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This report describes the results of Task T1.1 concerning European experiences and best practices in Conservation, Preservation and Valorisation of monuments and sites, and of Task T1.3 concerning the state of the art in relevant technologies.

Using portable instruments for the preservation of artworks in heritage science is more and more common. Among the techniques, Macro X-Ray Fluorescence (MA-XRF) and digital radiography (DR) play a key-role in the field, therefore a number of MA-XRF scanners and radiographic apparatuses have been developed for this scope. Recently, the INFN-CHNet group, the network of the INFN devoted to cultural heritage, has developed a MA-XRF scanner for in-situ analyses. The instrument is fully operative, and it has already been employed in museums, conservation centres and out-door fields. In the present paper, the MA-XRF analysis conducted with the instrument on four Italian artworks undertaking conservation treatments at the conservation centre CCR “La Venaria Reale” are presented. Results on the preliminary test to combine DR with MA-XRF in a single apparatus are also shown.

The LABEC laboratory, the INFN ion beam laboratory of nuclear techniques for environment and cultural heritage, located in the Scientific and Technological Campus of the University of Florence in Sesto Fiorentino, started its operational activities in 2004, after INFN decided in 2001 to provide our applied nuclear physics group with a large laboratory dedicated to applications of accelerator-related analytical techniques, based on a new 3 MV Tandetron accelerator. The new accelerator greatly improved the performance of existing Ion Beam Analysis (IBA) applications (for which we were using since the 1980s an old single-ended Van de Graaff accelerator) and in addition allowed to start a novel activity of Accelerator Mass Spectrometry (AMS), in particular for 14C dating. Switching between IBA and AMS operation became very easy and fast, which allowed us high flexibility in programming the activities, mainly focused on studies of cultural heritage and atmospheric aerosol composition, but including also applications to biology, geology, material science and forensics, ion implantation, tests of radiation damage to components, detector performance tests and low-energy nuclear physics. This paper describes the facilities presently available in the LABEC laboratory, their technical features and some success stories of recent applications.

Detectors are a key feature of the contemporary scientific approach to cultural heritage (CH), both for diagnostics and conservation. INFN-CHNet is the network of the Italian National Institute of Nuclear Physics that develops and applies new instrumentation for the study of CH. This process results in both optimized traditional state-of-the-art and highly innovative detection setups for spectrometric techniques. Examples of the former are X-rays, gamma-rays, visible-light and particles spectrometers tailored for CH applications, with optimized performances, reliability, weight, transportability, cost, absorbed power, and complementarity with other techniques. Regarding the latter, examples are ARDESIA, the array of detectors at the DAΦNE-Light facility, the MAXRS detection setup at the Riken-RAL muon beamline and the imaging facilities at the LENA Laboratory. Paths for next-generation instruments have been suggested, as in the case of the X-ray Superconductive Detectors and X-ray Microcalorimeter Spectrometers, allowing astonishing improvement in energy resolution. Many issues in CH can now be addressed thanks to scientific techniques exploiting the existing detectors, while many others are still to be addressed and require the development of new approaches and detectors.

The first part of this study reports on the wide campaign for the extension of the database of both trace and minor elements concentration in diopside by means of μ-PIXE measurements and of luminescence spectra in diopside and wollastonite by means of μ-IL measurements. Diopside and wollastonite are actually two of the most common lapis lazuli-forming minerals. For this former part of the study, we analysed rocks of known provenance at the microbeam line of the LNL laboratories in Legnaro (PD) of the Istituto Nazionale di Fisica Nucleare (INFN). The latter part of the paper is dedicated to the non-invasive Ion Beam Analyses (IBA) characterisation of six pieces of the “Collezione Medicea”. The collection is exhibited at the Museum of Natural History (University of Firenze) and belonged to the Medici family. It includes artworks made of lapis lazuli manufactured in the 16th and 17th centuries but there is not precise information about the provenance of the used raw material. Results on the artworks show, as expected, that the Chilean provenance of the material used for the analysed artworks has to be excluded. Lapis lazuli used for five of the analysed artworks can be ascribed to the Afghan quarry district, while one object cannot be attributed only on the base of diopside and wollastonite analysis.

