V. Lazic

Self-absorption model in quantitative laser induced breakdown spectroscopy measurements on soils and sediments ☆

Abstract Application of laser induced breakdown spectroscopy (LIBS) in the quantitative analysis of elemental composition of soils with different origins and Antarctic marine sediments has been considered. The analytical method followed includes the usual plasma modeling at local thermal equilibrium (LTE) based on average temperature and electron density values, as well as spectra normalization, introduced in order to reduce the effects related both to the substrate optical and thermal properties and to the influence of laser parameters on quantitative data. The computational algorithm takes into account only atomic species and their first ionization states, which is sufficient at the plasma temperature measured in the experiments. Calibration curves are finally generated for each element of interest measured on certified samples with different provenience and matrix composition. In this paper a model is developed which takes into account the effects responsible for non-linearities in the relationship between line intensity and elemental concentration. The model properly includes line re-absorption and contributions from space regions with different plasma densities. Its application permits us to obtain the correlation coefficients between the LIBS measured and certified concentration of each element analyzed. These coefficients, specific for a given experimental layout and atomic lines data base, are successively applied in analytical LIBS measurements allowing for the direct determination of a single element concentration in any sample, regardless of its unknown matrix composition. The LIBS method presented here was tested on a priori unknown samples, and gave uncertainties in concentration varying from 15 to 40% over a large concentration range covering several orders of magnitude. The measuring error depends on element type, on the concentration value and also on the number of certified samples used for the initial calibration. The present results are already significant for some field application, such as on-board marine sediment analysis where a significant matrix variation with layer depth is common.

On board LIBS analysis of marine sediments collected during the XVI Italian campaign in Antarctica

Abstract The Laser-induced Breakdown Spectroscopy technique was applied on board the R/V Italica during the XVI Antarctic campaign (2000–2001) to carry out elemental chemical analysis of marine sediments collected using different sampling systems. To this end, a compact system has been built, which was suitable to operate also in the presence of mechanical vibrations, induced by the ship motion. Qualitative and quantitative analyses were performed on dried samples, without any further pre-treatment. Qualitative analyses have shown similar elemental composition among different collected sediments, except for significant differences in the case of rock fragments and manganese nodule. The latter also contains some heavy metals that in sediment layers were detected only in traces. The methodology to retrieve relative or absolute elemental concentration in heterogenous samples has been optimized and is scarcely sensitive to variations of sediment physical properties with depth, and to experimental parameters such as laser defocusing because of surface irregularities, and laser energy fluctuations. The relative distribution of the major elemental constituents, both from a bio-organic and mineral origin, was measured as a function of sediment depth. Measurements, once limited to specific spectral sections, and data analyses are fast and very reproducible. Most of the elements show a gradually varying distribution along the sampled core, except for silicon and barium, whose steep decrease with depth is strongly related to their biogenic origin. Quantitative LIBS analyses were performed on a limited number of samples and the results reported here, are comparable to the certified element contents in a reference sample of Antarctic sediments.

Detection of explosives at trace levels by laser-induced breakdown spectroscopy (LIBS)

In order to realize a compact instrument for detection of explosive at trace levels, LIBS was applied on residues from different explosives and potentially interfering materials. The residues were simply placed on aluminum support and the measurements were performed in air. Spectral line intensities from the characteristic atoms/molecules and their ratios, are strongly varying from one sampling point to another. The reasons for such variations were studied and explained, allowing establishing a suitable procedure for material recognition. Correct classification was always obtained for five types of explosives, while for TATP, nitroglycerine, DNT and EGDN this occurred only for very thin residues. In all the cases, the estimated detection threshold is between 0.1 ng and 1 ng.

Study of laser produced plasma in Cu-based alloys

The effects of energy and pulse duration in laser ablation experiments have been investigated in the case of copper based alloys. Experiments were carried out near 530nm by using two laser sources with different widths (8 ns and 250 fs). The craters generated by lasers were examined and their characteristics were related to different mechanisms involved in the ablation by laser pulses acting on different timescales. The optical emission of plasma produced was analyzed by LIPS, acquiring time resolved line intensities of the major elements contained in the samples, and determining plasma characteristics (temperature, electron density). Experiments demonstrated that fs and ns laser pulse must be modeled by different ablation regimes, the onset of which can be used to decrease the effect of fractionation on brasses and bronzes.

