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The Sant Genis Formation is located in the NE of the Iberian Peninsula (Catalonia, Spain) and is dated to the Priabonian (upper Eocene), being part of the evaporitic formations of the margin of the Ebro Basin. It is formed by a succession of sandy lutites, occasional limestone layers, marls, and local stratified gypsum and cherts, including the Sant Marti de Tous chert. The Sant Marti de Tous chert type is confirmed by its abundance at specific locations within the territory (NE Iberian Peninsula). This is an important raw material procurement area, as evidenced by the presence of this chert in the main prehistoric sites of the region (e.g., Abric Romani) and the constant discovery of new sites in the area around the Sant Genis Formation, especially from the Neolithic period onwards (e.g., Cal Sitjo, La Guinardera Nord workshop). All these features, together with the great heterogeneity of the Cenozoic evaporitic cherts, prompted us to carry out a multi-proxy characterization for obtaining a valid criterion by which to identify this chert in the archaeological record. This very heterogeneity hampers the macroscopic characterization of archaeological cherts (e.g., at Abric Romani), but through petrographic analysis we have been able to identify their origins and, albeit to a lesser extent, their lithostratigraphic unit of provenance within the formation. The complementary mineralogical and geochemical techniques applied in this study show that, although it is difficult to establish an exact origin, through intensive sampling and criteria such as the differential presence of Fe and Ca, some differences among the siliceous varieties within a formation can be detected. CLT009/22/000044; PID2019-103987 GB-C3; PID2021-123092NB-C21; PID2019-105796 GB-I00; GV/2021/054; CEX2019-000945-M info:eu-repo/semantics/publishedVersion

This paper contributes to current debates on the technologies and practices of prehistoric artists using the rock art site of el Carche (Jalance, Spain) as a case study. The site preserves both Levantine and Schematic paintings, yet poorly understood from an analytical point of view. In the past, it has even been argued how little differentiation there is between these two post-Paleolithic traditions in terms of paint composition. Our aim with this paper was to identify pigments, paint recipes and technologies and decipher the order of the superimpositions, both between Levantine motifs of different styles, and between these and the Schematic ones. To do so, we adopted a multi-stage and multi-technical analytical strategy, trying to find a balance between sound scientific investigation and impact on the art, considering the irreplaceable nature of this World Heritage rock art. As such, our approach begins with in situ non-invasive investigations using portable EDXRF, to then collect micro-samples for non-destructive analyses by means of Optical Microscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX), micro-Raman Spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR). One of the key highlights of these paper is the identification of up to four different paint compositions, produced with various hematite-based raw materials and different processing techniques. This variability had not been previously documented. Interestingly though, no direct correlations appear to exist between styles or sub-styles and recipes. Some of these paint mixtures were even shared by both traditions. These results are discussed in cultural terms, challenging previous interpretations suggesting a similar pigment composition between Levantine and Schematic art. Microstratigraphic analysis of the cross-sections only partially clarified the overlapping sequence unveiling the complexity of these analysis. They also revealed several degradation layers and external crusts related to rock alteration processes and biological formations. Their role in rock art conservation is also discussed.

El Tesoro de Llíria (Valencia, España) constituye probablemente, por el número de monedas que lo integran, el tesoro de denarios más importante de España y uno de los más importantes de Europa. En el conjunto de monedas están representadas las emisiones de diversos emperadores altoimperiales, que en su mayor porcentaje corresponden al s. II d.C. Este trabajo se centra en los denarios acuñados bajo el reinado del emperador Adriano (117-138 d.C.) y uno de sus objetivos es la caracterización elemental de la aleación en superficie y el estudio de la variación porcentual de la plata en los denarios emitidos durante ese periodo. Con este propósito, se han analizado, mediante fluorescencia de rayos-X (XRF), 50 denarios de plata seleccionados entre los emitidos durante el reinado de Adriano. Los análisis no destructivos realizados aportan información sobre las aleaciones y sugieren un enriquecimiento superficial en plata. Junto a la plata, elemento mayoritario de la aleación, se ha observado la presencia de cobre, plomo, oro y otros elementos traza. Las concentraciones de plata obtenidas varían entre el 89% y el 97% e indican una cierta uniformidad en las aleaciones, acorde con el periodo de estabilidad económica y política del reinado de Adriano.