Ants possess several features that make them good candidates as indicators of environmental contamination. Concentrations of six metals (Cu, Cd, Ni, Mn, Pb and Zn) were investigated in Crematogaster scutellaris , a myrmicine ant common throughout the Mediterranean basin. Concentrations of metals in ant bodies and soil samples from polluted and unpolluted sites were compared. Tissue-specific distribution of metals in a non-soluble form was examined using a novel technique that coupled histological imagery and micro-PIXE analysis. Zinc and cadmium accumulated in ants with respect to the soil. Copper body burdens were independent of soil concentration, while lower concentrations of nickel, manganese and lead were found in ants than in the soil, although ant body content was correlated with soil concentrations. Most of the metals were concentrated in the midgut, the Malpighian tubules and fat body, supporting the role of these organs as primary sites of metal storage and contaminant immobilization.

Lapis lazuli has been used for glyptics and carving since the fifth millennium BC to produce jewels, amulets, seals, inlays, etc; the identification of the origin of the stone used for carving artworks may be valuable for reconstructing old trade routes. Since ancient lapis lazuli art objects are precious, only non-destructive techniques can be used to identify their provenance, and ion beam analysis (IBA) techniques allow us to characterise this stone in a fully non-invasive way. In addition, by using an ion microprobe, we have been able to focus the analysis on single crystals, as their typical dimensions may range from a few microns to hundreds of microns. Provenance markers, identified in previous IBA studies and already presented elsewhere, were based on the presence/absence of mineral phases, on the presence/quantity of trace elements inside a phase and on characteristic features of the luminescence spectra. In this work, a systematic study on pyrite crystals, a common accessory mineral in lapis lazuli, was carried out, following a multi-technique approach: optical microscopy and SEM-EDX to select crystals for successive trace element micro-PIXE measurements at two Italian facilities, the INFN Laboratori Nazionali di Legnaro and the INFN LABEC laboratory in Firenze. The results of this work allowed us to obtain new markers for lapis lazuli provenance identification.

An accurate control of the optical properties of single crystal diamond during microfabrication processes such as ion implantation plays a crucial role in the engineering of integrated photonic devices. In this work we present a systematic study of the variation of both real and imaginary parts of the refractive index of single crystal diamond, when damaged with 2 and 3 MeV protons at low-medium fluences (range: 10^15 - 10^17 cm^-2). After implanting in 125x125 um^2 areas with a scanning ion microbeam, the variation of optical pathlength of the implanted regions was measured with laser interferometric microscopy, while their optical transmission was studied using a spectrometric set-up with micrometric spatial resolution. On the basis of a model taking into account the strongly non-uniform damage profile in the bulk sample, the variation of the complex refractive index as a function of damage density was evaluated., 13 pages, 7 figures. arXiv admin note: text overlap with arXiv:1608.07122

In this paper we report about the micro-PIXE characterisation of lapis lazuli, for a provenance study of this semi-precious stone, used for glyptic as early as 7000 years ago. The final aim is to find markers permitting to identify the origin of the raw material coming from three quarries in regions of historical importance: Afghanistan, Pamir Mountains and Siberia. This may help to reconstruct trade routes, especially for ancient objects for which written testimonies are scanty or absent at all. Due to the heterogeneity of lapis lazuli we concentrate our attention on single phases instead of the whole stone; in particular we focused on two of the main phases: lazurite, responsible for the blue colour, and diopside, the most frequent accessory mineral. This study was preceded and completed by means of microanalysis with Scanning Electron Microscopy (SEM-EDX) and Cold-Cathodoluminescence (cold-CL) analysis. Despite the limited number of analysed samples, results are sufficient to exclude/suggest a few features as provenance markers, partly confirming what has been previously published in literature.

