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Glass fragments found in crime scenes may constitute important forensic evidence when properly analyzed, for example, to determine their origin. This analysis could be greatly helped by having a large and diverse database of glass fragments and by using it for constructing reliable machine learning (ML)-based glass classification models. Ideally, the samples that make up this database should be analyzed by a single accurate and standardized analytical technique. However, due to differences in equipment across laboratories, this is not feasible. With this in mind, in this work, we investigated if and how measurement performed at different laboratories on the same set of glass fragments could be combined in the context of ML. First, we demonstrated that elemental analysis methods such as particle-induced X-ray emission (PIXE), laser ablation induct i v e l y coupled plasma mass spectrometry (LA-ICP-MS), scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDS), particle-induced Gamma-ray emission (PIGE), instrumental neutron activation analysis (INAA), and prompt Gamma-ray neutron activation analysis (PGAA) could each produce lab-specific ML-based classification models. Next, we determined rules for the successf u l combinations of data from different laboratories and techniques and demonstrated that when followed, they give rise to improved models, and conversely, poor combinations wi l l lead to poor-performing models. Thus, the combination of PIXE and LA-ICP-MS improves the performances by similar to 10-15%, while combining PGAA with other techniques provides poorer performances in comparison with the lab-specific models. Finally, we demonstrated that the poor performances of the SEM-EDS technique, sti l l in use by law enforcement agencies, could be greatly improved by replacing SEM-EDS measurements for Fe and Ca by PIX E measurements for these elements. These findings suggest a process whereby forensic laboratories using different elemental analysis techniques could upload their data into a unified database and get reliable classification based on lab-agnostic models. This in tur n brings us closer to a more exhaustive extraction of information from glass fragment evidence and furthermore may form the basis for international-wide collaboration between law enforcement agencies.

Acoustics recordings from laser-induced plasmas are becoming increasingly regarded as a complementary source of information from the inspected sample. The propagation of these waves is susceptible to be modified by the physicochemical traits of the sample, thus yielding specific details that can be used for sorting and identification of targets. Still, the relative fragility of the acoustic wave poses major challenges to the applicability of laser-induced acoustics. Echoes and reflections sourcing from intrasample parameters as well as from interactions of the acoustic wave with the surroundings of the inspected target can dilute the analytical information directly related to the object contained within the recordings. The present work aims to experimentally scrutinize the impact of different parameters internal and external to the sample into the final acoustic signal from laser-induced plasmas in order to accurately use this information source for characterization purposes. Variables inherent to the sample such as dimensions, porosity and absorption coefficient, which guides the laser-matter coupling process, have been, for the first time, systematically studied using ad-hoc solids to thoroughly isolate their influence on the signal. Moreover, modulation of soundwave induced by the surroundings of the probed target and the anisotropy of the acoustic signal because of the angle at which the plasma is formed, have been evaluated. The present research has been supported with funding provided by the projects UMA18-FEDERJA-272 from the Junta de Andalucía and PID2020-119185GB-I00 from Ministerio de Ciencia e Innovación, Spain. M.B. is grateful to the Specific Research Project, Masaryk University MUNI/A/1412/2021. P.P. is grateful to the European Union's Next Generation EU (NGEU) plan and the Spanish Ministerio de Universidades for his Margarita Salas fellowship under the program ʺAyudas para la Recualificación del Sistema Universitario Españolʺ. Funding for open access charge: Universidad de Málaga / CBUA

