Laser-induced breakdown spectroscopy (LIBS) was tested for all of the relevant issues in forensic examinations of commercial inks, including classification of pen inks on one paper type and on different paper types, determination of the deposition order of layered inks, and analysis of signatures and toners on one questioned document. The scope of this work was to determine the potential of a single LIBS setup that is compatible with portable instruments for different types of ink analysis, rather than building a very large database for inks and papers. We identified up to seven metals characteristic for the examined inks, which allowed to fully discriminate all eight black inks on one type of printing paper. When the inks were tested on ten different papers, the correct classification rates for some of them were reduced for reasons thoroughly studied and explained. The replicated tests on three crossing points, each one involving a pair of blue or black inks, were successful in five cases out of six. In the test simulating documents of forensic interest (questioned documents), LIBS was able to correctly identify the differences in three inks used for signatures on one of the three pages and the use of different printing inks on each page of the document.

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, 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.

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.

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).

An innovative hyperspectral LIDAR instrument has been developed for applications in marine environment monitoring research activities, remotely detecting the fluorescence spectra produced in the spectral interval between 400 nm and 720 nm. The detection system is composed by a custom made photomultiplier charge integrating and measuring (CIM) unit, which makes automatic background signal subtraction, and a liquid crystal tunable filter (LCTF). The new instrument therefore has hyperspectral resolution and allows automatic background subtraction; it is compact and automated by custom software that permit to adapt the instrument properties depending on the environmental conditions. Laboratory tests to characterize the instrument performance have been carried out, concluding that this sensor can be employed in remote sites for Chl-a detection.