Proceedings of the 12th European Conference on Accelerators in Applied Research and Technology (ECAART12).-- et al., This work presents a detailed study of a series of silver plates gilded via electroplating techniques in which the characteristics of the coating gold layers are investigated as a function of the electroplating variables (voltage, time, anode surface and temperature). Some reference samples were coated by radio frequency sputtering in order to compare gold layer homogeneity and effective density. Surface analysis was performed by means of atomic and nuclear techniques (SEM-EDX, EDXRF, PIXE and RBS) to obtain information about thickness, homogeneity, effective density, profile concentration of the gold layers and Au-Ag diffusion profiles. The gold layer thickness obtained by PIXE and EDXRF is consistent with the thickness obtained by means of RBS depth profiling. Electroplated gold mass thickness increases with electroplating time, anode area and voltage. However, electrodeposited samples present rough interfaces and gold layer effective densities lower than the nominal density of Au (19.3 g/cm), whereas sputtering produces uniform layers with nominal density. These analyses provide valuable information to historians and curators and can help the restoration process of gold-plated silver objects., This work has been partially supported by the project HAR2015-67113-P of the Spanish Ministry of Economy and Competitiveness. Simona Scrivano thanks the “V Plan Propio de Investigación” of the University of Seville for her contract.

This paper presents the characterization of the Joaquin Sorolla's gouache sketches for the oil on canvas series “Vision of Spain” commissioned by A. M. Huntington to decorate the library of the Hispanic Society of America in New York. The analyses were focused on the identification of the elemental composition of the gouache pigments by means of portable EDXRF spectrometry in a non-destructive mode. Additionally, SEM-EDX and FTIR analyses of a selected set of micro-samples were carried out to identify completely the pigments, the paint technique and the binding media. The obtained results have confirmed the identification of lead and zinc white, vermillion, earth pigments, ochre, zinc yellow, chrome yellow, ultramarine, Prussian blue, chromium based and copper–arsenic based green pigments, bone black and carbon based black pigments, and the use of gum arabic as binding media in the gouache pigments.

An innovative multi-analytical approach for the classification of ancient pottery sherds was tested. Twenty Roman amphorae fragments belonging to different known typologies and twenty-seven unclassified ones from a complex Sagunto Archaeological Museum (Spain) collection were studied by multielement analysis (X-ray fluorescence spectroscopy and inductively coupled plasma mass spectrometry), Fourier-transform near infrared spectroscopy and voltammetry of immobilized microparticles employing a minimal amount of sample. Chemometric analysis based on principal component analysis allowed the identification of most of the unclassified samples, proving the importance and reliability of the developed methodological approach for ceramic classification insights.

The study and the characterisation of modern and contemporary oil paintings is still a challenging issue, in particular considering the significant changes in paint production across the 19th and 20th centuries. This paper presents the results of the first physico-chemical integrated study of the artistic materials used in six paintings from the School of Art and Higher Design of Valencia (Escola d'Art i Superior de Disseny, EASD-Valencia), artworks created between 1871 and 1943 by four famous Valencian artists: Salustiano Asenso Arozarena, Salvador Abril I Blasco, Enrique Navas Escuriet and Jose Bellver Delmas. A wide range of inorganic and organic compounds was identified through a multi-analytical approach by means of visible reflectance spectroscopy, XRF, μ-Raman, FTIR and GC–MS. The investigation on the binding media suggests the use of commercial paint formulations including mixtures of drying, slow- and non-drying oils and the presence of Gum Arabic as well. Traditional pigments (such as vermillion, earth pigments, lead white) and modern pigments (such as zinc white, cobalt and chromium-based pigments) were identified together with fillers and extenders. Degradation products, in particular zinc and lead soaps having strong conservation implications, were also detected. This work, focusing on the identification of the palettes and the binding media used by the selected artists, aims at providing meaningful data and interesting case studies that are useful beyond the Valencian painters solely. This study provides new insight into the use of 19th–20th century commercial oil paints and the selection of painters' palette and their artistic production techniques. Besides, this work highlights the necessity of a multi-analytical approach to obtain valuable information for documentation and preventive conservation.

