Acting Role of Background Gas in the Emission Response of Laser-Induced Plasmas of Energetic Nitro Compounds.

This study focuses on the analysis of the optical emission response obtained by laser-induced breakdown spectroscopy from energetic nitro compounds in condensed phase sampled in atmospheres of variable composition. The influence of different background gases was evaluated from the characteristic emissions of the excited species coexisting in the plasma plume and conclusions concerning the main pathways involved in the generation of such emission species were extracted. Different reactive (O2, N2, H2) and inert (Ar, He) gases were tested to establish the comparative emission features of organic compounds.

Pressure effects in laser-induced plasmas of trinitrotoluene and pyrene by laser-induced breakdown spectroscopy (LIBS).

The influence of the ambient atmosphere on the dynamics of plasma expansion, besides the interaction between excited plasma and gas molecules, has been studied for specific organic aromatic compounds. To analyze the influence of air on the formation pathways of atomic and molecular species inside the plasma plume, the spectral emissions in laser-induced breakdown spectroscopy (LIBS) of 2,4,6-trinitrotoluene (TNT) and pyrene were compared at different pressure environments, from high vacuum to atmospheric pressure. Pelletized samples of the compounds were introduced in a vacuum chamber for excitation with the fourth harmonic output of an Nd : YAG laser (266 nm). The optical emission signal was collected with an optical fiber connected to a spectrograph fitted with a intensified charge-coupled device detector. Results from LIBS spectra indicate that changes in pressure level affect the kinetics of the characteristic excited species and their spatial distribution inside the plasma plume.

Condensed-phase laser ionization time-of-flight mass spectrometry of highly energetic nitro-aromatic compounds.

RATIONALE: Analysis of explosive compounds represents an interesting field of work due to the obvious social relevance of these compounds. Direct laser ionization allows the analysis of these high internal energy compounds without sampling or preparation procedures. We have studied nitro-aromatic compounds to understand their mass spectra when directly ionized in the condensed phase, different from the gas-phase studies commonly conducted. METHODS: Direct condensed-phase laser ionization time-of-flight mass spectrometry of high energy density materials has been performed using a 5 ns width quadrupled Nd:YAG laser. No matrix assistance was used. Fine control of the laser energy allowed the study of the fragmentation processes from values close to the ionization threshold to ones where atomic-only mass spectra were recorded. RESULTS: The influence of the variation of extraction conditions on the recorded mass spectra was investigated. For low extraction width pulses, ions with low m/z values were mainly observed, whereas, at higher widths, higher mass fragment ions were also detected while the total ion current was maintained. Therefore, the mass spectra can be modulated to obtain mass spectra containing molecular or atomic information. The onset of ion generation for the different fragment ions was also studied, yielding information that can help to understand the processes involved in the fragmentation pathways of the molecule and in the dissociation mechanisms. Two sampling procedures allowed the prospective use of LIMS as a screening technique for nitro-aromatic-based highly energetic explosives. CONCLUSIONS: Direct analysis of explosive compounds has been performed by laser ionization. A large dependence of the resultant spectra on the laser energy was observed that might be useful for studies of fragmentation pathways. For forensic applications, two sampling procedures might allow the use of LIMS as a screening technique.

Secondary ion mass spectrometry of powdered explosive compounds for forensic evidence analysis.

RATIONALE: Residual quantities of explosives deposited on, or absorbed in, nearby surfaces can be of forensic value in post-blast analysis. As secondary ion mass spectrometry (SIMS) may be a suitable analytical approach for the screening of such residues, its performance was evaluated. METHODS: The analyses were carried out in a SIMS instrument fitted with a quadrupole analyzer. The sample was sputtered at a 45º incidence angle with a 100 µm primary Ar(+) beam (3 keV, 500 nA). Surface sample compensation was performed with low-energy electrons (500 eV, 0.75 mA). RESULTS: TNT, RDX, PETN and cloratite were deposited in powdered form on double-sided tape and introduced into the mass spectrometer, without further handling, for SIMS analysis. The analysis conditions including compensation were optimized. A mixture of energetic compounds commonly used for explosive preparation was also analyzed, proving the potential of SIMS in forensic analysis. CONCLUSIONS: This study demonstrated the possibility of detecting explosives by SIMS making use of a simple sampling procedure consisting of sticking the sample in powdered form (compatible with the collection performed in forensic post-blast analysis) onto double-sided tape without handling or preparation.

Energy-resolved depth profiling of metal-polymer interfaces using dynamic quadrupole secondary ion mass spectrometry.

Quadrupole secondary ion mass spectrometry (qSIMS) characterization of a metallized polypropylene film used in the manufacturing of capacitors has been performed. Ar(+) primary ions were used to preserve the oxidation state of the surface. The sample exhibits an incomplete metallization that made it difficult to determine the exact location of the metal-polymer interface due to the simultaneous contribution of ions with identical m/z values from the metallic and the polymer layers. Energy filtering by means of a 45 degrees electrostatic analyzer allowed resolution of the metal-polymer interface by selecting a suitable kinetic energy corresponding to the ions generated in the metallized layer but not from the polymer. Under these conditions, selective analyses of isobaric interferences such as (27)Al(+) and (27)C(2)H(3) (+) or (43)AlO(+) and (43)C(3)H(7) (+) have been successfully performed.

Two-pulse delayed 532-nm laser ionization of metals using collinear sub-threshold beams.

Two frequency-doubled Nd:YAG lasers collinearly aligned were used to ionize different metals at specific interpulse delays. The beams were independently operated in order to attain full control over the energy. Each laser beam was always set at fluences below the ionization threshold and an evaluation of the effect that the interpulse delay has on the material ionization and the LIMS signal was performed. The different metallic targets studied (Cu, Si, Al, Ti, Fe, 314 AISI stainless steel) exhibit a characteristic ionization feature consisting of a clear enhancement in the ionization yield at interpulse delays around 60 ns when analyzed as pure foils. In addition, an improvement in the spectral resolution is observed at the specific interpulse delay. Our results indicate that proper control of the energy allows optimization of the different steps in the ionization process and they suggest that the effect of the first laser pulse impinging on the surface enhances the way in which the second pulse interacts with the solid.

Remote, real-time, on-line monitoring of high-temperature samples by noninvasive open-path laser plasma spectrometry.

A remote detection system based on optical emission spectrometry of laser-induced plasmas has been developed to record spectra in the visible region from samples placed at remote distances from the excitation source. Unlike from fiber-optic-based systems, light collection is performed remotely as well. Laboratory-scale experiments have shown the possibility of performing real-time analysis of samples placed remotely. The application in the noninvasive analysis of hot samples (at 1,200 degrees C) has been demonstrated as well, allowing the dynamic monitoring of selective elemental migration.

Hadamard transform time-of-flight mass spectrometry: a high-speed detector for capillary-format separations.

This work demonstrates that with an intrinsic duty cycle of 50% and spectral storage speeds up to 277 spectra s(-1) Hadamard transform time-of-flight mass spectrometry (HT-TOFMS) is a promising detector for any capillary-format separation that can be coupled to MS by electrospray ionization. Complete resolution of the components of a nine-peptide standard was achieved by coupling pressurized-capillary electrophoresis (pCE) to HT-TOFMS. The addition of pressure to the separation capillary decreased analysis times and stabilized the electrospray ionization source. Pulsed-pressurized injection of reserpine was used to experimentally simulate narrower peaks than those obtained in the pCE. HT-TOFMS was able to sample peaks having widths in the millisecond range.