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To control the spread of COVID-19, exceptional restrictive measures were taken in March 2020 that imposed a radical change on the lifestyle of millions of citizens around the world, albeit for a short period. The national lockdown, which lasted from 10 March to 18 May 2020 in Italy, was a unique opportunity to observe the variation in air quality in urban environments under conditions comprising almost total traffic restriction and a strong reduction in work activities. In this paper, the data from 17 urban monitoring sites in Tuscany are presented, and the PM and NO2 concentrations in the 2 months before the start of the lockdown and the 2 months after lockdown are compared with the corresponding months of the previous 3 years. The results show that the total loads of PM2.5 and PM10 (particulate matter with an aerodynamic diameter smaller than 2.5 and 10 µm, respectively) decreased, but they did not exhibit significant changes compared to previous years, whereas NO2 underwent a drastic reduction. For three of these sites, the chemical composition of the collected samples was measured using thermal–optical techniques, ion chromatography, and particle-induced X-ray emission analysis, and the application of multivariate positive matrix factorization analysis also allowed for PM10 source identification and apportionment. Using these analyses, it was possible to explain the low sensitivity of PM10 to the lockdown effects as being due to different, sometimes inverse, behaviors of the different sources that contribute to PM. The results clearly indicate a decline in pollution levels related to urban traffic and an increase in the concentration of sulfate for all sites during the lockdown period.

International audience; Target properties such as thickness and composition are essential ingredients in nuclear physics experiments, therefore, dedicated analyses to evaluate them before and/or after the measurement are often performed. In some experimental techniques, the exploited detectors allow for the evaluation of these properties on-line, i.e. directly during the experiment. In this paper, we report on the use of analysis methods coming from the Rutherford backscattering spectroscopy technique to obtain on-line information on the target used in a nuclear physics experiment. This measurement was performed at INFN LNL by exploiting the low-energy Coulomb excitation technique. The results have been compared with an independent Rutherford backscattering spectroscopy analysis of the same target performed at INFN LABEC in Florence.

There is a considerable interest in developing new analytical tools to fight the illicit trafficking of heritage goods and particularly of easel paintings, whose high market values attract an ever-increasing volume of criminal activities. The objective is to combat the illicit traffic of smuggled or forged paintworks and to prevent the acquisition of fakes or looted artefacts in public collections. Authentication can be addressed using various investigation techniques, such as absolute dating, materials characterization, alteration phenomena, etc.; for paintings this remains a challenging task due to the complexity of the materials (paint layers, ground, varnish, canvas, etc.) and preferable use of non-destructive methods. This paper outlines results from concerted action on detecting forged works of art within the framework of a Coordinated Research Project of the International Atomic Energy Agency (IAEA) called Enhancing Nuclear Analytical Techniques to Meet the Needs of Forensic Sciences

Elemental and organic carbon content of flame-generated soot nanoparticles produced under different operating conditions of equivalence ratio and particle residence time is determined by thermo-optical-transmission measurements, while particle carbon structure is characterized by Raman spectroscopy analysis. The sampled soot nanoparticles are produced in slightly-rich, almost bluish, flames and comprise small 2–4 nm nascent soot nanoparticles, often neglected in the primary carbonaceous emissions from combustion systems, and larger 4–15 nm soot particles. The application of the NIOSH-like protocol for the thermo-optical-transmission analysis allows the separation of the total carbon (TC) into fractions of organic carbon (OC), pyrolytic carbon (PC), and elemental carbon (EC). The lowest amount of elemental carbon is measured in young soot nanoparticles and it is progressively larger in mature soot particles. The organic carbon has the opposite trend and shows that it is the “pyrolyzable” carbon fraction of the young soot nanoparticles that transforms into elemental carbon in the primary soot. Raman spectroscopy showed consistent results as compared to the thermo-optical-transmission analysis indicating a analogous trend in the graphitization order of the different soot particles. Most importantly, the logarithm of the intensity of the measured photoluminescence background shows a linear dependence with the OC/EC ratio. Mass absorption coefficients (MAC) were retrieved by the thermo-optical-transmission analysis for the four soot samples; the estimated MAC coefficient ranged from 2 to 6 m2/g, dependently from the relative percentage of EC component. The data are in excellent agreement with currently available literature data and extend the determination of MACs to carbonaceous particles with a larger OC/TC content.

CERN has been building a transportable RFQ for use in the examination of art masterpieces based mainly on the PIXE (Proton Induced X-ray Emission) technique with an extracted beam. This new PIXE-RFQ accelerator is very compact, only one meter in length with a power consumption of less than 6 kVA for a beam energy of 2 MeV and an average current of 5 nA. The PIXE-RFQ will be used for the MACHINA (Movable Accelerator for Cultural Heritage In-situ Non-destructive Analysis) project developed jointly by CERN and INFN. This paper will present the detailed design and performances of the PIXE-RFQ as well as the fabrication technologies used and the current status of the project. The beam size and the peak current/duty cycle of the RFQ have been optimised for the Ion Beam Analysis (IBA) of artwork objects.