In the Edo (1615–1868) and Meiji (1868–1912) periods, Japanese woodblock prints were a commercial form of art that reproduced the everyday life of ordinary people (the ukiyo-e style). Since different dyes and pigments were used to produce these prints, changing over time, the knowledge of these materials can be very important for the history and the conservation of ukiyo-e prints. This study will present the results of the investigation of several woodblock prints, produced between the 18th and 19th centuries. The artworks belong to the Asian art collection at the Museum of Zaragoza (Spain). The aim of the study is the identification of organic colorants and inorganic pigments employed by Japanese printers, specially emphasising the introduction of new synthetic compounds in the 19th and 20th centuries. Because prints are fragile artworks, several non-invasive methods in a multi-analytical approach were employed, as hyperspectral imaging in the visible and NIR range (HSI), in-situ point-by point Diffuse Reflectance Spectroscopy (DRS), LED µ-spectrofluorimetry, and Fiber Optic Reflectance Spectroscopy in the near-infrared range (FORS NIR) and mid-infrared spectroscopy (MIR), combined with X-ray Fluorescence to confirm the presence of some elements. The identification of the diverse materials was made upon a dedicated database involving Japanese pigments, dyes, mixtures (blue, green, orange, purple colours) and papers. By combining all these methods, all the inorganic compounds were identified, and also some organic colourants, especially for the blue and red areas. Finally, a chronology of the use of the colourants in the ukiyo-e woodblock prints between 1700 and 1900 is proposed.

In this work the development results of the TRITIUM project is presented. The main objective of the project is the construction of a near real-time monitor for low activity tritium in water, aimed at in-situ surveillance and radiological protection of river water in the vicinity of nuclear power plants. The European Council Directive 2013/51/Euratom requires that the maximum level of tritium in water for human consumption to be lower than 100 Bq/L. Tritium levels in the cooling water of nuclear power plants in normal operation are much higher than the levels caused by the natural and cosmogenic components, and may easily surmount the limit required by the Directive. The current liquid-scintillation measuring systems in environmental radioactivity laboratories are sensitive to such low levels, but they are not suitable for real-time monitoring. Moreover, there is no currently available device with enough sensitivity and monitoring capabilities that could be used for surveillance of the cooling water of nuclear power plants. A detector system based on scintillation fibers read out by photomultiplier tubes (PMTs) or silicon photomultiplier (SiPM) arrays is under development for in-water tritium measurement. This detector will be installed in the vicinity of Almaraz nuclear power plant (Spain) in Spring 2019. An overview of the project development and the results of first prototypes are presented., Comment: 6 pages, 11 figures, IEEE NSS-MIC Conf Record 2018

Instrumental neutron activation analysis of small flakes from the same flint fragment of archeological artefacts from Palaeolithic sites (''Abrigo de la Quebrada'', ''Cova de les Cendres'' and ''Cova Negra''), and geological sources (Chelva, Valencia, and Alcoi, Alicante) from the eastern Spain, was performed. The chemical contents of 27 elements were obtained. Ga, Ce, Nd, Yb, Zr and Hf were discarded due to high variations within the same fragment. The identification of chemical fingerprints within hetero- geneous flint fragments was able to differentiate flint types and variants (''Domeno'' and ''Serreta''), contributing to provenance and human mobility in ancient times.

This work summarizes the characterization of flint artefacts from the Middle Palaeolithic site ‘Abrigo de la Quebrada’ (Chelva, Valencia, Spain) and flint geological samples collected in the Chelva area. Additionally, some flint artefacts located outside this geographical zone were also analysed and compared with the samples from the Abrigo de la Quebrada site. Flint samples have been studied using methods of macroscopic description and physicochemical analysis [energy dispersive X-ray fluorescence spectrometry (EDXRF) and X-ray diffraction (XRD)]. Multivariate statistical analysis of the EDXRF data and the determination of the crystalline index of quartz, obtained from the XRD patterns, are suitable methods to discriminate between local and allochthonous flint artefacts in agreement with the macroscopic classification. These results provide new analytical information of the flint artefacts on a geographical area that had not been studied so far. Copyright © 2015 John Wiley & Sons, Ltd.

