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Tritium (T) inventory in Plasma Facing Components (PFCs) will be one of the critical issues for ITER because of the impact tritium can have on the machine operation and safety. Laser Induced Breakdown Spectroscopy (LIBS) is a promising technique to accomplish this task, providing both qualitative and quantitative composition of the chemical elements retained in PFCs. LIBS does not require sample pretreatment or manipulation, it can work in-situ between fusion discharges or during maintenance periods, it is suitable for measurements at different residual pressures, with different background gases. It can detect all the chemical elements through their spectral emission. This paper presents the results of LIBS measurements at 100 mbar nitrogen pressure on metallic coating (W-Al-D) simulating the superficial composition of ITER divertor PFCs contaminated with nuclear fuel and material eroded from the first wall. LIBS spectra showed clear W, Al, D emission lines. A quantitative estimation of their relative concentration was performed by applying the Calibration Free (CF) analysis. CF does not require reference samples, so it's particularly suitable for this purpose. CF results were compared with the nominal concentrations and were found in good agreement with the latter.

A detailed characterization of painting materials by Raman and time-gated laser-induced fluorescence (TG-LIF) spectroscopy is proposed. The complementary capabilities of the considered techniques are investigated on a set of laboratory samples realized simulating real artworks. The achieved results confirmed the capability of Raman spectroscopy to characterize pigments and dyes, while the identification of binders and protective materials proved to be difficult because of their intense fluorescence. For this reason, the analyzed samples were also classified by TG-LIF spectroscopy in terms of their characteristic emission wavelengths and decay times. The complementary capabilities of Raman and TG-LIF techniques are confirmed, and a correlation between their results is assessed in order to obtain a complete characterization of the analyzed samples.

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.

Table S1. The DD-SIMCA model results. The yellow boxes represent the simulations in which the model did not identify as extraneous respect to the current model all the test samples.

The research and the individuation of tumour markers in biological fluids are currently one of the main tools to support diagnosis, prognosis, and monitoring of the therapeutic response in oncology. Although the identification of tumour markers in asymptomatic patients is crucial for early diagnosis, its application is still limited by the relatively low sensitivity and the complexity of existing methods (i.e. ELISA, mass spectrometry). We developed an easy, fast, and ultrasensitive surface-enhanced Raman scattering (SERS)–based system, for the detection and quantitation of the LGALS3BP (90K) biomarker that was used as a model, based on the development of antibody-functionalized nanostructured gold surfaces. The detection system was effective for the ultrasensitive detection and characterization of samples of different biochemical compositions. In conclusion, this work could provide the foundation for the development of a medical diagnostic device with the highest predictive power when compared with the methods currently used in cancer diagnostics. Electronic supplementary material The online version of this article (10.1007/s00216-020-02903-2) contains supplementary material, which is available to authorized users.

In this work we report on the Laser-Induced Breakdown Spectroscopy (LIBS) characterization of the Frascati Tokamak Upgrade (FTU) first wall (FW) and toroidal limiter after the spring-summer 2019 experimental campaign. We performed our analysis by using a compact LIBS system mounted on the FTU robotic arm, entering the FTU vacuum vessel (VV) and measuring the FW elements in-situ. The LIBS system was expressly designed and developed for this task and, to our knowledge, it represents the first prototype of LIBS mounted on a robotic arm for analyses inside a tokamak. It allows to perform measurements at (1) atmospheric pressure or (2) in vacuum (down to 10−2–10−3 mbar) or (3) under gas flux (He, Ne, Ar etc.) and is suitable for 4) single pulse or 5) double pulse LIBS measurements. The LIBS analyses revealed the main chemical components of the stainless-steel FTU FW, Mo and Ti from the Titanium-Zirconium-Molybdenum alloy (TZM) tiles of the toroidal limiter. A superficial contamination of Li, originating from past liquid lithium limiter experiments was also clearly revealed. To simulate a LIBS analysis of a component of the ITER divertor region we placed a metallic sample at the bottom of the FTU VV through a sample holder and we measured it with the LIBS system. The stratigraphy of this ITER-like sample, composed of an Al/D superficial layer 3 μm thick (D 5% atomic concentration, Al as proxy for Be) on a W substrate simulates ITER PFCs in the divertor baffle and was characterized with high axial resolution (few hundreds nm for each laser shot) although the D signal from the Dα emission line at 656.1 nm was found strongly interfering with the corresponding Hα emission at 656.28 nm from the environmental hydrogen.