To control the spread of COVID-19, in March 2020 exceptional restrictive measures were taken imposing a radical change in the lifestyle of millions of citizens around the world, albeit for a short period of time. The national lockdown, which in Italy lasted from 10 March to 18 May 2020, was a unique opportunity to observe the variation in air quality in urban environments in a condition of almost total traffic block and a strong reduction in work activities. In this paper, the data from seventeen urban monitoring sites in Tuscany are presented by comparing PM and NO2 of the two months before the start of the lockdown and the two after with the corresponding months of the previous three years. The results show that the total load of PM2.5 and PM10 decreased but it did not exhibit significant changes compared to previous years, while NO2 undergoes a drastic reduction. For three of these sites, the chemical composition of the collected samples was measured by thermo-optical, ion chromatography and PIXE analysis, and the application of multivariate PMF analysis allowed the PM10 source identification and apportionment. Thanks to these analyses it was possible to explain the low sensitiveness of PM10 to the lockdown effects as due to different, sometimes opposite, behaviors of the different sources that contribute to PM. The results clearly indicated a decline in pollution levels related to urban traffic and an increase in the concentration of sulfate for all sites during the lockdown period.

This study reports on a novel, flexible, proton beam detector based on mixed 3D-2D perovskite films deposited by solution onto thin plastic foils. The 3D-2D mixture allows to obtain micrometer-thick and highly uniform films that constitute the detector's active layer. The devices demonstrate excellent flexibility with stable electric transport properties down to a bending radius of 3.1 mm. The detector is characterized under a 5 MeV proton beam with fluxes in the range [4.5 × 10

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.

The direct detection of 5-MeV protons by a flexible organic thin-film device is here reported., The direct detection of 5-MeV protons by flexible organic detectors based on thin films is here demonstrated. The organic devices act as a solid-state detector, in which the energy released by the protons within the active layer of the sensor is converted into an electrical current. These sensors can quantitatively and reliably measure the dose of protons impinging on the sensor both in real time and in integration mode. This study shows how to detect and exploit the energy absorbed both by the organic semiconducting layer and by the plastic substrate, allowing to extrapolate information on the present and past irradiation of the detector. The measured sensitivity, S = (5.15 ± 0.13) pC Gy−1, and limit of detection, LOD = (30 ± 6) cGy s−1, of the here proposed detectors assess their efficacy and their potential as proton dosimeters in several fields of application, such as in medical proton therapy.

2nd-century stucco fragments from the roman Domus Valeriorum were analyzed by Raman spectroscopy (Raman), imaging X-ray fluorescence (XRF) and energy dispersive X-ray microanalysis (EDX) in order to identify the pigments and materials thereon. Cinnabar, malachite, hematite, goethite and Egyptian blue were detected by the synergistic use of these techniques whereas calcite, with some traces of gypsum, was detected as materials for the bas-relief figures and the pictorial background. This non-destructive characterization is the first carried out on the Domus Valeriorum finds. The multi-analytical approach highlighted the complementarity and versatility of these techniques, suitable for both laboratory and in-situ analysis, on macroscopic or microscopic fragments without preliminary manipulation.

A particulate matter (PM) source apportionment study was carried out in one of the most polluted districts of Tuscany (Italy), close to an old waste incinerator plant. Due to the high PM10 levels, an extensive field campaign was supported by the Regional Government to identify the main PM sources and quantify their contributions. PM10 daily samples were collected for one year and analysed by different techniques to obtain a complete chemical characterisation (elements, ions and carbon fractions). Hourly fine (2.5 μm) and coarse (2.5-10 μm) aerosol samples were collected by a Streaker sampler for a shorter period and hourly elemental concentrations were obtained by PIXE. Positive Matrix Factorization (PMF) analysis of daily and hourly data allowed the identification of 10 main sources: six anthropogenic (Biomass Burning, Traffic, Secondary Nitrates, Secondary Sulphates, Incinerator, Heavy Oil combustion), two natural (Saharan Dust and Fresh Sea Salt) and two mixed sources (Local Dust and Aged Sea Salt). Biomass burning turned out to be the main source of PM, accounting for 30% of the PM10 mass as annual average, followed by Traffic (18%) and Secondary Nitrates (14%). Emissions from the Incinerator turned out to be only 2% of PM10 mass on average. PM10 composition and source apportionment have been assessed in a polluted area near a waste incinerator, by PMF analysis on daily and hourly compositional data sets.

With the aim to establish advantages and limitations of techniques commonly employed for material characterization of Cultural Heritage objects, we performed comparative measurements by LIBS, X-ray Fluorescence (XRF) and Particle Induced X-ray Emission (PIXE) on four typologies of materials. The samples include: 1) egg tempera pigments on gypsum ground; 2) oil paints on gypsum ground with light or dark imprimitura; 3) fragments of decorated glazed ceramic, and 4) ancient Roman coins. The optimal choice of an analytical instrument depends also on the sample type, its dimensions and transportability, and for these reasons our measurements involved two types of instruments per technique. The LIBS probing was done by a table-top instrument (on coins and ceramics) and by a stand-off system at distance of 9.5 m (on pigments). The XRF measurements involved a laboratory micro-XRF system (on coins) and a portable instrument (on pigments and ceramics). The PIXE analyses were obtained by TOP-IMPLART accelerator at ENEA Frascati, using a low energy line that produces the proton beam with adjustable energy between 3 and 7 MeV (used for the pigments and ceramics), and by INFN-LABEC system with proton energy of 3 MeV and complemented by Elastic Backscattering Spectrometry (EBS), for coin samples. Results relevant to quantitative analysis of major sample constituents, identification of trace components, and stratigraphy are reported and discussed for the examined typologies of samples.