The Iberian Mediterranean Basin is home to one of the largest groups of prehistoric rock art sites in Europe. Despite the cultural relevance of prehistoric Spanish Levantine rock art, pigment composition remains partially unknown, and the nature of the binders used for painting has yet to be disclosed. In this work, we present the first omic analysis applied to one of the flagship Levantine rock art sites: the Valltorta ravine (Castellón, Spain). We used high-throughput sequencing to provide the first description of the bacterial communities colonizing the rock art patina, which proved to be dominated by Firmicutes species and might have a protective effect on the paintings. Proteomic analysis was also performed on rock art microsamples in order to determine the organic binders present in Levantine prehistoric rock art pigments. This information could shed light on the controversial dating of this UNESCO Cultural Heritage, and contribute to defining the chrono-cultural framework of the societies responsible for these paintings., This research was developed as a part of the project ‘NEOSOCWESTMED’ (no. 628428) under the Marie Curie Actions in the 7th Programme of the European Commission (FP7/2007–2013) and the “Projet Émergent 2016” of TRACES UMR 5608 of the French National Center for the Scientific Research (CNRS).

Since at least 5000 years ago, gilding techniques have been used for decoration purposes or to make artefacts appear as made of solid gold. Investigation of ancient gildings inevitably requires measuring their thickness, which is usually done either through the observation of cross-sections or by methods such as Rutherford backscattering spectroscopy, particle-induced X-ray emission and X-ray fluorescence. Whereas the former method requires sampling, the latter ones are non-invasive and therefore preferable. These non-invasive methods, however, measure the number of atoms per unit area, which can be converted into thickness only if the density is known. So far this has not been considered a problem and, in most cases, density has been assumed as that of bulk gold. This paper aims at highlighting the real extent of the issue by comparing the results obtained by scanning electron microscopy and the above-mentioned non-destructive methods on a group of samples gilded by electroplating. As a result of this work, the density of the gold layers has been found to be three times lower than the theoretical density, presumably due to the presence of micro-porosity, which brings to underestimate the thickness by the same factor. Caution is therefore recommended when providing results on intrinsically porous gildings such as fire gilding and depletion gilding, where the presence of voids precludes a realistic estimation of density., This work has been partially financed by the MINECO Projects HAR2012-33002 and HAR2015-67113-P.

In this article, analytical results will be presented and discussed regarding a selected set of figurines from the ancient Maya settlement of La Blanca in Peten, Guatemala. The objective is to characterize the ceramic material by two analytical complementary techniques: X-ray diffraction (XRD) and total reflection X-ray fluorescence (TXRF). The data obtained by means of both XRD and TXRF were compared and analyzed by multivariate statistical techniques in order to obtain sample groups according to their chemical composition. The results of this archaeometric study have been compared to those that have been obtained through macroscopic characterization by means of the traditional classification system know as Type-Variety. Discordances have been found between the clusters obtained by the Type-Variety classification system and the multivariate classification procedures performed on analytical data.

In this paper a general method based on energy-dispersive X-ray fluorescence (EDXRF) analysis has been tested to assess its possible use as a tool to reconstruct the structure and determine the thickness of two and/or multi-layered materials. The method utilizes the X-ray intensity ratios of Kα/Kβ or Lα/Lβ peaks (or the ratio of these peaks) for selected elements present in multi-layered objects of various materials (Au alloys, gilded Cu, gilded Ag, gilded Pb, Ag–Au Tumbaga, stone surfaces with protective treatments, Zn or Nickel plating on metals). Results show that, in the case of multi-layered samples, a correct calculation of the peak ratio (Kα /Kβ and/or Lα/Lβ) of relevant elements from energy-dispersive X-ray fluorescence spectra, can provide important information in assessing the exact location of each layer and for calculating its thickness. The methodological approach shown may have important applications not only in materials science but also when dealing with the conservation and restoration of multi-layered cultural heritage objects where the use of a Non-Destructive techniques to determine slight chemical and thickness variations in the layered structure is often of paramount importance to achieve the best results.