Metals are one of the major classes of environmental contaminants and raise concerns for their adverse effects on ecosystems. Ants are good candidates as bioindicators for metal contamination assessment; previous studies indeed showed that ants are able to selectively accumulate some metals within their tissues. Available works provide only whole-body burdens of these contaminants, with scarce information on the fine-scale localisation in tissues and organs, although this information is important to better understand the behaviour of metals in living organisms and to clarify their effects in ecosystems. At the Florence external scanning microbeam, we are carrying on a Particle Induced X-ray Emission (PIXE) study on a common ant species sampled from sites with different environmental metal availabilities. Measurements were carried out on resin-embedded, self-standing sections for a direct localisation of metal deposits and an easy determination of their content. The combined use of the PIXE and the external scanning microbeam made it possible to map element distributions with good spatial resolution and sensitivity, restricting quantitative analyses to the metal accumulation regions. To determine in which tissues/organs metals concentrated, we compared PIXE maps with histological images on sections contiguous to the analysed slices. Measurements in the external set-up allowed us to avoid sample damaging. Differences in metal concentrations in ants from different sites resulted from quantitative PIXE analyses. Copyright © 2011 John Wiley & Sons, Ltd.

Fluid inclusions are small portions, usually smaller than 100 μm, of fluid trapped within minerals during or after growth. Their characteristics provide therefore fundamental information on nature and evolution of fluids present in the past in different geological environments. At the LABEC laboratory in Firenze, high-salinity fluid inclusions in quartz crystals, coming from the Apuan Alps metamorphic complex, were analysed at the external scanning microbeam. Results, although still preliminary, have already provided us with hints on fluid-rock interaction processes during the metamorphism of the Apuan Alps.

A new ionoluminescence (IL) apparatus has been successfully installed at the external scanning microbeam facility of the 3 MV Tandetron accelerator of the INFN LABEC in Firenze; the apparatus for photon detection has been fully integrated in the existing ion beam analysis (IBA) set-up, for the simultaneous acquisition of IL and PIXE/PIGE/BS spectra and maps. The potential of the new set-up is illustrated in this paper by some results extracted by the analysis of art objects and advanced semiconductor materials. In particular, the adequacy of the new IBA set-up in the field of cultural heritage is pointed out by the coupled PIXE/IL micro-analysis of a lapis lazuli stone; concerning applications in material science, IL spectra from a N doped diamond sample were acquired and compared with CL analyses to evaluate the relevant sensitivities and the effect of ion damage.

The Western Alps of Northern Italy mostly consist of lithotectonic units which re-crystallised and were metamorphosed at high depth in a subduction zone. During their exhumation to shallow crustal levels, however, the high-pressure (high-P) mineral assemblages were pervasively re-equilibrated under low-pressure (low-P) conditions, making difficult to estimate the metamorphic thermal peak. Rutile [TiO 2 ] is a typical high-P mineral, occurring as relict phase in low-P re-equilibrated metamorphic rocks. Recent studies suggest that, in thermodynamic systems buffered by the occurrence of quartz and zircon in the rock, Zr content in rutile is a temperature-dependent function that can be modelled quantitatively. An application of rutile Zr-geothermometer to continental and oceanic rocks of the Western Alps, pervasively re-equilibrated under low-P conditions, is presented. The selected rutile crystals were analysed by PIXE using a microbeam set-up at the LABEC laboratory of INFN in Florence. The PIXE spectra and maps were processed by Geopixe software package. Micro-PIXE analyses allowed determining the concentration and the distribution of Zr. Results obtained by applying the rutile Zr-geothermometer gave a more precise indication about the temperatures of the metamorphic conditions suffered by Alpine metamorphic rocks with respect to phase relations and conventional geothermometry, showing that determination of Zr concentration by micro-PIXE technique is a useful tool to reconstruct metamorphic events. The continental units, outcropping in separate zones of Western Alps, show two slightly different thermal peaks (T mean = 530 ± 10 °C and T mean = 555 ± 10 °C) for the same metamorphic event. The oceanic units provide T mean estimates of 575 ± 10°C slightly higher than the continental units.