The market of falsified or sub-standard medical products is a global scale phenomenon. This issue affects a wide range of medications, including life-saving medical products. In high-income countries the most falsified products are those defined "lifestyle", which include foremost anabolic steroids and phosphodiesterase 5 inhibitors. The spread of these products in the last years has been possible also because of their online purchase, since they can be bought anonymously and without any medical supervision or prescription. Their use can pose a serious threat for public health, especially because often are manufactured without adherence to quality standards. This leads to final products containing active ingredients different from those declared, at the wrong or unknown dose and contaminated with metals, synthesis by-products and other chemical substances. In this work, we present results on characterisation of illegal pharmaceutical products and doping agents by combining different techniques: chromatography coupled to mass spectrometry for organic analysis and accelerator-based nuclear analytical techniques, such as ion beam analysis (IBA), for elemental analysis. Three IBA techniques, namely PIXE (particle induced X-ray emission), PIGE (particle induced gamma-ray emission) and EBS (elastic backscattering spectrometry) were used in external beam mode to provide an elemental characterisation of the as-is material, placed simply in front of the proton beam, thus avoiding the need of preparing them with pre-analytical steps and greatly enhancing the measurement throughput. Several elements (F, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Br and Sr) were identified in the analysed products. External beam IBA measurements provided the quantitative elemental characterisation of the illegal pharmaceutical products and doping agents under study, complementary to the organic analysis results by chromatography and mass spectrometry thus allowing a rapid (a few minutes) and non-destructive direct assessment of the material for forensic purposes. For the first time IBA results from doping products are reported and further analysis by IBA involving two different accelerator laboratories (one in Italy and one in Brazil) allowed the comparison of results obtained on the same pharmaceutical product. Starting from the results obtained in our study, the actualisation of new research plans should be evaluated, which could lay the foundation for a classification system of illegal pharmaceutical products, doping products. and other substances, based on chromatography, mass spectrometry and IBA measurements; this could allow drawing inferences about the common characteristics of these substances, e.g. provenience of bulk materials, site of production etc. With this purpose, results obtained from two samples of the same pharmaceutical product by IBA in two different accelerator laboratories (one in Italy and one in Brazil) are compared.

The electromagnetic structure of Zn66 at low excitation energy was investigated via low-energy Coulomb excitation at INFN Legnaro National Laboratories, using the Gamma Array of Legnaro Infn Laboratories for nuclEar spectrOscopy (GALILEO) γ-ray spectrometer coupled to the SPIDER (Silicon PIe DEtectoR). A set of reduced E2, E3, and M1 matrix elements was extracted from the collected data using the gosia code, yielding 12 reduced transition probabilities between the low-spin states and the spectroscopic quadrupole moment of the 21+ state. The B(E2) values for transitions depopulating the 02+ state have been determined for the first time, allowing for the lifetime of this state to be deduced and, consequently, the ρ2(E0;02+→01+) monopole transition strength to be extracted. In addition, the B(E3;31−→01+) value has been determined for the first time in a Coulomb excitation experiment. The obtained results resolve the existing discrepancies between literature lifetimes and demonstrate that Zn66 cannot be described by using simple collective models. Therefore, new state-of-the-art beyond-mean-field and large-scale shell-model calculations were performed in order to interpret the structure of this nucleus. Both the experimental and theoretical results suggest that the triaxial degree of freedom has an important impact on electromagnetic properties of Zn66, while the unique features of the 02+ state indicate its distinct and rather isolated structure.