Trace detection of explosive compounds by different laser-based techniques at the ENEA Laboratories

The ENEA Laser Application Section has participated to the European project ISOTREX (Integrated system for on-line trace explosives detection in solid and vapor state), funded in the frame of the PASR 2006 with the main aim to exploit different laser based techniques. Standard explosive compounds and their precursors have been investigated through an atomic technique (LIBS; Laser-Induced Breakdown Spectroscopy), an absorption technique (LPAS; Laser Photoacoustic Spectroscopy) and vibrational techniques (Laser Raman and SERS; Surface-Enhanced Raman Spectroscopy). LIBS and SERS reached a sub ng level of detection, supported by a high rank of discrimination of the components via chemometric analysis. This selectivity skill is also quite evident in the LPAS technique. These results assume particular relevance due to the inclusion of interferents, such as dust, fingerprint oil and lubricant oil, into the investigated compounds. The results of the measurements are presented in view of the possible integration of the three techniques in a single device for trace detection, might contribute also to drastically limit the number of false positives.

Laser-induced breakdown spectroscopy for the remote detection of explosives at level of fingerprints

We report the results of the application of Laser-Induced Breakdown Spectroscopy (LIBS) for the detection of some common military explosives and theirs precursors deposited on white varnished car’s external and black car’s internal or external plastic. The residues were deposited by an artificial silicon finger, to simulate material manipulation by terrorists when preparing a car bomb, leaving traces of explosives on the parts of a car. LIBS spectra were acquired by using a first prototype laboratory stand-off device, developed in the framework of the EU FP7 313077 project EDEN (End-user driven DEmo for CBRNe). The system operates at working distances 8-30 m and collects the LIBS in the spectral range 240-840 nm. In this configuration, the target was moved precisely in X-Y direction to simulate the scanning system, to be implemented successively. The system is equipped with two colour cameras, one for wide scene view and another for imaging with a very high magnification, capable to discern fingerprints on a target. The spectral features of each examined substance were identified and compared to those belonging to the substrate and the surrounding air, and those belonging to possible common interferents. These spectral differences are discussed and interpreted. The obtained results show that the detection and discrimination of nitro-based compounds like RDX, PETN, ammonium nitrate (AN), and urea nitrate (UN) from organic interfering substances like diesel, greasy lubricants, greasy adhesives or oils in fingerprint concentration, at stand-off distance of some meters or tenths of meters is feasible.

Spectroscopic Monitoring of the Laser Cleaning Applied to Ancient Marbles from Mediterranean Areas

Laser Induced Breakdown Spectroscopy (LIBS) analysis by Nd:YAG laser emitting at 355nm were performed on different clean and dirty surfaces of marble fragments collected from ancient quarries in Greece, Turkey and Italy, in order to determine semi-quantitavely the atomic composition of the bulk material and encrustation. The method here developed for element concentrations retrieval could be applied during laser cleaning process to supply the information about the effective crust composition at different depths and the point where the process should be interrupted. The knowledge of the crust composition along successive layers is also important for determining the restoration procedures. The elements measured in the encrustations, such as Si, Al, Ca, C, Ti, Mn, Mg, Na, Ba, Sr and Cu are also present in the bulk, but at different concentrations whose determination allows for the process monitoring. The only element here observed in the crusts and not detected in the bulk materials is Chromium, whose progressive disappearance from LIBS spectra could be used as another indicator of the laser cleaning effectiveness. On a sample from Turkey also Vanadium was detected in the encrustation. The present LIBS measuring method was validated by SEM-EDX and ICP analyses. The clean marble surface and encrustations were further analysed by Laser Induced Fluorescence (LIF), which could be used as an alternative technique for the on-line control of the cleaning effectiveness. Better discrimination between dirty and clean marble surface was obtained when 266nm excitation was applied instead of 355 nm. Characteristic LIF spectral signatures allows for the discrimination between different type of the natural stones, even under the water.