This work will present preliminary results concerning the use of time-resolved ion beam induced luminescence applied to provenance studies of lapis lazuli. Measurements were performed at the pulsed beam facility at LABEC laboratory in Florence. Lapis lazuli is a semi-precious gemstone, used as ornament since the early civilizations that can be found in few places on Earth. The importance of this work lies in understanding the origin of various samples of lapis lazuli, from which it may be possible to gain insight into trade routes from ancient times. The samples studied in this work originated from Chile, Afghanistan, Tajikistan, Myanmar, and Siberia. The stones were irradiated with 3 MeV protons and the resulting luminescence was detected by a photomultiplier tube, whose output was acquired using a sampling digitizer VME module (CAEN/V1720). Wavelength discrimination was performed at 430 nm utilizing a range of beam currents. The results showed that, by changing the beam current intensity, one can study different features of lapis lazuli, and this may aid in distinguishing lapis lazuli from different provenances.

In studies of Cultural Heritage, there is a growing demand for methods of material investigation. X-Ray Fluorescence (XRF) analyses have proven to be essential tools in these material studies. The XRF scanning spectrometer, developed at the LABEC laboratory in Florence, can perform both elemental mapping, on areas up to 20 × 20 cm 2 , and single spot analyses. Thanks to our close and long lasting collaboration with the Opificio delle Pietre Dure in Florence, one of the most prestigious restoration centers in the world, we had the opportunity to use the new XRF spectrometer in analyzing the painting “La Muta” of Raffaello Sanzio, one of the “Old Masters” of the Italian Renaissance. Beyond identification of the painting palette, the XRF study further allowed for structural analysis in cases where single spot XRF measurements would not be adequate. For example, the new system allowed us to deduce Raffaello's use of bone black pigment and to analyze various instances of “pentimenti” (underlying image in a painting, evidence of revision by the artist).

The external microbeam facility at the 3 MV Tandetron accelerator of the LABEC Laboratory of INFN in Florence has been used to determine, by PIXE, major, minor and trace element abundances of minerals and groundmass in the lavas from the active Nyiragongo Volcano (Democratic Republic of Congo), which is well known for its lava lake intra-crateric activity [e.g. 1, 2]. During the last eruption of this volcano (January, 2002), two main flows entered the Goma town producing major devastation, forcing the rapid exodus of about 300,000 people and causing the death of 150 persons [3]. After this eruption, the interest of the scientific community on this volcanic area suddenly increased. In this respect, determination of major and trace element abundances in mineral phases and groundmass of lavas may allow to constrain the evolution of magma within the volcanic system from a quantitative view point, thus helping to better understand the way this volcano works.

We present a multi-analytical and multi-instrumental approach to a petrologic study of garnets from metapelites characterized by different metamorphic grades. The comparison between major, minor and trace element (Y) distribution in garnets crystallized at different temperatures was performed by electron microprobe (EDS and WDS) and the Proton Induced X-ray Emission microprobe (µ-PIXE). Two garnet samples were selected from metapelite rocks at different metamorphic grades from the tectonic unit of Stilo, Calabrian–Peloritanian Arc, Southern Italy. Quantitative spot analysis profiles and compositional X-ray maps of major elements and yttrium are reported. The major element zoning of garnets is mostly characterized by a smoothed and gradual concentric variation of all elements from core to rim. The Y concentration reveals a marked zoning with its distribution decreasing from about 7000 ppm to about 100 ppm from core to rim, respectively. The precise determination of the Y content by µ-PIXE technique allowed us to better define the rock thermal history, by applying the Y geothermometer. In particular, a common starting temperature of about 450 °C was calculated for the beginning of the garnet growth from all over the unit, but different temperatures in the range from 520 °C to 670 °C were estimated for the peak event in garnets from different areas, in agreement with the P–T values given by the main rock mineral assemblages, reflecting a different metamorphic grade.

Quantitative micro-PIXE and electron microprobe analyses, as well as micro-PIXE compositional mapping of trace elements were performed on monazite [(Ce, La, Nd, Th)PO4] inclusions in pyrope megablasts from Dora Maira Massif, Western Italian Alps for petrological and geochronological purposes.