While more and more studies are being conducted on carbonaceous fractions—organic carbon (OC) and elemental carbon (EC)—in urban areas, there are still too few studies about these species and their effects in polar areas due to their very low concentrations, further, studies in the literature report only data from intensive campaigns, limited in time. We present here for the first time EC–OC concentration long-time data records from the sea-level sampling site of Ny-Ålesund, in the High Arctic (5 years), and from Dome C, in the East Antarctic Plateau (1 year). Regarding the Arctic, the median (and the interquartile range (IQR)) mass concentrations for the years 2011–2015 are 352 (IQR 283–475) ng/m3 for OC and 4.8 (IQR: 4.6–17.4) ng/m3 for EC, which is responsible for only 3% of total carbon (TC). From both the concentration data sets and the variation of the average monthly concentrations, the influence of the Arctic haze on EC and OC concentrations is evident. Summer may be interesting owing to high concentration episodes mainly due to long-range transport (e.g., from wide wildfires in the Northern Hemisphere, as happened in 2015). The average ratio of EC/OC for the summer period is 0.05, ranging from 0.02 to 0.10, and indicates a clean environment with prevailing biogenic (or biomass burning) sources, as well as aged, highly oxidized aerosol from long-range transport. Contribution from ship emission is not evident, but this result may be due to the sampling time resolution. In Antarctica, a 1 year-around data set from December 2016 to February 2018 is shown, which does not present a clear seasonal trend. The OC median (and IQR) value is 78 (64–106) ng/m3, for EC, it is 0.9 (0.6–2.4) ng/m3, weighing for 3% on TC values. The EC/OC ratio mean value is 0.20, with a range of 0.06–0.35. Due to the low EC and OC concentrations in polar areas, correction for the blank is far more important than in campaigns carried out in other regions, largely affecting uncertainties in measured concentrations. Through the years, we have thus developed a new sampling strategy that is presented here for the first time: samplers were modified in order to collect a larger amount of particulates on a small surface, enhancing the capability of the analytical method since the thermo-optical analyzer is sensitive to carbonaceous aerosol areal density. Further, we have recently coupled such modified samplers with a sampling strategy that makes a more reliable blank correction of every single sample possible.

An extensive field campaign was carried out in Florence (Tuscany) to investigate the PM2.5 composition and to identify its sources. The scientific objective of this study is providing a reliable source apportionment, which is mandatory for the application of effective mitigation actions. Particulate matter (PM) was collected for one year, simultaneously in a traffic site, in an urban background, and in a regional background site. While the use of two filter types (quartz and Teflon) allowed obtaining a comprehensive chemical characterization (elemental and organic carbon, ions, elements) by the application of different analytical techniques, the location of the three sampling sites allowed getting a better separation among local, urban, regional and transboundary sources. During shorter periods, the aerosol was also collected by means of a streaker sampler and PIXE (Particle Induced X-ray Emission) analysis of these samples allowed the assessment of hourly resolution elemental time trends. Positive matrix factorisation (PMF) identified seven main sources: traffic, biomass burning, secondary sulphate, secondary nitrates, urban dust, Saharan dust and marine aerosol. Traffic mass concentration contributions were found to be strong only at the traffic site (~8 &mu, g&middot, m&minus, 3, 33% of PM2.5). Biomass burning turned out to be an important PM2.5 source in Florence (~4 &mu, 3), with very similar weights in both city sites while at the regional background site its weight was negligible. Secondary sulphate is an important PM2.5 source on a regional scale, with comparable values in all three sites (~3.5 &mu, 3). On average, the contribution of the &ldquo, natural&rdquo, components (e.g., mineral dust and marine aerosols) to PM2.5 is moderate (~1 &mu, 3) except during Saharan dust intrusions where this contribution is higher (detected simultaneously in all three sites). High-time resolution data confirmed and reinforced these results.

International audience; SPIDER is a new array of segmented silicon detectors for low-energy Coulomb-excitation experiments, designed as an ancillary device for modern γ -ray spectrometers such as GALILEO and AGATA. Currently, it is used at the INFN Legnaro National Laboratories (LNL) for experiments with the GALILEO γ -ray array and the stable beams provided by the Tandem-XTU, ALPI-PIAVE accelerator complex. In this paper, a detailed description of SPIDER is presented, as well as the outcomes from the first in-beam experiment of the array coupled with GALILEO. In particular, radiation damage and cross-talk/charge-sharing effects induced by energetic heavy ions in SPIDER are investigated and the capabilities of the array to perform on-line Rutherford back-scattering analysis of the exploited target are presented. The material reported here can be used to plan future experiments with the GALILEO-SPIDER setup with the presently available stable beams at LNL and paves the way for future experimental campaigns with the radioactive beams provided in the near future by the SPES facility at LNL.

Scientific investigation is very important in studies addressing issues of archaeological and historical objects. Ion beam analysis (IBA) and macro X-ray fluorescence (MA-XRF) spectroscopy are remarkable tools to obtain information about elemental composition and imaging of historical artefacts with a non-invasive character. These investigation techniques were employed in the framework of a project aimed at supporting the characterization of materials and techniques related with the Roman wall painting. The archaeological excavations at Villa della Piscina in Rome have revealed a luxury building with a large pool (about 50 m long) and thermal baths and numerous fragments of plaster, coming from intentional demolitions referable to two distinct architectural contexts of the Villa during the imperial age, have been found. This work deals with studying the interesting wall pictorial apparatus of great cultural value of the heritage inherited from the Roman age in the area of the ancient city of Rome. The colour palette of the pigments investigated, in particular, by MA-XRF and particle-induced X-ray emission (PIXE) and has revealed Fe, Cu, Pb, Si and Hg as main elements. Traces of other constituents uncover the choice of the different colours chosen by the artists who had embellished the rooms of the Villa.