The presence of multilayered structures is common in such cultural artefacts as paintings, corroded metals, objects that underwent a whatever form of surface qualification. One of the most usual and complete ways to investigate such structures is observing a cross section, which requires sampling. There are however situations where at least part of the stratigraphic information can be derived non-destructively: the literature shows that X-ray fluorescence (XRF) has frequently been used, in recent years, for this purpose, with special regard to paintings and gilded metals. Aim of this paper is to further explore the suitability of XRF-based techniques to characterise multilayered structures. This is achieved by introducing improvements, with respect to previous works, in both equipment and data processing. The method, that has been developed for gilded and enamelled silver artefacts, relies on optimum excitation conditions provided for silver and on the relationship existing between the ratio AgKα/AgKβ of its fluorescence lines and the gilding thickness itself. The coating (gilding or enamel) thickness is derived by verifying the condition C Kα,Ag = C Kβ,Ag , where C Kα,Ag and C Kβ,Ag are the mass fractions of silver calculated on the lines AgKα and AgKβ, respectively. The calculations are carried out by PyMCA, a Fundamental Parameters code that implements the analysis of multilayered samples. As a case study we investigated in situ the four processional crosses of Borbona, Sant'Elpidio, Rosciolo and Forcella, made of a wood core with attached gilt and embossed silver sheets and enamelled silver plates. The analyses allowed to distinguish ancient restorations from original parts, to characterise the enamels and find their composition consistent with the dates of manufacturing and, as regards the cross of Rosciolo, to hypothesize the contribution of different “hands” in its manufacturing.

Parpallo cave (Gandia, Spain) is one of the most important Palaeolithic sites in the Spanish Mediterranean region. It is characterized by a mobiliary art whose archaeological sequence covers a dilated period (26,000–11,000 BP) and includes plaquettes decorated with black and different shades of red and yellow pigments. The aim of this paper is to present the results of analyses of the nature of black pigments used in the decoration of Parpallo plaquettes. The analyses were carried out by a non-destructive technique, by means of EDXRF. Furthermore, a colorimetric data bank has been created for conservation purposes. EDXRF measurements directly identify the use of manganese black pigments and indirectly the use of wooden charcoal based black pigments, in both zoomorphic motifs and undefined signs. No differentiation between manganese and non-manganese based black pigments was found from colorimetric measurements, but the data obtained will prove to be a useful reference for further studies as pigments fade with time.

EDXRF spectrometry was used to determine the pigment composition of the Pentecost Triptych, a Flemish masterpiece located at the Church of Sao Pedro de Miragaia (Porto, Portugal). The triptych was restored at the beginning of the 20th century and presents a great number of zones with repaints and colour alterations that can be observed on the whole of their surface. The identification of the original pigments and restoration pigments was based on their characteristic colour and the correlation between the detected elements and the named “key elements” of ancient pigments (Ca, Fe, Cu, Hg, Pb,…) and modern pigments (Ti, Ba, Cr, Zn, Co, Cd,…). The analysis of the triptych has been carried out in situ by means of portable instrumentation.

In this work we analyze the pigments used in the decoration of red and yellow motifs present in the portable art of the Parpallo Cave (Gandia, Spain), one of the most important Palaeolithic sites in the Spanish Mediterranean region. Energy dispersive X-ray fluorescence spectrometry (EDXRF) and spectrophotometry in the visible region (CIEL*a*b*color coordinates and spectral reflectance curves) were used to perform in situ fast analyses of the red and yellow motifs with portable equipment and to characterize their elemental composition and their colorimetric perception, respectively. According to the elemental composition, the intensity of the fluorescence iron signals in red and yellow motifs are higher than average values in the rock substrates. As expected, red motifs possess high values of the chromatic coordinate a* and yellow motifs possess high values of b*. This characterization was complemented with FT-IR analyses of microsamples detached from the red and yellow colored zones of a small set of plaquettes. Our results show that the artists used red and yellow pigments in the decoration likely derived from natural iron oxides as hematite and goethite.