Micro-fabrication in diamond is involved in a wide set of emerging technologies, exploiting the exceptional characteristics of diamond for application in bio-physics, photonics, radiation detection. Micro ion-beam irradiation and pulsed laser irradiation are complementary techniques, which permit the implementation of complex geometries, by modification and functionalization of surface and/or bulk material, modifying the optical, electrical and mechanical characteristics of the material. In this article we summarize the work done in Florence (Italy) concerning ion beam and pulsed laser beam micro-fabrication in diamond., 14 pages, 5 figures

Oltre che gli esami autoptici, che sono serviti anche a realizzare degli elaborati grafici con mappe tematiche della tecnica di esecuzione della pittura, il dipinto è stato oggetto di numerose indagini diagnostiche, quasi tutte di tipo non invasivo. Alcune di queste analisi sono accuratamente descritte in interventi che fanno sempre parte di questo articolo.

Broad beam ionoluminescence (IL) microscopy is a promising technique for the non-destructive characterisation of rocks and stone objects. Luminescence imaging by means of broad ion beams has been sporadically used by other authors but, to our knowledge, its potential has not yet been fully investigated, neither in geological science nor in other fields. The in-air broad beam IL microscope was developed and installed at the INFN-LABEC external microbeam in Florence. Similar to the cathodoluminescence (CL) microscope, the apparatus exploits a CCD colour camera collecting images (few square millimetres wide, with ∼10-μm spatial resolution) of the luminescence emitted by the sample hit by a defocused megaelectron volt (MeV) proton beam. The main differences with the well-established and widespread CL are the possibility of working in air (no sampling or conductive coatings required) and the possibility of combining the analysis with microbeam analysis, such as, for example, μ-IL and μ-PIXE (particle-induced X-ray emission). To show the potential of the technique, IL images of thin sections of lapis lazuli are compared with those obtained by means of an in-vacuum cold CL. An application to the study of stone artworks is also reported. This technique and apparatus will provide a valuable help for interdisciplinary applications, e.g. in geological sciences and in the cultural heritage field.

We demonstrate the feasibility of fabricating light-waveguiding microstructures in bulk single-crystal diamond by means of direct ion implantation with a scanning microbeam, resulting in the modulation of the refractive index of the ion-beam damaged crystal. Direct evidence of waveguiding through such buried microchannels is obtained with a phase-shift micro-interferometric method allowing the study of the multi-modal structure of the propagating electromagnetic field. The possibility of defining optical and photonic structures by direct ion writing opens a range of new possibilities in the design of quantum-optical devices in bulk single crystal diamond., Comment: 10 pages, 4 figures

In this paper an overview is given on recent results obtained in the framework of an Italian/Croatian collaboration aimed to explore the potential of techniques based on focused MeV ion beams to locally modify the structural, electrical and optical features of diamond.Experiments were carried out using light (H, He, C) ion beams with energies of the order of MeV, focused to micrometer-size spot and raster scanned onto the surface of monocrystalline (IIa or Ib) diamond samples. Different energies, ion species and fluences were used, in conjunction with variable thickness masks and post annealing processes, to define three-dimensional structures in diamond, whose electrical/optical/structural properties have been suitably characterized. Finite element numerical methods have been employed in the modeling of the material modification and in device design.

A fine control of the variation of the refractive index as a function of structural damage is essential in the fabrication of diamond-based optical and photonic devices. We report here about the variation of the real part of the refractive index at lambda=632.8 nm in high quality single crystal diamond damaged with 2 and 3 MeV protons at low-medium fluences (10^13 - 10^17 ions cm^-2). After implanting the samples in 125x125 um^2 areas with a raster scanning ion microbeam, the variation of optical thickness of the implanted regions was measured with laser interferometric microscopy. The results were analyzed with a model based on the specific damage profile. The technique allows the direct fabrication of optical structures in bulk diamond based on the localized variation of the refractive index, which will be explored in future works., 15 pages, 4 figures

This paper reports on the investigation of the electronic properties of a thin film CdS/CdTe solar cell with the Ion Beam Induced Charge (IBIC) technique. The device under test is a thin film (total thickness around 10 um) multilayer heterojunction solar cell, displaying an efficiency of 14% under AM1.5 illumination conditions. The IBIC measurements were carried out using focused 3.150 MeV He ions raster scanned onto the surface of the back electrode. The charge collection efficiency (CCE) maps show inhomogeneous response of the cell to be attributed to the polycrystalline nature of the CdTe bulk material. Finally, the evolution of the IBIC signal vs. the ion fluence was studied in order to evaluate the radiation hardness of the CdS/CdTe solar cells in view of their use in solar modules for space applications., Comment: 22 pages, 12 figures