The combination of data yielded by laser-induced breakdown spectroscopy (LIBS) and laser-induced plasma acoustics (LIPAc) is a topic of many prospective applications as these coexisting phenomena can cover different sample traits. Among the most interesting features that LIPAc could add to the expanded target picture is in-formation concerning structure and geophysical characteristics elusive to LIBS. In the present work, frequency spectra of minerals were explored to discriminate between chemically similar mineralogical phases. Several replicas of four different Fe-based minerals were analyzed to identify spectral traits linked to their chemistry in the frequency domain. First, the similarity between replicas of the same mineral family was verified and then, the cosine and Euclidian distances to minerals of different species were calculated to evaluate the discrimination capabilities of frequency spectra with results being compared to those obtained by LIBS. A partial least-squares one-vs-all model is described seeking to demonstrate sample classification by frequency means exclusively. As the use of LIBS-LIPAc for in-field mineral sorting has sparked interest, experiments reported were performed in stand-off within a thermal vacuum chamber (TVC). The TVC allowed data acquisition under Earth and Mars-like conditions, with the latter serving as a test of high relevance to assess the general applicability of the conclusions reached in Earth environment. Thorough discussion of data treatment is included with a focus on the impact of interference patterns arising from the laser-induced shockwave interaction with the medium surrounding the sample to avoid non-sample related information in the data processing schemes.

Li7La3Zr2O12 (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li+/H+ exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li+/H+ exchange and its dependence on microstructural features, accelerated Li+/H+ exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 °C hot water. The resulting chemical changes were quantified by analytical methods, i.e. inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser induced breakdown spectroscopy (LIBS). From the time dependence of the Li+ enrichment in the water, measured by ICP-OES, a bulk interdiffusion coefficient of Li+/H+ could be determined (7 × 10−17 m2 s−1 at 80 °C). Depth dependent concentrations were obtained from the LIBS data for both ions after establishing a calibration method enabling not only Li+ but also H+ quantification in the solid electrolyte. Short interdiffusion lengths in the 1 μm range are found for the single crystalline Ga:LLZO, in accordance with the measured bulk diffusion coefficient. In polycrystalline Ta:LLZO, however, very long diffusion tails in the 20 μm range and ion exchange fractions up to about 70% are observed. Those are attributed to fast ion interdiffusion along grain boundaries. The severe compositional changes also strongly affect the electrical properties measured by impedance spectroscopy. This study highlights that microstructural effects may be decisive for the Li+/H+ ion exchange kinetics of LLZO.

The forensic scenario, on which the round robin study was based, simulated a suspected intentional manipulation of a real estate rental agreement consisting of a total of three pages. The aims of this study were to (i) establish the amount and reliability of information extractable from a single type of evidence and to (ii) provide suggestions on the most suitable combination of compatible techniques for a multi-modal imaging approach to forgery detection. To address these aims, seventeen laboratories from sixteen countries were invited to answer the following tasks questions: (i) which printing technique was used? (ii) were the three pages printed with the same printer? (iii) were the three pages made from the same paper? (iv) were the three pages originally stapled? (v) were the headings and signatures written with the same ink? and (vi) were headings and signatures of the same age on all pages? The methods used were classified into the following categories: Optical spectroscopy, including multispectral imaging, smartphone mapping, UV-luminescence and LIBS ; Infrared spectroscopy, including Raman and FTIR (micro-)spectroscopy ; X-ray spectroscopy, including SEM-EDX, PIXE and XPS ; Mass spectrometry, including ICPMS, SIMS, MALDI and LDIMS ; Electrostatic imaging, as well as non- imaging methods, such as non-multimodal visual inspection, (micro-)spectroscopy, physical testing and thin layer chromatography. The performance of the techniques was evaluated as the proportion of discriminated sample pairs to all possible sample pairs. For the undiscriminated sample pairs, a distinction was made between undecidability and false positive claims. It was found that none of the methods used were able to solve all tasks completely and/or correctly and that certain methods were a priori judged unsuitable by the laboratories for some tasks. Correct results were generally achieved for the discrimination of printer toners, whereas incorrect results in the discrimination of inks. For the discrimination of paper, solid state analytical methods proved to be superior to mass spectrometric methods. None of the participating laboratories deemed addressing ink age feasible. It was concluded that correct forensic statements can only be achieved by the complementary application of different methods and that the classical approach of round robin studies to send standardised subsamples to the participants is not feasible for a true multimodal approach if the techniques are not available at one location.