In order to try to improve spectral separation for hydrogen isotope detection in plasma facing components, a flow of noble gas at reduced pressure is proposed as alternative to atmospheric pressure experiments in air during maintenance of fusion vessels. To this aim the already realized compact LIBS probe has been equipped with a sealable tip where a noble gas could flow. The tip was in contact with the selected point of the target and its proper positioning was guaranteed by an adjustable metallic cone. Laboratory measurements were carried out by flowing either He or Ar on ITER-like tiles. A positive effect of Ar flow on Hα signal intensity was observed, while a significant narrowing of the Hα band was obtained upon He addition. Additional measurements on deuterium doped samples simulating the tile's composition in ITER divertor region were performed by applying a local vacuum in the point of analysis or utilizing the set-up in double pulse (DP) mode. These experiments were aimed at optimizing the acquisition parameters of the LIBS setup (e.g, single or double pulse excitation, gate delay, gate width, interpulse delay) when operated in different conditions (vacuum, atmospheric pressure, under gas flow) in order to resolve the two nearby emission bands Hα and Dα, still preserving a satisfactory Signal-to-Noise-Ratio (SNR). Finally, considerations on applicability of Calibration Free (CF) method for the quantification of hydrogen isotopes are presented.

Laser Induced Breakdown Spectroscopy (LIBS) provides chemical information from atomic and ionic plasma emissions generated by laser vaporization of a sample. At the ENEA research center, in collaboration with IPPLM, an equipment has been set up to qualitatively and quantitatively determine the chemical composition of impurities deposited on Plasma Facing Components (PFC). The strength of the LIBS, for its capability of light elements detection, is fully exploited to determine the deuterium content since this element can be considered as the best choice proxy for tritium; the latter being is of great importance in assessing safe conditions to assure the continuous operation in nuclear fusion tokamak. Here we present the results of the Double Pulse LIBS (DP-LIBS) probing of deuterated samples with the simultaneous optical detection by medium-resolution and high-resolution spectrometer. Deuterium emission at 656.1 nm has been detected then the elemental composition has been quantified by applying the Calibration Free (CF) approach. The obtained results demonstrate that the DP-LIBS technique combined with CF analysis is suitable for the quantitative determination of tritium content inside the PFCs of next fusion devices like ITER.

The amount of hydrogen isotopes retained in plasma facing components (PFCs) and the determination of their surface layer composition are among the most critical issues for the next generation fusion device, ITER, under construction in Cadarache (France). Laser Induced Breakdown Spectroscopy (LIBS) is currently under evaluation as a technique suitable for quantitative, in situ, non-invasive measurements of these quantities. In order to detect traces of contaminant in metallic samples and improve its limit of detection (LOD), the Double Pulse LIBS (DP-LIBS) variant can be used instead of the standard Single Pulse LIBS (SP-LIBS), as it has been proven by several authors that DP-LIBS can considerably raise the analytical performances of the technique. In this work Mo samples coated with a 1.5–1.8 μm thick W-Al mixed layer, contaminated with co-deposited deuterium (D) were measured by SP- and DP-LIBS under vacuum (p ~ 5 × 10− 5 mbar), with an experimental set-up simulating conditions that can be found in a real fusion device between plasma discharges. A partial Calibration Free procedure (pCF) was applied to the LIBS data in order to retrieve the relative concentration of W and Al in the mixed layer. The amount of deuterium was then inferred by using tungsten as internal standard, accounting for the intensity ratio between the Dα line and nearby W I lines. The results are in satisfactory agreement with those obtained from preliminary Ion Beam Analysis measurements performed immediately after the specimen's realization. © 2017 Elsevier B.V.

In this paper the Laser Induced Breakdown Spectroscopy (LIBS) measurement of the deuterium (used as a proxy for tritium) retained in and the surface elemental composition of the FTU Mo (TZM) toroidal limiter tiles, carried out from remote (∼2.5 m) during short breaks of the operations or during machine maintenance, are reported. Single pulse technique has been used with the FTU vessel under high vacuum or in Nitrogen or Argon atmosphere. In vacuum experiments Dα and Hα lines have been detected with good resolution, while in Ar atmosphere (5 × 104 Pa) the two lines were partially overlapped due to Stark broadening. First results of measurements in N2 atmosphere (105 Pa) showed no presence of Dα and Hα lines. These measurements were also carried out for supporting the foreseen use of a robotic arm for an extended LIBS analysis of retained deuterium in the FTU vessel components. Keywords: LIBS, FTU tokamak, Toroidal limiter, Deuterium retention

This contribution to ECPD2019 is dedicated to the memory of Anatoly Faenov. During a period of approximately thirteen years 1994–2006, Anatoly and his wife Tatiana Pikuz (simply “Tania” for friends), accepting the frequent invitations of the National Institute for Nuclear Physics (INFN) and of the Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), cooperated with many Italian research laboratories dedicated to EUV and soft X-ray generation, spread in different towns (L'Aquila, Frascati, Milano, Padova, Pisa, Roma, etc.). In spite of the fact that they could stay in Italy only about one or two months per year, their activity was so intense that more than 50 peer- reviewed publications were generated from their experimental and theoretical work (just considering only the results obtained at L'Aquila and Tor Vergata—Rome Universities and at the ENEA Research Center of Frascati), without mentioning the cultural atmosphere that they stimulated in the field of Science and Humanity. The numerous experimental spectra obtained at ENEA by means of their spherically bent mica spectrometers, together with the corresponding theoretical simulations performed in Moscow, allowed to study the changing role of different excitations mechanisms for various plasma conditions, and to characterize at best the ENEA laser-plasma source for different applications: polychromatic and monochromatic micro-radiography of dried biological samples at 1 keV, soft X-ray contact microscopy (SXCM) of living cells in the water-window spectral region, spectroscopy of hollow atoms, etc. In this memorial paper, the main results of biological samples imaging on lithium fluoride (LiF) detectors, obtained with the ENEA and Tor Vergata University laser-plasma sources, are presented. In particular, the improvement of the micro-radiography and of the SXCM techniques obtained after moving from photoresist detectors and photographic films to lithium fluoride (LiF) detectors are discussed, for both dried and wet biological samples.

