understand the reactions that take place during the immersion processes.

Microprobe EXAFS analysis of lustre decoration from a late 13th century Hispano–Moresque potsherd has been used to examine the metallic oxide to metal ratios in different shaded copper lustre finishes. A single specimen from 13th century Paterna, exhibiting typical red and green colorations, is found to contain different copper/silver ratios depending on the color. EXAFS has been used to determine the local atomic environment of the copper and reveals a corresponding variation in the metal to oxide ratio of the copper content which is related to the visual effect.

The information that can be retrieved from the study of ancient materials and studies on their conservation rely strongly on the development and application of new techniques of physical analysis. This is particularly important at a time when global changes affecting our environment and way of life impose new stresses putting heritage preservation at risk. For this purpose, synchrotron techniques are particularly suited to the non- (or micro-) destructive characterisation of such heterogeneous materials, and a steep increase in the number of publications has been noticed recently from cultural heritage works using synchrotron radiation. In 2004, an interface dedicated to archaeology and cultural heritage was launched at the SOLEIL synchrotron to allow researchers from the international scientific community to be granted specific expertise. This interface aims at easing the access of researchers to the synchrotron, facilitating contacts, providing technical support and informing the community. The very first applications of SOLEIL beamlines in the heritage field are illustrated through works recently carried out at the first beamline of SOLEIL, LUCIA, currently located at the Swiss Light Source (SLS). The setup of the beamline is succinctly described.

This research is aimed at assessing the particular kind of damage caused by the interaction between atmospheric pollution and the marble surface of a magnificent late gothic church, Milan Cathedral, restored in the early 1970s. On the basis of visual inspections and diagnostic investigations the facade appears to be seriously damaged by surface erosion and thick black crusts; biological crusts, micro-fractures and detachments are widely present.