The SuperCam instrument suite provides the Mars 2020 rover, Perseverance, with a number of versatile remote-sensing techniques that can be used at long distance as well as within the robotic-arm workspace. These include laser-induced breakdown spectroscopy (LIBS), remote time-resolved Raman and luminescence spectroscopies, and visible and infrared (VISIR; separately referred to as VIS and IR) reflectance spectroscopy. A remote micro-imager (RMI) provides high-resolution color context imaging, and a microphone can be used as a stand-alone tool for environmental studies or to determine physical properties of rocks and soils from shock waves of laser-produced plasmas. SuperCam is built in three parts: The mast unit (MU), consisting of the laser, telescope, RMI, IR spectrometer, and associated electronics, is described in a companion paper. The on-board calibration targets are described in another companion paper. Here we describe SuperCam's body unit (BU) and testing of the integrated instrument. The BU, mounted inside the rover body, receives light from the MU via a 5.8 m optical fiber. The light is split into three wavelength bands by a demultiplexer, and is routed via fiber bundles to three optical spectrometers, two of which (UV and violet; 245-340 and 385-465 nm) are crossed Czerny-Turner reflection spectrometers, nearly identical to their counterparts on ChemCam. The third is a high-efficiency transmission spectrometer containing an optical intensifier capable of gating exposures to 100 ns or longer, with variable delay times relative to the laser pulse. This spectrometer covers 535-853 nm ( 105 - 7070 cm − 1 Raman shift relative to the 532 nm green laser beam) with 12 cm − 1 full-width at half-maximum peak resolution in the Raman fingerprint region. The BU electronics boards interface with the rover and control the instrument, returning data to the rover. Thermal systems maintain a warm temperature during cruise to Mars to avoid contamination on the optics, and cool the detectors during operations on Mars. Results obtained with the integrated instrument demonstrate its capabilities for LIBS, for which a library of 332 standards was developed. Examples of Raman and VISIR spectroscopy are shown, demonstrating clear mineral identification with both techniques. Luminescence spectra demonstrate the utility of having both spectral and temporal dimensions. Finally, RMI and microphone tests on the rover demonstrate the capabilities of these subsystems as well., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

SuperCam is a highly integrated remote-sensing instrumental suite for NASA’s Mars 2020 mission. It consists of a co-aligned combination of Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), Visible and In frared Spectroscopy (VISIR), together with sound recording (MIC) and high-magnification imaging techniques (RMI). They provide information on the mineralogy, geochemistry and mineral context around the Perseverance Rover. The calibration of this complex suite is a major challenge. Not only does each technique require its own standards or references, their combination also introduces new requirements to obtain optimal scientific output. Elemental composition, molecular vibrational features, fluorescence, morphology and texture provide a full picture of the sample with spectral information that needs to be co-aligned, correlated, and individually calibrated. The resulting hardware includes different kinds of targets, each one covering different needs of the instrument. Standards for imaging calibration, geological samples for mineral identification and chemometric calculations or spectral references to calibrate and eval uate the health of the instrument, are all included in the SuperCam Calibration Target (SCCT). The system also includes a specifically designed assembly in which the samples are mounted. This hardware allows the targets to survive the harsh environmental condi tions of the launch, cruise, landing and operation on Mars during the whole mission. Here we summarize the design, development, integration, verification and functional testing of the SCCT. This work includes some key results obtained to verify the scientific outcome of the SuperCam system., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