Here, we describe an innovative Integrated Laser Sensor (ILS) that combines four spectroscopic techniques and two vision systems into a unique, transportable device. The instrument performs Raman and Laser-Induced Fluorescence (LIF) spectroscopy excited at 355 nm and Laser-Induced Breakdown Spectroscopy (LIBS) excited at 1064 nm, and it also detects Laser Scattering (LS) from the target under illumination at 650 nm. The combination of these techniques supplies information about: material change from one scanning point to another, the presence of surface contaminants, and the molecular and elemental composition of top target layers. Switching between the spectroscopic techniques and the laser wavelengths is fully automatic. The instrument is equipped with an autofocus, and it performs scanning with a chosen grid density over an interactively-selected target area. Alternative to the spectroscopic measurements, it is possible to switch the instrument to a high magnification target viewing. The working distances tested until now are between 8.5 and 30 m. The instrument is self-powered and remotely controlled via wireless communication. The ILS has been fully developed at ENEA for security applications, and it was successfully tested in two outdoor campaigns where an automatic recognition of areas containing explosives in traces had been implemented. The strategies for the identification of nitro-compounds placed on various substrates as fingerprints and the results obtained at a working distance of 10 m are discussed in the following.

Laser-induced fluorescence (LIF), Raman spectroscopy and X-ray (XRF) fluorescence were used to study two frescoes at the S. Alexander catacombs complex, in Rome. LIF analysis has shown the presence of a transparent protective material probably deposited in previous restoration treatments and allowed to clearly distinguish the areas undergoing the current restoration process from the ones which still have to be treated. Raman and XRF analysis allowed to non-destructively characterizing most of the pictorial materials used for the artworks, including calcite (CaCO3), red ochre (Fe2O3), minium (Pb3O4), yellow ochre (α-FeOOH) and others. Therefore, thanks to the complementarity of the above-mentioned techniques, it was possible to obtain a detailed characterization of the studied frescoes. Finally, the whole ensemble of results constituted a valid tool to effectively plan the restoration of the frescoes. © 2018 Elsevier B.V.

We report the results of proximal Raman investigations at a distance of 7 m, to detect traces of explosives (from 0.1 to 0.8 mg/cm(2)) on common clothes with a new eye-safe apparatus. The instrument excites the target with a single laser shot of few ns (10(-9) s) in the UV range (laser wavelength 266 nm) detecting energetic materials like Pentaerythritol tetranitrate (PETN), Trinitrotoluene (TNT), Urea Nitrate (UN) and Ammonium Nitrate (AN). Samples were prepared using a piezoelectric-controlled plotter device to realize well-calibrated amounts of explosives on several cm(2). Common fabrics and tissues such as polyester, polyamide and leather were used as substrates, representative of base-materials used in the production of jackets or coats. Other samples were prepared by touching the substrate with a silicon finger contaminated with explosives, to simulate a spot left by contaminated hands on a jacket or bag during the preparation of an improvised explosive device (IED) by a terrorist. The observed Raman signals showed some peculiar molecular bands of the analyzed compounds, allowing us to identify and discriminate them with high sensitivity and selectivity, also in presence of the interfering signal from the underlying fabric. A dedicated algorithm was developed to remove noise and fluorescence background from the single laser shot spectra and an automatic spectral recognition procedure was also implemented, evaluating the intensity of the characteristic Raman bands of each explosive and allowing their automatic classification. Principal component analysis (PCA) was used to show the discrimination potentialities of the apparatus on different sets of explosives and to highlight possible criticalities in the detection. Receiver operating characteristic (ROC) curves were used to discuss and quantify the sensitivity and the selectivity of the proposed recognition procedure. To our knowledge the developed device is at the highest sensitivity nowadays achievable in the field of eye-safe, Raman devices for proximal detection.

Summary In this paper, the use of lithium fluoride (LiF) as imaging radiation detector to analyse living cells by single-shot soft X-ray contact microscopy is presented. High resolved X-ray images on LiF of cyanobacterium Leptolyngbya VRUC135, two unicellular microalgae of the genus Chlamydomonas and mouse macrophage cells (line RAW 264.7) have been obtainedutilizingX-rayradiationinthewaterwindowenergy rangefromalaserplasmasource.Theusedmethodisbasedon loading of the samples, the cell suspension, in a special holder wheretheyareinclosecontactwithaLiFcrystalsolid-stateXrayimagingdetector.Afterexposureandsampleremoval,the imagesstoredinLiFbythesoftX-raycontactmicroscopytechniquearereadbyanopticalmicroscopeinfluorescencemode. The clear image of the mucilaginous sheath the structure of the filamentous Leptolyngbya and the visible nucleolus in the macrophage cells image, are noteworthiness results. The peculiaritiesoftheusedX-rayradiationandoftheLiFimaging detectorallowobtainingimagesinabsorptioncontrastrevealing the internal structures of the investigated samples at high spatialresolution.Moreover,thewidedynamicrangeoftheLiF imagingdetectorcontributestoobtainhigh-qualityimages.In particular, we demonstrate that this peculiar characteristic of LiF detector allows enhancing the contrast and reveal details even when they were obscured by a nonuniform stray light.