The Physics Demo Project at the University of Valencia ( www.uv.es/fisicademos ) has developed a collection of physics demonstrations to be used during lectures. It consists of more than 130 experimental demos about different physics topics. More than 30 professors borrow them whenever they lecture on physics in any of our 40 courses in 17 different science or technical degrees, involving 246 ECTS and more than 3500 students. Each demo kit with a simple experimental set displays a particular physics phenomenon. An on-line user guide highlights the main physics principles involved, instructions on how to use it and advices of how to link it to the theoretical concepts or to technical applications. Demo lectures (and collections) are a usual and widespread practice in many countries but not in Spain. This unique initiative aims at the recovery of this practice by involving a growing collaborative team of users and with the aid of educational innovation projects. Here we explain the project content, organization and recent developments. Our experience, together with the positive students comments, allows us to draw the following conclusions: demos introduce the real sensible world in the lecture hall, providing the necessary link between concepts and everyday life, and becoming, again, something more than “chalk and talk”.

The results of the first elemental and structural physicochemical analyses (SEM–EDX, TXRF, XRD, FTIR, GC and EDXRF) of Early Neolithic red pigment samples from the region of Valencia confirm one of the earliest uses of cinnabar (HgS) in Spain (5300 to 5000 cal bc). They also inform on the storage of massive quantities of hematite and the development of specific technologies of hematite-based paint production and use. The samples were recovered at the three most significant Early Neolithic sites of the Mediterranean coast of Spain: Cova de l'Or (Beniarres, Alacant), Cova de la Sarsa (Bocairent, Valencia) and Cova Fosca (Vall d'Ebo, Valencia), which together have provided the most important European collection of Cardial ceramic ware (chronoculturally diagnostic of the Early Neolithic).

In this work, portable energy dispersive X-ray fluorescence (EDXRF) spectrometry was employed to the characterisation of the palette used by the Spanish artist Joaquin Sorolla (1863–1923) in the paintings ‘Vision of Spain’, a set of 14 oils on canvas painted by Sorolla between 1911 and 1919 by order of Mr Archer Huntington to decorate the library of the Hispanic Society of America (HSA) in New York. The analyses, sponsored by BANCAJA and provided by the HSA, were carried out in situ, prior to the cleaning and restoration process, while the paintings hanging on the walls of the library of the HSA. The results revealed that the paintings were made over different priming layers containing, respectively, lead white, zinc and barium compounds, lead white mixed with zinc white or lead white mixed with zinc and barium compounds. The EDXRF analyses of coloured zones identified up to 29 inorganic pigments and, in some cases, the probable use of organic pigments. Sorolla used traditional pigments as earth pigments, lead white, vermillion, etc., and modern pigments as cadmium yellow, zinc white, cobalt-based blue, chromium-based green, manganese-based violet, etc. These results provide valuable information about the Sorolla's palette during the last stage of his life. Copyright © 2011 John Wiley & Sons, Ltd.

The results of the analyses of elemental composition of red and black pigments of Levantine rock art from La Saltadora rock shelters (Valltorta gorge, Castellon, Spain) are presented in this paper. Nondestructive analyses were carried out using a portable energy dispersive X-ray fluorescence (EDXRF) spectrometer developed for in situ analysis. The results revealed the strong presence of calcium in all the analyzed locations due to the contribution of the underlying calcareous bedrock and the overlying crust. Iron is the main element detected in red pigments and manganese in black pigments. Iron and calcium ratios have been found indicative of the degree of preservation of the pictorial layer. Trace elements detected in the pigment composition confirm the use of different raw materials. Therefore, this work illustrates the potential of the portable EDXRF spectrometers for in situ analysis of rock art paintings. Copyright © 2010 John Wiley & Sons, Ltd.

Historical stained glass has a clear tendency to form a crusted layer on its surface due to the environmental exposure. One of the most delicate aspects to be faced during the restoration of historic glass windows is the cleaning of these thick corrosion crusts. For several centuries, stained glass windows have been cleaned using damaging mechanical (scalpel) and chemical (high acidic or alkaline solutions) methods. Today's understanding of the cleaning process comprises two complementary aims: improving the readability of the glass and reducing the weathering process of the historical glass. The act of removing deposits and encrustations resulting from corrosion should not endanger the artwork itself. Mechanical methods, cleaning solutions or gel pads are now being developed. However, these methods could present further problems. In this study, we examine a new cleaning method that can be employed to remove encrustations in a quick and efficient way. Results up to now, obtained on specific stained glass windows are promising; further researches are in process for other cases. We propose an optimized solution to dissolve calcium carbonates and lead sulphates from Avila Cathedral glass windows crust. This system is tailored to control pH, temperature, conductivity and concentration of Ca2+. Continuous on-line analysis of these parameters allows us to monitor the cleaning process. In particular, the Ca2+ concentration in the cleaning solution is controlled by means of a Ca2+ ion selective analyzer.