Low-energy Coulomb excitation is one of the simplest and most known tools to study the nuclear shape; for this reason it is nowadays widely used at radioactive beam facilities. The SPES facility, for the acceleration of radioactive beams will soon provide the first exotic beams at the Laboratori Nazionali di Legnaro (LNL) in Italy.a#13; To this end a new particle detector (Silicon PIe DEtectoR) to be used for Coulomb excitation studies has been installed at LNL. SPIDER has been coupled to the GALILEO array of germanium detectors, and a number of experiments have been already successfully performed. This paves the way for future experiments with the radioactive beams provided by the SPES facility.

International audience; The low-energy electromagnetic structure of 110Cd was studied using safe-energy Coulomb excitation at the Heavy Ion Laboratory, University of Warsaw. The preliminary results on the quadrupole deformation of lowlying 0+ states in 110Cd are presented and compared to the recent beyondmean-field and General Bohr Hamiltonian calculations.

The line for the pulsed beam of the 3 MeV Tandetron accelerator at LABEC (Florence) has been upgraded for ion implantation experiments aiming at the fabrication of single-photon emitters in a solid-state matrix. A system based on Al attenuators has been calibrated in order to extend the energy range of the implanted ions from MeV down to the tens of keV. A new motorized XY stage has been installed in the implantation chamber for achieving ultra-fine control on the position of each implanted ion, allowing to reach the scale imposed by lateral straggling. A set-up for the activation of the implanted ions has been developed, based on an annealing furnace operating under controlled high-vacuum conditions. The first experiments have been performed with silicon ions implanted in diamond and the luminescent signal of the silicon-vacancy (SiV) center, peaked at 738 nm, has been observed for a wide range of implantation fluences (108 ÷ 1015 cm−2) and implantation depths (from a few nm to 2.4 µm). Studies on the efficiency of the annealing process have been performed and the activation yield has been measured to range from 1% to 3%. The implantation and annealing facility has thus been tuned for the production of SiV centers in diamond, but is in principle suitable for other ion species and solid-state matrices.

At the 3 MV Tandetron accelerator of the LABEC laboratory of INFN (Florence, Italy) an external beam facility is fully dedicated to PIXE-PIGE measurements of the elemental composition of atmospheric aerosols. All the elements with Z > 10 are simultaneously detected by PIXE typically in one minute. This setup allows us an easy automatic positioning, changing and scanning of samples collected by different kinds of devices: long series of daily PM (Particulate Matter) samples can be analysed in short times, as well as size-segregated and high time-resolution aerosol samples. Thanks to the capability of detecting all the crustal elements, PIXE-PIGE analyses are unrivalled in the study of mineral dust: consequently, they are very effective in the study of natural aerosols, like, for example, Saharan dust intrusions. Among the detectable elements there are also important markers of anthropogenic sources, which allow effective source apportionment studies in polluted urban environments using a multivariate method like Positive Matrix Factorization (PMF). Examples regarding recent monitoring campaigns, performed in urban and remote areas, both daily and with high time resolution (hourly samples), as well as with size selection, are presented. The importance of the combined use of the Particle Induced Gamma Ray emission technique (PIGE) and of other complementary (non-nuclear) techniques is highlighted.

The correct determination of the X-ray peak areas in PIXE spectra by fitting with a computer program depends crucially on accurate parameterization of the detector peak response function. In the Guelph PIXE software package, GUPIXWin, one of the most used PIXE spectra analysis code, the response of a semiconductor detector to monochromatic X-ray radiation is described by a linear combination of several analytical functions: a Gaussian profile for the X-ray line itself, and additional tail contributions (exponential tails and step functions) on the low-energy side of the X-ray line to describe incomplete charge collection effects. The literature on the spectral response of silicon X-ray detectors for PIXE applications is rather scarce, in particular data for Silicon Drift Detectors (SDD) and for a large range of X-ray energies are missing. Using a set of analytical functions, the SDD response functions were satisfactorily reproduced for the X-ray energy range 1–15 keV. The behaviour of the parameters involved in the SDD tailing functions with X-ray energy is described by simple polynomial functions, which permit an easy implementation in PIXE spectra fitting codes.

Within the framework of research projects focusing on the sampling and analysis of airborne particulate matter, Particle Induced X-ray Emission (PIXE) and Energy Dispersive X-ray Fluorescence (ED-XRF) techniques are routinely used in many laboratories throughout the world to determine the elemental concentration of the particulate matter samples. In this work an inter-laboratory comparison of the results obtained from analysing several samples (collected on both Teflon and quartz fibre filters) using both techniques is presented. The samples were analysed by PIXE (in Florence, at the 3 MV Tandetron accelerator of INFN-LABEC laboratory) and by XRF (in Elche, using the ARL Quant’X EDXRF spectrometer with specific conditions optimized for specific groups of elements). The results from the two sets of measurements are in good agreement for all the analysed samples, thus validating the use of the ARL Quant’X EDXRF spectrometer and the selected measurement protocol for the analysis of aerosol samples. Moreover, thanks to the comparison of PIXE and XRF results on Teflon and quartz fibre filters, possible self-absorption effects due to the penetration of the aerosol particles inside the quartz fibre-filters were quantified.