Surface Enhanced Raman Spectroscopy (SERS), has been employed as a rapid and accurate tool for recognition and classification of different microorganisms. The vibrational spectrum intrinsically provides the fingerprint of the molecular structure of microorganisms, without sample preparation. The characterization of Bacillus spp., used as a simulants of the dangerous Bacillus anthracis by means of SERS technique has been carried out. The positive results on the use of the SERS substrate functionalized with phages specific for bacteria are showed. This work is a part of the RAMBO project (Rapid Air particle Monitoring against BiOlogical threats) funded by EDA (European Defense Agency) whose goal is the development of an advanced “detect to warn sensor” of cells and spores of dangerous bacteria, with high performance, good selectivity and reliability.

Optical and spectroscopic techniques offer unique possibilities for non destructive or micro-destructive characterization of surfaces, with widespread applications, starting from in-line monitoring of industrial processes. A significant group of industrial applications concerns nuclear grade material characterization and plasma diagnostics relevant to the thermonuclear fusion process. However, technologies and methodologies originally developed for specific in-vessel utilization, can easily find additional in-situ and remote application to environmental and cultural heritage (CH) diagnostics addressed to preventive conservation and restoration of surfaces. At ENEA Frascati different prototypes have been developed and patented to collect reflectance and fluorescence images excited at different ultraviolet and visible laser wavelengths, Raman and LIBS signals. Portable integrated instruments suitable for operation at different distances from a 1.5 to 30 m, have been assembled and operated in laboratory on multilayered samples and in field campaigns for Security and on CH painted surfaces. Significant results relevant to the cross fertilization among different applications will be presented and discussed.

Surface-enhanced Raman spectroscopy (SERS) measurements on 1,3,5-trinitroperhydro-1,3,5-triazine were performed with a table-top micro-Raman system exciting the analyte with a diode laser emitting at 785nm. The main Raman features of 1,3,5-trinitroperhydro-1,3,5-triazine were clearly identified, and a careful optimization of acquisition parameters was performed in order to increase the overall sensitivity of the apparatus. The amount of the sampled substance was determined through the analysis of high-resolution scanning electron microscope images of the substrate covered with the residual explosive and resulted to be of the order of few tens of picograms. This value demonstrates the applicability of commercial substrates to the ultrasensitive surface-enhanced Raman spectroscopy detection of explosives, allowing for their identification in real time. Copyright © 2013 John Wiley & Sons, Ltd. Additional supporting information may be found in the online version of this article at the publisher’s web site.

High temperature plasma in hydrogen isotopes is peculiar of thermonuclear fusion devices. The study of plasma-wall interaction is of paramount importance for avoiding both damage of plasma facing components (PFCs) and pollution of the plasma. To assure continuous and fault-free operation a strict control must be exerted on the amount of impurities deposited on, and of the fuel retained in the PFCs. This requirement makes Laser-Induced-Breakdown-Spectroscopy (LIBS) an ideal candidate for on-line quantitative monitoring of the walls of the current as well as of the next generation fusion devices like the International Thermonuclear Experimental Reactor (ITER). An experimental setup has been designed and realized in order to optimize the characteristics of a LIBS system working at low pressure and remotely, and it has been utilized in combination with calibration free procedures for quantitative analysis. In this work, a partial calibration free method has been developed for single shot analysis of hydrogen isotopes retention at the PFCs-like surfaces, based on the acquisition of high resolution spectra in a narrow wavelength range. Results of calibration free and partial calibration free have been obtained on suitably deuterated samples; preliminary spectroscopic considerations on tritium detection are also presented. © 2013 Elsevier B.V. All rights reserved.

Methods for rapid identification of explosives and their associated compounds at trace level quantities are needed for security screening applications. In this paper, we apply the surface-enhanced Raman spectroscopy (SERS) to detect and identify traces (as low as tens of pg) of pentaerythritol tetranitrate (PETN), ethylene glycol dinitrate (EGDN), cyclotrimethylene-trinitramine (RDX) and trinitrotoluene (TNT) using commercially available substrates (Klarite®, Renishaw diagnostics). High quality spectra were achieved within 10 s with a compact Raman spectrometer. Principal component analysis (PCA) of the data was performed to understand what factors affected the spectral variation across the samples. It was found that 76% of the spectral variation was explained by the first three PCs. Score plots for these components showed that the energetic materials can be clearly classified on the basis of SERS spectra also at trace level quantity. Our measurements further demonstrate the potential for using SERS as fast, in situ analytical tool for safety devices, with a sensitivity which competes and, in some cases, overcomes other techniques. Copyright © 2013 John Wiley & Sons, Ltd.