A novel velocimetry method is proposed for point velocity measurement, which is based on tracking a laser-induced plasma in a flow. The plasma’s behaviour is first analysed spatially, temporally and spectrally in quiescent air. The dependence of this technique on the delay time between subsequent plasma images and the processing methods are described. It is found that, for optimized operation of the technique in a turbulent air jet (exit diameter 10.0 mm from a 480 mm long pipe; with an averaged velocity of 50 m/s at the jet exit resulting in Reynolds number of 34,000) with 100 µs time delay between plasma images, the systematic and random components of the velocity uncertainty are − 0.51 m/s and ± 3.6 m/s along the laser beam direction, and 1.25 m/s and ± 0.86 m/s along other directions perpendicular to the laser beam. These uncertainties are mainly caused by the asymmetric laser energy deposition during the formation of plasma, and the associated spatial resolution (in this realisation of the instrument) of 5 mm. The mean velocity measurements in the turbulent air jet flow are consistent with the reported flow behaviour in the literature for mean velocity: the turbulent intensity of axial velocity fluctuations is comparable to those in the literature but difference arises due to the limited spatial resolution. This velocimetry method is an alternative to traditional tracer-based velocimetry methods, because it does not require ‘seeding’ of particles or other substances in the flow. It also has the ability to measure local gas mixture composition, using laser-induced breakdown spectroscopy approach, simultaneously with flow velocity, but this aspect is not explored in the current study. Concept of Laser-Induced Plasma Image Velocimetry (LIPIV) applied to a turbulent jet flow. The LIPIV technique measures the flow velocity vector by using the temporal displacement of the laser-induced plasma in a flowing fluid. For this reason, two sequential images of the plasma with time delay Δt are used.

Mobile instrumentation is of growing importance to archaeometry research. Equipment is utilized in the field or at museums, thus avoiding transportation or risk of damage to valuable artifacts. Many spectroscopic techniques are nondestructive and micro-destructive in nature, which preserves the cultural heritage objects themselves. This review includes over 160 references pertaining to the use of mobile spectroscopy for archaeometry. Following a discussion of terminology related to mobile instrumental methods, results of a literature survey on their applications for cultural heritage objects is presented. Sections devoted to specific techniques are then provided: Raman spectroscopy, X-ray fluorescence spectrometry, Fourier transform infrared spectroscopy, laser-induced breakdown spectroscopy, and less frequently used techniques. The review closes with a discussion of combined instrumental approaches.

Double-pulse laser-induced breakdown spectroscopy (LIBS) was recently proposed for the analysis of underwater samples, since it overcomes the drawbacks of rapid plasma quenching and of large continuum emission, typical of single-pulse ablation. Despite the attractiveness of the method, this approach suffers nevertheless from a poor spectroscopic reproducibility, which is partially due to the scarce reproducibility of the cavitation bubble induced by the first laser pulse, since pressure and dimensions of the bubble strongly affect plasma emission. In this work, we investigated the reproducibility and the dynamics of the cavitation bubble induced on a solid target in water, and how they depend on pulse duration, energy, and wavelength, as well as on target composition. Results are discussed in terms of the effects on the laser ablation process produced by the crater formation and by the interaction of the laser pulse with floating particles and gas bubbles. This work, preliminary to the optimization of the spectroscopic signal, provides an insight of the phenomena occurring during laser ablation in water, together with useful information for the choice of the laser source to be used in the apparatus. (C) 2012 Optical Society of America

The applicability of laser ablation (LA) inductively coupled plasma (ICP) spectrometry for assessing elemental distributions in layered ceramics was investigated and compared with electron probe microanalysis (EPMA). Ordinary glazed wall tiles were employed as model specimens due to their defined structure and composition. They were used for calibration in the analysis of ancient pottery. A qualitative depth profile was acquired by single-spot laser drilling perpendicular to coatings with a Nd:YAG (1064 nm) laser coupled with an ICP optical emission spectrometer (OES). The lower lateral resolution associated with the laser spot diameter of 1.0 mm led to smoothing of the depth profile due to the averaging of local irregularities. In addition, transverse line scans by ablation across the tile section using an ArF* (193 nm) laser coupled with an ICP mass spectrometer (MS) were performed. LA-ICP-OES depth profiles and LA-ICP-MS transverse scans were validated by EPMA section scans and 2D back-scattered electrons images. The LA-ICP-OES acquisition was less dependent on sample surface and layer irregularities, whereas the transverse line scan over the tile section with the small-spot beam offered insight into the micromorphology of the individual layer. The combined approach revealed the occurrence of individual mineral grains, micro-heterogeneities and the character of interfaces between layers.