The quantification of the elemental concentration of ambient particulate matter is a challenging task because the observed elemental loadings are not well above the detection limit for most analytical techniques. Although non-destructive nuclear techniques are widely used for the chemical characterization of ambient aerosol, only one multi-element standard reference filter material that mimics ambient aerosol composition has become recently available in the market. To ensure accuracy, reliability and comparability of instruments performance, multiple reference materials with different elemental mass loadings are necessary. In this study, an intercomparison exercise was performed to evaluate the measurement uncertainty and instruments performance using multi-element dust standard reference samples deposited on PTFE filters. The filter samples, produced by means of dust dispersion, were tested in terms of homogeneity, reproducibility and long-term stability (≈40 months). Eight laboratories participated in the exercise. The evaluation of the results reported by the participants was performed by using two sets of reference values: a) the concentrations reported by the Expert Laboratory, b) the robust average concentrations reported by all participants. Most of the reported on the certificate of analysis elements were efficiently detected in the sample loadings prepared as representative for atmospheric samples by the Expert Laboratory. The average absolute relative difference between the reported and the reference values ranged between 0.1% (Ti) and 33.7% (Cr) (CRM-2584). The participants efficiently detected most of the elements except from the elements with atomic number lower than 16 (i.e. P, Al, Mg). The average absolute percentage difference between the participants results and the assigned value as derived by the expert laboratory was 17.5 ± 18.1% (CRM-2583; Cr, Pb excluded) and 16.7 ± 16.7% (CRM-2584; Cr, P excluded). The average “relative robust standard deviation” of the results reported by all participants was 25.1% (CRM-2583) and 22.8% (CRM-2584).

Proton laser-plasma-based acceleration has nowadays achieved a substantial maturity allowing to seek for possible practical applications, as for example Particle Induced X-ray Emission with few MeV protons. Here we report about the design, implementation, and characterization of a few MeV laser-plasma-accelerated proton beamline in air using a compact and cost-effective beam transport line based on permanent quadrupole magnets. The magnetic beamline coupled with a laser-plasma source based on a 14-TW laser results in a well-collimated proton beam of about 10 mm in diameter propagating in air over a few cm distance.

In the framework of the COBRA project, elemental analyses of cultural heritage objects based on the particle induced X-ray emission (PIXE) are planned in a collaboration between the APAM laboratory of ENEA-Frascati and the LABEC laboratory of INFN in Florence. With this aim a 3–7 MeV pulsed proton beam, driven by the injector of the protontherapy accelerator under construction for the TOP-IMPLART project, will be used to demonstrate the feasibility of the technique with a small-footprint pulsed accelerator to Italian small and medium enterprises interested in the composition analysis of ancient artifacts. The experimental set-up for PIXE analysis on the TOP-IMPLART machine consists of a modified assembly of the vertical beam line usually dedicated to radiobiology experiments: the beam produced by the injector (RFQ + DTL, a PL7 ACCSYSHITACHI model) is bent to 90° by a magnet, is collimated by a 300 μm aperture inserted in the end nozzle and extracted into ambient pressure by an exit window consisting of a Upilex foil 7.5 μm thick. The beam is pulsed with a variable pulse duration of 20–100 μs and a repetition rate variable from 10 to 100 Hz. The X-ray detection system is based on a Ketek Silicon Drift Detector (SDD) with 7 mm2 active area and 450 μm thickness, with a thin Beryllium entrance window (8 μm). The results of the calibration of this new PIXE set-up using thick target standards and of the analysis of the preliminary measurements on pigments are presented.

Based at Izaña Observatory (~2400 m a.s.l. in Tenerife), we performed 1-h resolution measurements of elemental composition of dust in the Saharan Air Layer (SAL) and studied the variability of the ratios of these elements to aluminium (elemental ratios). In a period (~1 week) of continuous dust presence (50–200 μg/m), we observed rapid variations of dust composition; some elemental ratios changed by a factor 2 in a few (5–8) hours. The lowest variability (Normalized Variability Range, %) was found for Si/Al (9%) and Fe/Al (9%), followed by the ratios of K, Ti, Mg, Mn, Ca and Sr to Al (20–80%), and the highest for S/Al, Na/Al and Cl/Al (110–160%) and a number of trace metals (Cr, Cu, Ni, Zn, Zr) and Br (>200%). This variability was induced by the alternating impacts of three of the large North African dust sources: NE Algeria (rich in evaporite minerals bearing Ca, S, Sr, K and Mg and in illite mineral), Western Sahara to Bechar region (containing Na, S and Cl rich Yermosol soils) and SW Sahara – Western Sahel (rich in illite and hematite). We traced the variability in large-scale meteorology using the so-called North African Dipole Intensity (NAFDI: strength of the subtropical Saharan high -Morocco-to the monsoon tropical low -Nigeria-). The mobilization of dust from the different sources was associated with westward propagating Harmattan pulses linked to the change of phase of NAFDI (- to +), the associated westward shifts of the Saharan Heat Low and convective monsoon inflow. We found a correlation between dust composition in the SAL and NAFDI: moderate NAFDI values (0 to +2.5) were associated with Ca, K, Na, Mg and S rich dust linked to dust sources in NE Algeria, whereas higher NAFDI values (+2.5 to +4) were linked to Fe rich dust (Ca, Na and S depleted) linked to dust sources in SW Sahara – Western Sahel. The results of this study also show that some trace elements (Br, Cr, Ni, Zn and Zr) are influenced by industrial emissions into North Africa., This study was performed within the project VARDUST-SAL (PGC2018-099166-BI00), funded by the Ministry of Science, Research and Innovation of Spain, the Research State Agency of Spain and the European Regional Development Fund (ERDF). JLD is awarded with a posdoc contract Agustín de Bethencourt, funded by the Program Fomento de Transferencia del Conocimiento, funded by the Cabildo de Tenerife. A stage of JLD at the INFN was funded by the Universidad de La Laguna