Several bacteria evolve in spore if the environmental conditions get to adverse e.g. for nutrient deprivation. The bacteria of genus Bacillus are Gram-positive aerobic bacteria and they are able to produce endospores (physiological inactive and resistant form), usually dispersed as aerosols. Endospores can survive for long time, until the conditions get back favourable. The genera Bacillus include pathogens, as Bacillus anthracis, used in the past as biological weapon. Prompt, accurate and sensitive detection is crucial for its control as pathogens or bioterrorism attacks. In case of the contamination with spores of B. anthracis, the time is essential to assure success in rescue. So, in this context, the early and fast analytical techniques, that need no or negligible sample preparation, is strongly required. Raman spectroscopy, and in particular Surface Enhanced Raman Spectroscopy (SERS), that can amplify nonlinearly the inherently weak Raman signal by several orders of magnitude, have become recognized and versatile analytical techniques also in microorganisms detection. These techniques can be used as sensitive tools for the detection and classification of biological threats, they can provide the chemical fingerprint of samples without complex and time-consuming pre-treatment samples preparation. Furthermore the development of in-field portable compact Raman platforms allows for using SERS for routine analysis. In the framework of the RAMBO (Rapid Air particle Monitoring against BiOlogical threats) project the feasibility of the SERS technique for the rapid identification and classification of few units of Bacillus spp (B. atrophaeus and B. thuringiensis) spores was investigated. B. atrophaeus and B. thuringiensis are harmless but genetically similar to the deadly B. anthracis. The RAMBO project purpose is the development of an advanced sensor with high performances, capable of detecting few spores or bacilli, with high selectivity and reliability, by means of two sensing techniques: SERS for early warning of bioagents dispersed in air or in water, and Polymerase Chain Reaction (PCR) technique for final recognition and validation. SERS and PCR will work in a microfluidic chip. In order to bind selectively the endospores, specific peptide receptors for B. thuringiensis have been selected to functionalize SERS substrates. To characterize the substrates, with and without spores to assess the effective immobilization of target, microscopy inspections, by optical microscope and Scanning Electron Microscope (SEM), were also carried out. The results show up the poor selectively of these peptides for B. thuringiensis, used as target, compared with the non specific Bacillus control. The performance of the system seems to be quite similar for both of them: the data processing by Principal Component Analysis and the following clustering analysis suggest the presence of indistinct answers for any bound endospore on the surface, and this is confirmed by microscope inspection. It could decrease the discrimination power of the sensor. Despite of such poor receptor selectivity, the SERS spectra of B. thuringiensis endospores show characteristic signals that can be related to DNA fragments or, much more probably, to the peptidoglycan (component of the external coat). This spectral feature could be used to detect the presence of B. thuringiensis endospores.

A study on the application of surface-enhanced Raman spectroscopy (SERS) in detecting biological threats is here reported. Simulants of deadly Bacillus anthracis endospores were used. This study proposes an automated device where SERS is used as a fast, pre-alarm technique of a two-stage sensor equipped with a real-time polymerase chain reaction (PCR). In order to check the potentialities of SERS in terms of sensitivity and specificity for on-site, real-time, automatic detection and identification of biological agents, two strains of genetically and harmless closely B. anthracis-related spores, Bacillus thuringiensis and Bacillus atrophaeus, were used as simulants. In order to assure the selectivity of the SERS substrate against B. thuringiensis spores, the substrate was functionalized by specific peptides. The obtained SERS measurements are classified as positive or negative hits by applying a special data evaluation based on the Euclidian distance between each spectrum and a reference spectrum of blank measurement. Principal component analysis (PCA) was applied for discriminating between different strains representing dangerous and harmless spores. The results show that the SERS sensor is capable of detecting a few tenths of spores in a few minutes, and is particularly sensitive and fast for this purpose. Post-process analysis of the spectra allowed for discrimination between the contaminated and uncontaminated SERS sensors and even between different strains of spores, although not as clearly. For this purpose, the use of a non-functionalized SERS substrate is suggested.

Surface-enhanced Raman spectroscopy (SERS) measurements of some common military explosives were performed with a table-top micro-Raman system integrated with a Serstech R785 miniaturized device, comprising a spectrometer and detector for near-infrared (NIR) laser excitation (785 nm). R785 was tested as the main component of a miniaturized SERS detector, designed for in situ and stand-alone sensing of molecules released at low concentrations, as could happen in the case of traces of explosives found in an illegal bomb factory, where solid microparticles of explosives could be released in the air and then collected on the sensor’s surface, if placed near the factory, as a consequence of bomb preparation. SERS spectra were obtained, exciting samples in picogram quantities on specific substrates, starting from standard commercial solutions. The main vibrational features of each substance were clearly identified also in low quantities. The amount of the sampled substance was determined through the analysis of scanning electron microscope images, while the spectral resolution and the detector sensitivity were sufficiently high to clearly distinguish spectra belonging to different samples with an exposure time of 10 s. A principal component analysis procedure was applied to the experimental data to understand which are the main factors affecting spectra variation across different samples. The score plots for the first three principal components show that the examined explosive materials can be clearly classified on the basis of their SERS spectra.

