Adriana Puiu

Submersible Spectrofluorometer for Real-Time Sensing of Water Quality

In this work, we present a newly developed submersible spectrofluorometer (patent pending) applied to real-time sensing of water quality, suitable for monitoring some important indicators of the ecological status of natural waters such as chlorophyll-a, oil and protein-like material. For the optomechanical realization of the apparatus, a novel conceptual design has been adopted in order to avoid filters and pumps while maintaining a high signal-to-noise ratio. The elimination of filters and pumps has the advantage of greater system simplicity and especially of avoiding the risk of sample degradation. The use of light-emitting diodes as an excitation source instead of Xe lamps or laser diodes helped save on size, weight, power consumption and costs. For sensor calibration we performed measurements on water samples with added chlorophyll prepared in the laboratory. The sensor functionality was tested during field campaigns conducted at Albano Lake in Latium Region of Italy as well as in the Herzliya Harbor, a few kilometers North East of Tel Aviv in Israel. The obtained results are reported in the paper. The sensitivity achieved for chlorophyll-a detection was found to be at least 0.2 µg/L.

Application of micro-Raman spectroscopy for fight against terrorism and smuggling

Abstract. We report the results of Raman measurements on some common military explosives and explosives precursors deposited on clothing fabrics, both synthetic and natural, in concentration comparable to those obtained from a single fingerprint or mixed with similar harmless substances to detect illegal compounds for smuggling activities. Raman spectra were obtained using an integrated portable Raman system equipped with an optical microscope and a 785-nm laser in an analysis of <1  min. The spectral features of each illicit substance have been identified and distinguished from those belonging to the substrate fabric or from the interfering compound. Our results show that the application of Raman spectroscopy (RS) with a microscope-based portable apparatus can provide interpretable Raman spectra for a fast, in-situ analysis, directly from explosive particles of some μm3, despite the contribution of the substrate, leaving the sample completely unaltered for further, more specific, and propedeutic laboratory analysis. We also show how the RS is suitable for detecting illegal compounds mixed with harmless substances for smuggling purposes or for counterfeiting activities.

Raman spectroscopy for the detection of explosives and their precursors on clothing in fingerprint concentration: a reliable technique for security and counterterrorism issues

In this work we report the results of RS measurements on some common military explosives and some of the most common explosives precursors deposited on clothing fabrics, both synthetic and natural, such as polyester, leather and denim cotton at concentration comparable to those obtained from a single fingerprint. RS Spectra were obtained using an integrated portable Raman system equipped with an optical microscope, focusing the light of a solid state GaAlAs laser emitting at 785 nm. A maximum exposure time of 10 s was used, focusing the beam in a 45 μm diameter spot on the sample. The substances were deposited starting from commercial solutions with a Micropipetting Nano-Plotter, ideal for generating high-quality spots by non-contact dispensing of sub-nanoliter volumes of liquids, in order to simulate a homogeneous stain on the fabric surface. Images acquired with a Confocal Laser Scanning Microscope provided further details of the deposition process showing single particles of micrometric volume trapped or deposited on the underlying tissues. The spectral features of each substance was clearly identified and discriminated from those belonging to the substrate fabric or from the surrounding fluorescence. Our results show that the application of RS using a microscope-based apparatus can provide interpretable Raman spectra in a fast, in-situ analysis, directly from explosive particles of some μm3 as the ones that it could be found in a single fingerprint, despite the contribution of the substrate, leaving the sample completely unaltered for further, more specific and propaedeutic laboratory analysis. The same approach can be envisaged for the detection of other illicit substances like drugs.

Lidar sounding of volcanic plumes

Accurate knowledge of gas composition in volcanic plumes has high scientific and societal value. On the one hand, it gives information on the geophysical processes taking place inside volcanos; on the other hand, it provides alert on possible eruptions. For this reasons, it has been suggested to monitor volcanic plumes by lidar. In particular, one of the aims of the FP7 ERC project BRIDGE is the measurement of CO2 concentration in volcanic gases by differential absorption lidar. This is a very challenging task due to the harsh environment, the narrowness and weakness of the CO2 absorption lines and the difficulty to procure a suitable laser source. This paper, after a review on remote sensing of volcanic plumes, reports on the current progress of the lidar system.

Trace detection of explosives and their precursors by surface enhanced Raman spectroscopy

Surface Enhanced Raman Spectroscopy measurements on some common military explosives were performed with a table-top micro-Raman system integrated with a Serstech R785 minispectrometer. Serstech R785 is a miniaturised spectrometer suitable for Raman and NIR measurements. Integration of R785 in our table-top system aims to the realization of a portable SERS detector, able to perform in-situ measurements. SERS Spectra were obtained exciting the substance of interest with a 785 nm diode-laser, while these substances were deposited starting from commercial solutions on commercial SERS substrates, to improve the detection sensitivity. The amount of the sampled substance was determined through the analysis of images of the substrate covered with the residue of explosive. In fact, once the solvent is completely evaporated, the residue of explosive was observed to be uniformly distributed on the substrate surface. Images acquired with a Scanning Electron Microscope provided further details of the deposition process showing that a fraction of the active SERS sites are completely covered with the analyte while other sites appear to be empty; from the analysis of the images the sampled quantity was estimated to be about 200 pg. The main Raman features of each substance were clearly identified, the spectral resolution was sufficiently high to clearly distinguish spectra belonging to different substances.