The IAEA coordinated research project entitled ‘Enhancing Nuclear Analytical Techniques to Meet the Needs of Forensics Sciences’ (CRP F11021) [1, 2] develops a specific program targeting the authentication of Cultural Heritage goods. One application domain is the analysis of precious metals, in particular of collectible ancient silver coinage potentially exposed to counterfeiting, for which the synergetic analytical merits of IBA and neutron activation analysis (NAA) and their non- destructive character (which allows to preserve evidence) are highly adapted. The contribution reports the results of an inter-laboratory measurement program on reference silver targets and authentic ancient silver coins implying particle accelerators and neutron-based laboratories worldwide. First, the analytical performances of PIXE and of two NAA methods, namely prompt -ray activation analysis (PGAA) and instrumental neutron activation (INAA) were explored in terms of accuracy and sensitivity, and their complementarity for the determination of fineness, i.e. the concentration in Ag, was evaluated. XRF, a routine method for the analysis of alloys, was applied for sake of comparison. The second objective was to test and validate the interoperability of this approach through an international inter- comparison program. The studied materials are four Ag certified reference standards (MBH AGA1, AGA3, AGQ2 and Ag500) and a series of Portuguese Reis silver coins from the 17th to 19th centuries and French 5 Francs from the 1960’s. The results highlight the benefits of combining PIXE and neutron activation methods to determine the alloy composition for a wide range of elements where they outperform XRF in terms of precision and sensitivity. When measuring coins instead of standard reference materials, ascertaining the well-established legal Ag-Cu alloy content may be hindered by the Cu surface loss over time. The Cu concentrations measured using PIXE appear biased by the low probing depth of the method (max 20 µm) while NAA, as a bulk analyzing technique, gives the correct composition. PIXE allows measuring a dozen of impurities of the silver alloy, notably Au, Pb, Bi, Zn, Pd and Sb which are potential tracers of the origin of the metal. In spite of the coins surface composition alteration it is shown that the trace element concentrations determined by PIXE still reflect the silver fingerprint. [1] https://www.iaea.org/newscenter/news/new- research-project-to-focus-on-use-of-nuclear- techniques-in-forensic-science

The present work is a part of a scientific study conducted among several Arab countries in west Asia, under an International Atomic Energy Agency (IAEA) regional technical cooperation project for Arasia region. The project aims at producing for the first time a database of particulate matter (PM) elemental concentrations in the region that will help in future air quality studies in order to identify commonalities and differences in the presence and contribution of fingerprint pollution sources among the Arasia Member States. The first regional campaign was launched simultaneously in Lebanon, Iraq, Jordan, Syria and United Arab Emirates, using a harmonized sampling and analysis protocol of PM 10 and PM 2.5 samples. Different samples, collected between October 2014 and February 2015, from the participating countries, were analyzed by PIXE technique and gravimetric measurements were also carried out. The first results of the study will be discussed in a regional perspective. Our study shows that concentrations of fine aerosol fractions are often exceeding the WHO standard values as well as showing some disparities in the obtained values between the different sampling sites. However, some trend similarities of variations with time could also be observed, suggesting a common influence by trans-boundary or external sources of air pollution.

Particle-Induced Gamma-ray Emission (PIGE) is a powerful analytical technique that exploits the interactions of rapid charged particles with nuclei located near a sample surface to determine the composition and structure of the surface regions of solids by measurement of characteristic prompt γ rays. The potential for depth profiling of this technique has long been recognized, however, the implementation has been limited owing to insufficient knowledge of the physical data and lack of suitable user-friendly computer codes for the applications. Although a considerable body of published data exists in the nuclear physics literature for nuclear reaction cross sections with γ rays in the exit channel, there is no up-to-date, comprehensive compilation specifically dedicated to IBA applications. A number of PIGE cross-section data had already been uploaded to the Ion Beam Analysis Nuclear Data Library (IBANDL) ( http://www-nds.iaea.org/ibandl ) by members of the IBA community by 2011, however a preliminary survey of this body of unevaluated experimental data has revealed numerous discrepancies beyond the uncertainty limits reported by the authors. Using the resources and coordination provided by the IAEA, a concerted effort to improve the situation was made within the Coordinated Research Project on the Development of a Reference Database for PIGE spectroscopy, from 2011 to 2015. The aim of the CRP was to create a data library for Ion Beam Analysis that contains reliable and usable data on charged particle γ-ray emission cross sections that would be made freely available to the user community. As the CRP has reached its completion, we shall present its main achievements, including the results of nuclear cross-section evaluations and the development of a computer code that will become available to the public allowing for the implementation of a standardless PIGE technique.