The study of plasma-wall interactions is of paramount importance for continuous and fault free operations in thermonuclear fusion research to monitor the damages of plasma facing components (PFCs), plasma pollution from impurities and wall retention of hydrogen isotopes, like tritium. These needs make laser-induced-breakdown-spectroscopy (LIBS) a suitable candidate for a real time monitoring of PFCs in the current and next generation fusion devices, like ITER. It is also worthwhile for the quantitative analysis of surfaces, with micro-destructivity of the sample and depth profiling capabilities with sub-micrometric sensitivity. In this paper LIBS spectroscopy is exploited as a valid diagnostic tool for PFCs at the ENEA Research Center in Frascati (Italy) and at the Institute of Plasma Physics and Laser Microfusion (IPPLM) of Warsaw (Poland). The activities have been focused on LIBS characterization of samples simulating PFCs surfaces eroded/redeposited or contaminated from nuclear fuel after or during the normal operation of the reactor. © 2016 The Royal Swedish Academy of Sciences.

Estimating the tritium amount retained in the plasma facing components and their surface layer composition is of crucial importance for ITER. Laser-induced breakdown spectroscopy (LIBS) is an analytical technique suitable for in situ measurements of both these quantities. For improving its sensitivity, the double pulse (DP) variant can be used, instead of the standard single pulse (SP). In this work Mo samples coated with 1.5-1.8 μm thick W-Al (as a proxy for Be) mixed layer, with co-deposited deuterium were analyzed under vacuum (∼5 10-5 mbar) by SP and DP LIBS, showing enhancement of the spectral intensity for the latter. Calibration free method was applied to the LIBS data for getting the elemental concentration of W and Al. Results are in satisfactory agreement with those obtained from preliminary, ion beam analysis measurements. Deuterium concentration was tentatively estimated by accounting for the intensity ratio between Dα and nearby WI lines. © 2016 EUROfusion.

A new Raman-based apparatus for proximal detection of energetic materials on people, was developed and tested for the first time. All the optical and optoelectronics components of the apparatus, as well as their optical matching, were carefully chosen and designed to respect international eye-safety regulations. In this way, the apparatus is suitable for civil applications on people in public areas such as airports and metro or railway stations. The acquisition software performs the data analysis in real-time to provide a fast response to the operator. Moreover, it allows for deployment of the apparatus either as a stand alone device or as part of a more sophisticated warning system architecture made up of several sensors. Using polyamide as substrate, the apparatus was able to detect surface densities of ammonium nitrate (AN), 2-methyl-1,3,5-trinitrobenzene (TNT), 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl] nitrate (PETN) and urea nitrate (UN) in the range of 100-1000 μg/cm2 at a distance of 6.4 m using each time a single laser pulse of 3 mJ/cm2. The limit of detection calculated for AN is 289 μg/cm2. AN and UN provided the highest percentages of true positives (>82% for surface densities of 100-400 μg/cm2 and fingerprints) followed by TNT and PETN (17%-70% for surface densities of 400-1000 μg/cm2 and fingerprints). © 2015, by the authors; licensee MDPI, Basel, Switzerland.

Laser Induced Breakdown Spectroscopy (LIBS) is nowadays a well established tool for qualitative, semi-quantitative and quantitative analyses of surfaces, with micro-destructive characteristics and capabilities for stratigraphy. LIBS is an appealing technique compared with many other types of elemental analysis thanks to the set up versatility facilitating non-invasive and remote analyses, as well as suitability to diagnostics in harsh environments. In this work, LIBS capabilities were used for the determination of the atomic composition of multilayered samples simulating the tiles of plasma facing components in the next generation fusion machines such as ITER. A new experimental setup was designed and realized in order to optimize the characteristics of an LIBS system working at low pressure and remotely, as it should be for an in situ system to be applied in monitoring the erosion and redeposition phenomena occurring on the inner walls of a fusion device. The effects of time delay and laser fluence on LIBS sensitivity at reduced pressure were examined, looking for operational conditions suitable to analytical applications. The quantitative analysis of some atomic species in the superficial layer has been carried out using a Calibration Free (CF) approach in the time window where Local Thermal Equilibrium (LTE) was assumed for an LIBS analysis.