Comprehensive Infrared Study of Tetryl, Dinitrotoluene, and Trinitrotoluene Compounds.

The present work describes an experimental and theoretical study of energetic materials used for detecting explosives in order to prevent terrorist actions, as well as for de-mining projects. Particular attention was devoted to examining the infrared absorption spectroscopy of classic explosives in order to create a useful mobile apparatus for on-field detection of explosives. This paper reports the vibrational absorption spectra of tetryl, dinitrotoluene, and trinitrotoluene molecules approached using two different spectroscopic techniques, Fourier transform infrared spectroscopy (FT-IR) and laser photoacoustic spectroscopy (LPAS). Diffuse reflectance Fourier transform infrared spectra of all samples were analyzed in a very wide spectral range (400–7500 cm−1) showing for the first time the existence of weak absorption bands attributable to overtones or combination bands, while laser photoacoustic spectroscopy spectra have been investigated in the fingerprint region of organic compounds that share the CO2 laser emission range (∼920–1100 cm−1). The Fourier transform infrared spectra of both matrix isolated dinitrotoluenes have been also investigated. The theoretical treatment of tetryl is reported for the first time.

Lidar/DIAL detection of acetone at 3.3 μm by a tunable OPO laser system

In this paper we report, for the first time to our knowledge, on lidar/DIAL detection of acetone vapors at 3.3 μm by means of an optical parametric tunable laser system. After a preliminary spectroscopic study in an absorption cell, the feasibility of a differential absorption (DIAL) lidar for the detection of acetone vapors has been investigated in the laboratory, simulating the experimental conditions of a field campaign. Having in mind measurements in a real scenario, a study of possible atmospheric intereferents has been performed, looking for all known compounds that share acetone IR absorption in the spectral band selected for its detection. Possible interfering species from urban and industrial atmospheres were investigated and limits of acetone detection in both environments were identified. This study confirmed that a lidar system can detect a low concentration of acetone at considerable distances.

Vibrational Spectrum of HMX at CO2 Laser Wavelengths: A Combined DRIFT and LPAS Study

The vibrational spectrum of solid standard HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) was investigated. Two spectroscopic techniques were adopted for their different sensitivity and resolution. A preliminary survey of the absorption bands of the compound was performed in the 8000–400 cm−1 spectral range by employing the diffuse reflectance infrared Fourier transform (DRIFT) technique at room temperature. The high-resolution line spectrum of HMX was obtained in the 9.2–10.8 μm spectral range by laser photoacoustic spectroscopy (LPAS) method, using a line tuneable 10 W stabilised cw CO2 laser light source. By comparing the data collected with the two techniques in the common frequency range, a very good agreement was observed.

Application of Laser Photoacoustic Spectroscopy and Chemometrics in Homeland Security

In the last decades, the military and Government organizations have an increasing interest in development of field-sensors for homeland security issues. In order to detect explosives (such as DNT, TNT, tetryl, RDX, HMX, TATP, PETN) and some precursors of Improvised Explosive Devices (i.e. potassium sulfate, potassium nitrate, magnesium sulfate, ammonium perchlorate, ammonium nitrate, acetone), we applied laser photoacoustic spectroscopy (LPAS) and a chemometric method (PCA, Principal Component Analysis) to speed up the identification process. The results indicated that the combination of LPAS and PCA is very useful for a rapid identification of these chemicals.

Spectroscopic study of some IED's precursors by means of laser photoacoustic spectroscopy combined with multivariate analysis

The Improvised Explosive Device (IED) is the most prevalent form of explosive device utilized by terrorists today being easy to realize and difficult to detect. These explosive devices are made by mixing different precursor substances that are generally cheap and commercially available. Thus, attention should be focused on developing fast and reliable methods able to identify such substances. In this paper we applied laser photoacoustic spectroscopy method for the spectral characterization and identification of a number of common chemicals used as precursors of IEDs: potassium sulfate, potassium nitrate, magnesium sulfate, ammonium perchlorate, ammonium nitrate, and acetone. The analyzed chemical species were classified by Principal Component Analysis applied to the collected spectral data. As conclusion of the study, the laser photoacoustic spectroscopy combined with chemometrics has confirmed to be a useful tool that could support the fight against the increased realization of modern bombs for criminal use.