In this paper, we describe the main features of the ionoluminescence (IL) apparatus recently installed at the external scanning microbeam facility of the 3 MV Tandetron accelerator of the INFN LABEC Laboratory in Firenze. The peculiarity of this IL set-up resides in the fact that the light produced by the ion irradiation of the specimen is collected by a bifurcated optical fiber, so that photons are shunted both to a CCD spectrometer, working in the 200–900 nm wavelength range, and to a photomultiplier (PMT). The accurate focusing of the optical system allows high photon collection efficiency and this results in rapid acquisition of luminescence spectra with low ion currents on luminescent materials; simultaneously, luminescence maps with a spatial resolution of 10 μm can be acquired through the synchronization of PMT photon detection with the position of the scanning focused ion beam. An optical filter with a narrow passband facing the photomultiplier allows chromatic selectivity of the luminescence centres. The IL apparatus is synergistically integrated into the existing set-up for ion beam analyses (IBA). The upgraded system permits simultaneous IL and PIXE/PIGE/BS measurements. With our integrated system, we have been studying raw lapis lazuli samples of different known origins and precious lapis lazuli artworks of the Collezione Medicea of Museum of Natural History, University of Firenze, aiming at characterising their composition and provenance.

Quantitative micro-PIXE and cathodoluminescence spectra obtained for amazonite crystals from Malawi and Brazil granitoids, in order to check the trace elements presumably responsible for their color. These granitoids, used as Natural Stones for inside coverings and furnishings, are precious and rare, and owe their preciousness to the color of the rock-forming aquamarine amazonite. The trace elements investigated by means of micro-PIXE show the occurrence of Fe, Rb, Pb and Ga at concentrations above the minimum detection limit. In particular, the Malawi amazonite has a higher Pb content than the Brazil amazonite, but for Pb content both samples show a nearly flat pattern profile along the whole crystals. The cathodoluminescence spectra in both samples display three main peaks at 284, 558 and 680 nm which may be attributed to the presence of Pb 2+ , Mn 2+ and Fe 3+ , respectively. As no Mn was detected by PIXE we suggest that its occurrence is below the PIXE detection limit. Micro-PIXE analysis and cathodoluminescence spectra of most common and uncolored K-feldspars do not reveal the presence of lead; therefore we support the hypothesis of Pb as the chromophore source.

We study the role of defects in the ``single-chain magnet'' CoPhOMe by inserting a controlled number of diamagnetic impurities. The samples are analyzed with unprecedented accuracy with the particle induced x-ray emission technique, and with ac and dc magnetic measurements. In an external applied field the system shows an unexpected behavior, giving rise to a double peak in the susceptibility. The static thermodynamic properties of the randomly diluted Ising chain with alternating $g$ values are then exactly obtained via a transfer matrix approach. These results are compared to the experimental behavior of CoPhOMe, showing qualitative agreement.

The economic interest in natural stones provides an interesting input to the study of coloured rock-forming minerals. Generally, the colour of a mineral is attributed either to the presence of intrinsically-coloured constituents or of trace elements substituting major elements in the crystallographic sites, or to physical factors such as crystal lattice defects. We have analysed the blue and blue-green silicate minerals dumortierite and amazonite, coming from Mozambique quartzites, and from Malawi and Brazil granitoids, respectively. This study was performed by a multiple analytical approach including (a) a comparison of different signals (optical light-polarized images, backscattered electron images and X-ray multielemental maps); and (b) a collection of quantitative data obtained by WDS systems for major elements, and by WDS and/or micro-PIXE facility for trace elements. A good correlation between Ti concentration zoning and pleochroism variations was observed in dumortierite. In addition, the blue dumortierite of Mozambique, with its unusual significant amounts of antimony (about 5 wt.% Sb2O3), represents a mineral with an intermediate composition between dumortierite and holtite. In amazonite the aquamarine colour seems to be related to the Pb content on the order of some hundreds of ppm.