The occurrence of several plasma-wall interaction processes, eventually affecting the overall system performances, is expected in a working fusion device chamber. Monitoring the changes in the composition of the plasma facing component (PFC) surface layer, as a result of erosion and redeposition mechanisms, can provide useful information on the possible plasma pollution and fuel retention. To this aim, suitable diagnostic techniques able to perform depth profiling analysis of the superficial layers on the PFCs have been developed. Due to the constraints commonly found in fusion devices, the measuring apparatus must be non invasive, remote and sensitive to light elements. These requirements make LIBS (Laser Induced Breakdown Spectroscopy) an ideal candidate for on-line monitoring the walls of current and of next generation (as ITER) fusion devices. LIBS is a well established tool for qualitative, semi-quantitative and quantitative analysis of surfaces, with micro-destructive characteristics and some capabilities for stratigraphy. In this work, LIBS depth profiling capability has been verified for the determination of the composition of multilayer structures simulating plasma facing components covered with deposited impurity layers. A new experimental setup has been designed and realized in order to optimize the characteristics of a LIBS system working in vacuum conditions and remotely, two noticeable properties for an ITER-relevant diagnostics. A quantitative analysis has been carried out in determining the elemental composition of the ITER-like samples.

In this paper a novel on-line tritium monitor is presented. It is made with a single crystal diamond detector (SCD) covered with a thin layer of LiF 95% enriched in 6Li. Thermal neutrons impinging on the LiF layer produce α and T ions which are detected by the active diamond. The pulse height spectrum shows two separated peaks due to α and T ions respectively. By a proper calibration in a reference thermal flux the number of 6Li atoms and thus the absolute n+6Li→α+T reaction rate per unitary flux can be established. Once calibrated the detector can be used to measure the tritium production. Due to the many outstanding properties of diamond this detector could operate in the harsh working conditions of a fusion breeding blanket. A test of this detector was performed at the 14 MeV Frascati Neutron Generator (FNG). The detector was inserted inside a mock-up of the European Helium Cooled Lithium Lead (HCLL) Tritium Blanket Module (TBM), designed to validate the neutronic database for fusion application. The mock-up of the TBM was designed to perform a full set of experiments to validate tritium production code prediction comparing the experimental results with calculations. The measured tritium rates with the Li-Diamond detector are described in this paper. Comparison with calculations is in progress and will be reported in a future paper.

We report about the light-emitting properties of colour centres in lithium fluoride thin films and crystals treated with low-penetrating extreme-ultraviolet radiation and soft X-rays. Experimental fluorescence-imaging results show that, under the same irradiation conditions, stronger photoluminescence, up to a factor eight, is released by colour centres in a film thermally grown on silicon substrate than in a crystal. By using a classical-electromagnetism model, we take into account the role of the silicon substrate in the enhancement of spontaneous emission over a broad spectral range to analyze such behaviour.

We present the realization and characterization of photoluminescent nanometric periodic patterns of color centers (CCs) in lithium fluoride (LiF) produced by an interferometric method based on a coherent soft X-ray laser beam. Among broad-band light-emitting materials, LiF, in the form of crystals and thin films, is a radiation-sensitive material well known in dosimetry and as a laser-active medium in optically pumped photonic devices. Primary and aggregate electronic defects can be produced in LiF by low-penetrating electromagnetic radiation, like soft X-ray. The high brightness and spatial coherence of a capillary discharge laser, with the emission wavelength of 46.9 nm, allowed writing periodic lines of stable CCs at a nanometric scale emitting visible light under optical pumping. Interferometric encoding of luminescent nano-structures in LiF proved to be a powerful tool for producing low-dimensionality optical devices for photonic applications.

An innovative X-ray imaging detector based on Optically Stimulated Luminescence from color centers in lithium fluoride is presented. Regular photoluminescent patterns produced on LiF samples by different intense X-ray sources, like synchrotrons, laser plasma sources and a capillary discharge laser have been investigated by a Confocal Laser Scanning Microscope. The use of a LiF-based imaging plate for X-ray microscopy is also discussed showing microradiographies of small animals.

A confocal laser scanning microscope has been used in a non-conventional approach to reconstruct the depth distribution of stable, optically active color centers induced at the surface of a lithium fluoride crystal by a low energy electron beam. The formation of F2 and F 3 + aggregate electronic defects was limited to the penetration depth of the electrons in the material, as obtained from Monte Carlo simulations. This novel measurement technique could be easily used for spatial characterization of luminescent optical waveguides in transparent dielectrics.

Laser Induced Breakdown Spectroscopy (LIBS) is an attractive analytical technique for the in situ analysis of the chemical composition of the components inside the vacuum vessel of ITER and for estimating the tritium content in the machine. To improve its sensitivity a dual pulse (DP) configuration, with two laser pulses delayed in the range of nanosecond to several microseconds can be used. In this work DP measurements carried out jointly by ENEA and IPPLM associations in the frame of EFDA task WP13-IPH-A01-P3-01 on samples resembling ITER in vessel components after material re-deposition (still including carbon) are presented. A DP Nd:YAG laser, operating at 1064 nm, with delay between pulses ranging from 20 ns to 80 ms and pulse duration of 8-12 ns was used to interact with tungsten sample coated with 3 μm thick mixed layer of C/Al/W (Al was used instead of Be). An enhancement of the spectroscopic emission of the elements was observed compared to the standard LIBS measurements. A Calibration Free method was applied to the data for getting the concentration of each element. Results are in good agreement with the concentrations found by the post-mortem energy dispersive X-ray (EDX) analysis. © 2015 Elsevier B.V. All rights reserved.