EDXRF analyses of cobalt-blue pigments were performed on 73 pieces of Valencian ceramics from the beginning of the 14th century up to the 20th century. In 67 of such samples, the pigment decoration was applied together with a tin opacified lead glaze cover on the clay body. In five samples the pigment was applied on the clay body without a glaze cover. The comparison between EDXRF spectra from coloured and non-coloured areas contains information about the pigment composition. Elements like Mn, Fe, Co, Ni, Cu, Zn and As are identified as characteristic of blue pigments; different associations of these elements were found and correlated with the chronology of the samples. The results can be used for identifying the different types of cobalt ores employed in the manufacture of blue pigments and their provenance.

In this paper, a Total-reflection X-ray Fluorescence (TXRF), a static and a portable Energy Dispersive X-ray Fluorescence (EDXRF) spectrometers are described. Both the equipments and the techniques employed in the field of the art and archeometry are compared. Some applications in this area are presented as well. The aim of the work is to know which spectrometer is the best suited depending on the work of art and the problem treated. The conclusion reached from the experience is that the portable EDXRF spectrometer is advisable to make “in situ” and online analysis in a multidisciplinary environment, the static EDXRF equipment is good to perform analysis on paper and metal pieces and the TXRF spectrometry is the best technique for very sensitive analysis of trace elements from micro-samples. Within the last technique, we propose to analyze the cottons used by the restorers in the different steps of the restoration process since it could be a good tool to study the composition of different layers and zones of the work of art.

The prints are fragile and delicate art objects that need for its examination a suitable technique for “in situ”, non-destructive and rapid analyses. The energy dispersive X-ray Fluorescence (EDXRF) spectrometry with portable instrumentation offers these analytical properties. In this work we present the EDXRF analyses of eight engravings elaborated with different techniques (etching and heliogravure) from the 17th to 20th centuries. The characterization of the paper is directly done from its EDXRF spectra, whereas the inks are characterized by the ink plus paper analysis after subtracting the background from the paper spectrum. Inorganic components of the paper engravings and inks have been identified from the EDXRF spectra and the results are discussed. Also, we present EDXRF analyses for the identification of inorganic components from six samples of modern inks.

The purpose of this work is the application of non-destructive analysis to differentiate underglaze and overglaze techniques used in the decoration of glazed ceramics from Valencia (Spain). This study was carried out by portable EDXRF spectrometry using an X-ray tube and a thermoelectrically cooled semiconductor detector. From the EDXRF spectra we have identified the main elements present in the tin-opacified lead glaze and in the cobalt pigments. The identification of the underglaze and overglaze decoration is based on the different ratios between the fluorescence line of the main component of the glaze (Pb-La line) and the fluorescence lines of the main components of the pigment (Co-Ka, Mn-Ka, Ni-Kα,... lines) when the incident angle of the X-ray beam varies. If the position of the detector is fixed, these ratios (Pb/Co, Pb/Mn, Pb/Ni,...) increase with the angle for underglaze decoration, and decrease for overglaze decoration.