In the present work, laser ablation of a graphite target submerged in pure water was tested as a methodology for the production of carbon-based nanoparticles. The effect of varying the external pressure imposed to the liquid was investigated for the first time, in the range from 1 to 146 atm. Single or double laser pulses were used to ablate the target and the produced nanoparticles were characterized by atomic force microscopy (AFM) and by Raman spectroscopy. A spectroscopic study of the laser induced plasma features was carried out with a Ti target and interpreted in terms of laser-induced cavitation phenomena. Tubular nanoparticles of 25 nm average diameter were obtained only by single pulse (SP) ablation of graphite, while particles formed with the double pulse (DP) technique mainly consisted of graphite particulates. At 1 atm, these tubular nanoparticles were few and mixed with diamondlike carbon, while at 146 atm they were produced in a larger amount, suggesting that the high density effect induced by pressure plays a key role for their generation.

A model, formerly proposed and utilized to understand the formation of laser induced breakdown spectroscopy (LIBS) plasma upon irradiation with nanosecond laser pulses at different fluences and wavelengths, has been extended to the irradiation with femtosecond laser pulses in order to control the fractionation mechanisms which heavily affect the application of laser-ablation-based microanalytical techniques. The model takes into account the different chemico-physical processes occurring during the interaction of an ultrashort laser pulse with a metallic surface. In particular, a two-temperature description, relevant to the electrons and lattice of the substrate, respectively, has been introduced and applied to different tertiary and quaternary copper-based alloys subjected to fs and ns ablation both in the visible (527 nm) and in the UV (248 nm). The model has been found able to reproduce the shorter plasma duration experimentally found upon fs laser ablation. Kinetic decay times of several copper (major element) emission lines have been examined together with those relevant to the main plasma parameters. The plasma experimental temperature, derived assuming a Boltzmann distribution, and the electron density following the Saha equation have been compared with the corresponding theoretical data. A satisfactory description of plasma parameters and main matrix constituent composition has been obtained in the time window where local thermal equilibrium was assumed for LIBS data analysis. Improved analytical capabilities are predicted upon delayed detection of plasma emission in femtosecond LIBS, in relation to the better LOD achieved and to the improved data reproducibility expected. Results support the utilization of ultrafast laser Sources for trace detection, despite the residual fractionation occurring in the examined range of fluences which affects the linearity of experimental calibration curves built for tin and lead after internal standardization on copper. The validation of model results by experimental data allowed highlighting, from first principles, of the ablation mechanisms for the two temporal regimes and information on how this affects the accurate microanalysis of Cu-based alloys.

The present study exploits the information based on concentration of trace elements and minerals in understanding the role/mechanism of action of freeze-dried fruit powder suspended in distilled water of Momordica charantia (family: Cucurbitaceae) in diabetes treatment. Laser-induced break down spectroscopy (LIBS) spectra of plant product was recorded under optimized experimental conditions and analyzed. Several atomic lines such as Na, K, Mg, Ca, Fe, Al, etc. have been observed in the LIBS spectra of the above plant product. The concentrations of these minerals are determined by using calibration-free LIBS method. Correlation between the concentration of these elements/minerals and their defined role in diabetes management was studied in normal as well as diabetic animal models.

The present study approaches the general problem of the authentication of copper alloy artefacts of art and historical interest using non-invasive analytical techniques. It aims to demonstrate that a suitable combination of time-of-flight neutron diffraction and laser-induced plasma spectroscopy in integrated multidisciplinary authentication methodologies can provide crucial data for discriminating between genuine archaeological objects and modern counterfeits. After introducing the methodology, which is dedicated in particular to copper alloy figurines of ancient style, two representative authentication case studies are discussed. The results of the work provide evidence that the combination of multiphase analysis using TOFND and elemental depth profiles provided by LIPS makes it possible to solve most of the present authentication problems.