It is demonstrated that Raman Spectroscopy is a fast and sensitive tool for the detection and classification of molecular species. The vibrational spectrum inherently serves as fingerprint of the chemical composition of each sample a thus makes identification and early warning of threats possible. Also microorganisms in areas susceptible to bacterial contamination can be sensed. However, to increase the sensitivity and selectivity of the technique various solutions have been studied such as Resonant Raman Spectroscopy or Surface-Enhanced Raman Spectroscopy (SERS). In this work we present our results on the application of the SERS technique for the characterization of Bacillus atrophaeus spores, a biological and genetic simulant of the deadly bacterium Bacillus anthracis, already used in terroristic attacks in 2001 against U.S. media and government offices causing the death of five people and the infection of other 22. This work is part of the RAMBO project (Rapid Air particle Monitoring against Biological threats) whose ultimate goal is the development of an advanced sensor with high performances, capable of detecting few spores or bacilli of dangerous species with good selectivity and reliability so as to be used as an early warning sensor. In this context, the SERS technique allows to recognize the characteristics vibrational bands of the spores with a scan duration of only few seconds, on amounts of few tenths of spores or less, demonstrating how it can be considered an effective and fast technique for early warning of biological threats as it has been considered in the RAMBO project. © Springer International Publishing Switzerland 2015.

In the framework of RAMBO (Rapid-Air Monitoring particle against biological threats) project of the European Defense Agency (EDA), the feasibility of an unattended Surface Enhanced Raman Spectroscopy (SERS) sensor for biological threats detection was investigated. Its main goal concern Bacillus anthrax detection, both as vegetative cells and endospores. However since such bacteria are classified in Risk Group 3 (very dangerous microorganism), Bacillus thuringiensis and Bacillus atrophaeus were used as simulants. In order to bind selectively the target bacilli, Phages properly selected were immobilized on an active commercially available SERS substrate (functionalization). The Phages are a type of virus that infect selectively, by means of receptors, specific bacteria. Moreover they can resist on water or air environments without losing their binding capabilities. The sensing surface was characterized by standard micro-Raman equipments to assess the background Raman features. The Raman measurements have been carried out from 10X to 100X of magnification to differentiate between average and local features. Moreover the fast response was acquired by limiting the measure time at less than 1 minute. Samples of vegetative cells and endospores of Bacilli were randomly dispersed on the functionalized SERS substrates. The results obtained are promising: samples with and without bacilli could be distinguished one from the other. This is a step toward the use of SERS as an effective and fast technique for early warning of biological threats.

In the last decades there have been several terroristic attacks with improvised explosive devices (IED) that have raised the need for new instrumentation, for homeland security applications, to obtain a reliable and effective fight against terrorism. Public transportation has been around for about 150 years, but terroristic attacks against buses, trains, subways, etc., is a relatively recent phenomenon [1]. Since 1970, transportation has been an increasingly attractive target for terrorists. Most of the attacks to transport infrastructures take place in countries where public transportation is the primary way to move. Terrorists prefer to execute a smaller-scale attack with certainty of success rather than a complex and demanding operation to cause massive death and destruction. [1]. Many commonly available materials, such as fertilizer, gunpowder, and hydrogen peroxide, can be used as explosives and other materials, such as nails, glass, or metal fragments, can be used to increase the amount of shrapnel propelled by the explosion. The majority of substances that are classified as chemical explosives generally contain oxygen, nitrogen and oxidable elements such as carbon and hydrogen [2]. The most common functional group in military explosives is NO2. That functionality can be attached to oxygen (ONO2) in the nitrate esters (PETN), to carbon (C-NO2) in the nitroarenes (TNT) and nitroalkanes (Nitromethane), and to nitrogen (N-NO2) as in the nitramines (RDX). Some organic peroxides, such as TATP and HMTD, are popular amongst terrorists because they are powerful initiators that can be easily prepared from easily available ingredients. Azides are also powerful primary explosives commonly used as initiators (commercial detonators) in civilian and military operations, therefore they could be potentially used by terrorists as initiators for IEDs. © 2014 SPIE.

Analytical performances of Laser Induced Breakdown Spectroscopy (LIBS) resulted not fully satisfactory in some cases such as historical bronzes, therefore, efforts should be focussed on improving ablation efficiency and on better understanding the plasma parameter evolution. To this aim a set of double pulse experiments have been carried out in almost collinear geometry at about 530 nm laser excitation. The first emitting source was either a ns or a fs laser the second a ns one. Data were collected as a function of the interpulse delay, in order to determine the ablation efficiency increase, to study the kinetics of plasma parameters (temperature, electron density) and the decay of atomic and ionic intensities with respect to the optical background. In parallel a previously developed model for laser ablation, ionization and following plasma decay, was implemented, adding a second laser pulse, to analyse the double pulse excitation in the considered geometry, and the time evolution of the same variables was investigated. Model results are able to reproduce the observed experimental trends and support the possibility of improving analytical performances by using the double pulse technique with inter-pulse delays in the entire investigated range. © 2014 Elsevier B.V.