Nowadays there is an intensive program for the conservation, restoration and analysis of the impressive and extensive Spanish cultural heritage. In the last few years, the Unidad de Arqueometria of the ICMUV has carry out a great quantity of in situ EDXRF analysis of pigments on materials of historic and cultural interest (altarpieces, frescoes, canvas, sculptures, etc.) from museums and churches of the whole of the Spanish geography. Here we present a few examples of the analysis of works of art using x-ray fluorescence spectrometry with a portable system based on x-ray tubes and a non-cryogenic Si-PIN detector. EDXRF qualitative and non-destructive analyses of stone, pigments and preparation layer of a polychrome sculpture from the Iberian period are compared with results obtained with destructive analytical techniques. The identification of inorganic key elements in a mural painting from the 14th and 15th centuries allowed the characterization of the pigments and techniques used by the artists and were a great help in the restoration process. The EDXRF analysis of a partially burnt medieval altarpiece allowed us to establish the elemental composition of the pigments from damaged and non-damaged areas. Finally, we present part of the systematic EDXRF analysis of the pigments on canvas from the work of Joaquin Sorolla with the objective of constructing a wide database on their pictorial materials. Copyright © 2002 John Wiley & Sons, Ltd.

Different flint types from the Middle Palaeolithic site of Abrigo de la Quebrada (Chelva, Valencia) are characterized, both macro- and microscopically, and compared with types found at other localities in the region. Although procurement predominantly concerned the immediate vicinity of sites, our results show the presence of the same types in assemblages separated by distances of up to 120 km. The long distances involved are suggestive of a pattern of North-South mobility of human groups along the coastline of central Mediterranean Iberia.

International audience; Spanish Levantine Rock Art is a unique pictorial expression within the prehistoric European context. Located in shelters in the inland regions of the Iberian Mediterranean basin, this art form, which must be necessarily studied in the frame of the process of neolithization of this territory, still lacks direct dating, and therefore its authorship is still open to debate. In this paper we present the first characterization of black pigments used in the Cova Remigia shelters in the Valltorta-Gassulla area (Castell on, Spain) by means of EDXRF spectrometry combined with SEM-EDS and Raman spectroscopy. Our aim is both to identify the raw material used for the preparation of black pigments and to make a first approach to the cultural choices involved in its use. The results are relevant for several reasons. Firstly, carbon-based black pigments have been identified for the first time in northern regions of Levantine rock art. Secondly, the recurrent use of black pigments in Cova Remigia questions the assumption of its restricted use in Spanish Levantine art. Thirdly, posterior repainting and graphic re-appropriation of black figures have been observed in Cova Remigia, giving rise to the combination of two colours, black and red, fact that is extremely rare in this rock art tradition. Finally, the identification of organic matter in the black pigments opens the possibility of radiocarbon dating.

We present examples of the application of the X-ray fluorescence (XRF) to the study of the artistic and cultural patrimony of the Comunidad Valenciana in the following areas: a) Valencian paintings of the XV and XVI centuries; b) silver ornaments coming from Iberian towns (s. III b.C.); c) ink and paper samples in manuscripts and engravings of the XVII and XIX centuries. The non destructive analyses are carried out “in situ” using a XRF system that consists of a tube of X-rays of 50 kV and 1 mA, and a detector of Si(Li) with an energy resolution 140 eV (FWHM at 5.9 keV).

XRF analysis has allowed a quick and precise detection and identification of the inorganic elements that compose the yellow pigments in altarpieces of the XV and XVI centuries painted by the Valencian artists Miguel Alcaniz, Vicente Macip, Juan de Juanes, Hernando Yanez de la Almedina and Hernando Llanos. The analyses have been carried out with an XRF portable system that consists of a tube of X-rays and detectors of Si(Li) and cadmium zinc telluride. This system has enabled a non-aggressive and non-destructive analysis of many pieces at the Museo de Bellas Artes of Valencia (Spain). Among the yellow pigments we have identified a pigment composed by lead and tin oxides named lead–tin yellow (Pb2SnO4), frequently used in European paintings from the XIV century until the first half of the XVIII century. This fact demonstrates the influence of elements and pictorial techniques from Europe to the region of Valencia.

Paraneoplastic syndromes are rarely described in animal models. It may be useful to have a suitable experimental model to study the mechanisms by which they are produced. In this study, we describe a murine lung adenocarcinoma, P07, which presents hypercalcemia, leukocytosis and cachexia. We determined the presence of PTHrP in plasma as well as GM-CSF produced by P07 cells. TNF-alpha, which is responsible for cachexia, could neither be detected in serum nor in P07 cell supernatants. We conclude that this model, which shows paraneoplastic syndromes similar to those of lung tumor patients, should be useful to study the pathways and significance of these signs.