Thick target yields for proton induced γ-ray emission (PIGE) on low-Z nuclei, namely B, N, Na, Al and Si, were measured for proton energies from 2.5 to 4.1 MeV and emission angles of 0°, 45° and 90°, at the 3 MV Tandetron laboratory of INFN-LABEC in Florence. The studied reactions were: 10B(p,α′γ)7Be (Eγ = 429 keV), 10B(p,p′γ)10B (Eγ = 718 keV) and 11B(p,p′γ)11B (Eγ = 2125 keV) for boron; 14N(p,p′γ)14N (Eγ = 2313 keV) for nitrogen; 23Na(p,p′γ)23Na (Eγ = 441 and 1636 keV) and 23Na(p,α′γ)20Ne (Eγ = 1634 keV) for sodium; 27Al(p,p′γ)27Al (Eγ = 844 and 1014 keV) and 27Al(p,α′γ)24Mg (Eγ = 1369 keV) for aluminum; 28Si(p,p′γ)28Si (Eγ = 1779 keV) and 29Si(p,p′γ)29Si (Eγ = 1273 keV) for silicon. The PIGE thick target yields have been measured with an overall uncertainty typically better than 10%. The use of the measured thick target yield to benchmark and validate experimental cross sections available in the literature is demonstrated.

Montale is a small town in Tuscany characterised by high PM10 levels. Close to the town there is a waste incinerator plant. There are many concerns in the population and in the press about the causes of the high levels of pollution in this area. Daily PM10 samples were collected for 1 year by the FAI Hydra Dual sampler and analysed by different techniques in order to obtain a complete chemical speciation (elements by PIXE and ICP-MS, ions by Ion Chromatography, elemental and organic carbon by a thermo-optical instrument); hourly fine ( Positive Matrix Factorization identified and quantified the major aerosol sources. Biomass burning turned out to be the most important source with an average percentage contribution to PM10 of 27% of and even higher percentages during the winter period when there are the highest PM10 concentrations. The contribution of the incinerator source has been estimated as about 6% of PM10.

Most air quality studies on particulate matter (PM) are based on 24-h averaged data; however, many PM emissions as well as their atmospheric dilution processes change within a few hours. Samplings of PM with 1-h resolution can be performed by the streaker sampler (PIXE International Corporation), which is designed to separate the fine (aerodynamic diameter less than 2.5 μm) and the coarse (aerodynamic diameter between 2.5 and 10 μm) fractions of PM. These samples are efficiently analyzed by Particle Induced X-ray Emission (PIXE) at the LABEC laboratory of INFN in Florence (Italy), equipped with a 3 MV Tandetron accelerator, thanks to an optimized external-beam set-up, a convenient choice of the beam energy and suitable collecting substrates. A detailed description of the adopted set-up and results from a methodological study on the detection limits for the selection of the optimal beam energy are shown; the outcomes of the research on alternative collecting substrates, which produce a lower background during the measurements, and with lower contaminations, are also discussed.

Particle Induced X-ray Emission (PIXE) analysis of aerosol samples allows simultaneous detection of several elements, including important tracers of many particulate matter sources. This capability, together with the possibility of analyzing a high number of samples in very short times, makes PIXE a very effective tool for source apportionment studies by receptor modeling. However, important aerosol components, like nitrates, OC and EC, cannot be assessed by PIXE: this limitation may strongly compromise the results of a source apportionment study if based on PIXE data alone. In this work, an experimental dataset characterised by an extended chemical speciation (elements, EC–OC, ions) is used to test the effect of reducing input species in the application of one of the most widely used receptor model, namely Positive Matrix Factorization (PMF). The main effect of using only PIXE data is that the secondary nitrate source is not identified and the contribution of biomass burning is overestimated, probably due to the similar seasonal pattern of these two sources.

Amongst Ion Beam Analysis (IBA) techniques applied to the study of atmospheric aerosol samples, Elastic Backscattering Spectrometry (EBS) and Particle Elastic Scattering Analysis (PESA) with MeV energy proton beams allows obtaining quantitative information about the concentration of C and other low-Z atoms like H, N and O in the sample. With these nuclear techniques a direct measurement of elemental carbon (EC) and organic carbon (EC) is not possible. Nevertheless, the detection of all the aforemetioned light elements may help to infer some information on the aerosol chemical composition. The H concentration obtained by PESA may be used as a proxy of OC; then, EC can be obtained as the difference between total carbon measured simultaneously by EBS and OC as estimated by PESA. The feasibility of the quantification of EC and OC following this approach in particulate matter samples collected on Teflon filters, where this information cannot be obtained by standard thermo-optical analyses, will be discussed. Moreover, thanks to the simultaneous measurements of H, C, N and O in the aerosol samples, the organic component of the aerosols (particulate organic matter, POM) can be directly calculated and thus the validity of the POM/OC conversion factors found in the literature can be tested.