Identification of high explosives using single-particle aerosol mass spectrometry

The application of single-particle aerosol mass spectrometry (SPAMS) to the real-time detection of micrometer-sized single particles of high explosives is described. Dual-polarity time-of-flight mass spectra from 1000 single particles each of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN), as well as those of complex explosives, Composition B, Semtex 1A, and Semtex 1H, were obtained over a range of desorption/ionization laser fluences between 0.50 and 8.01 nJ/microm2. Mass spectral variability with laser fluence for each explosive is discussed. The ability of the SPAMS system to identify explosive components in a single complex explosive particle ( approximately 1 pg) without the need for consumables is demonstrated.     

Laser desorption/in situ chemical ionization aerosol mass spectrometry for monitoring tributyl phosphate on the surface of environmental particles

The possibility of using real-time aerosol mass spectrometry (RTAMS) for the detection of surface-adsorbed tributyl phosphate (TBP) as an alkali metal adduct has been investigated. Environmental particles contain variable amounts of easily ionizable alkali metals. During laser desorption of surface-adsorbed TBP molecules, Na+ and K+ ions are generated by the interaction of the laser radiation with the particle's material. The alkali metal ions serve as in situ chemical ionization reagents of the neutral analyte molecules. The effect of laser fluence on the signal intensities of the potassium ion and cationized TBP was also studied. The best performance of the instrument was observed with laser fluences that produce high abundances of K+ but low abundances of ions from the particle's bulk material. The relatively low laser fluence, necessary to produce potassium ions, prevents the excessive fragmentation of the analyte. The instrument is capable of real-time monitoring of submonolayer coverage of TBP on the surface of micron-sized particles.     

Desorption/ionization fluence thresholds and improved mass spectral consistency measured using a flattop laser profile in the bioaerosol mass spectrometry of single Bacillus endospores

Bioaerosol mass spectrometry is being developed to analyze and identify biological aerosols in real time. Mass spectra of individual Bacillus endospores were measured with a bipolar aerosol time-of-flight mass spectrometer in which molecular desorption and ionization were produced using a single laser pulse from a Q-switched, frequency-quadrupled Nd:YAG laser that was modified to have an approximately flattop profile. The flattened laser profile allowed the minimum fluence required to desorb and ionize significant numbers of ions from single aerosol particles to be determined. For Bacillus spores, this threshold had a mean value of approximately 1 nJ/microm(2) (0.1 J/cm(2)). Thresholds for individual spores, however, could apparently deviate by 20% or more from the mean. Threshold distributions for clumps of MS2 bacteriophage and bovine serum albumin were subsequently determined. Finally, the flattened profile was observed to increase the reproducibility of single-spore mass spectra. This is consistent with the general conclusions of our earlier paper on the fluence dependence of single-spore mass spectra and is particularly significant because it is expected to enable more robust differentiation and identification of single bioaerosol particles.     

Classification of chemical and biological warfare agent simulants by surface-enhanced Raman spectroscopy and multivariate statistical techniques

Initial results demonstrating the ability to classify surface-enhanced Raman (SERS) spectra of chemical and biological warfare agent simulants are presented. The spectra of two endospores (B. subtilis and B. atrophaeus), two chemical agent simulants (dimethyl methylphosphonate (DMMP) and diethyl methylphosphonate (DEMP)), and two toxin simulants (ovalbumin and horseradish peroxidase) were studied on multiple substrates fabricated from colloidal gold adsorbed onto a silanized quartz surface. The use of principal component analysis (PCA) and hierarchical clustering were used to evaluate the efficacy of identifying potential threat agents from their spectra collected on a single substrate. The use of partial least squares-discriminate analysis (PLS-DA) and soft independent modeling of class analogies (SIMCA) on a compilation of data from separate substrates, fabricated under identical conditions, demonstrates both the feasibility and the limitations of this technique for the identification of known but previously unclassified spectra.     

Application of laser-induced incandescence to the detection of carbon nanotubes and carbon nanofibers

Laser-induced incandescence applied to a heterogeneous, multielement reacting flow is characterized by temporally resolved emission spectra, time-resolved emission at selected detection wavelengths, and fluence dependence. Two-pulse laser measurements are used to further probe the effects of laser-induced changes on the optical signal. Laser fluences above 0.6 J/cm2 at 1064 nm initiate laser-induced vaporization, yielding a lower incandescence intensity, as found through fluence-dependence measurements. Spectrally derived temperatures show that values of excitation laser fluence greater than this value lead to superheated plasmas with temperatures well above the vaporization point of carbon. The temporal evolution of the emission signal at these fluences is consistent with plasma dissipation processes, not incandescence from solidlike structures. Two-pulse laser experiments reveal that other material changes are produced at fluences below the apparent vaporization threshold, leading to nanostructures with different optical and thermal properties.     

Laser-induced breakdown spectroscopy detection and classification of biological aerosols

Laser-induced breakdown spectroscopy (LIBS) is examined as a potential method for detecting airborne biological agents. A spectrally broadband LIBS system was used for laboratory measurements on some common biological agent simulants. These measurements were compared to those of common, naturally occurring biological aerosol components (pollen and fungal spores) to determine the potential of LIBS for discriminating biological agents from natural background aerosols. A principal components analysis illustrates that linear combinations of the detected atomic lines, which are present in different ratios in each of the samples tested, can be used to discriminate biological agent simulants from other biological matter. A more sensitive, narrowband LIBS instrument was used to demonstrate the detection of single simulant (Bg) particles in the size range 1-5 microns. Ca, Mg, and Na, which are present in varying concentrations between 0.3 and 11% (by mass) in the Bg particles, were observed in single particles using LIBS.     

Femtosecond pulse shaping adds a new dimension to mass spectrometry

Phase-shaped femtosecond laser pulses and mass spectrometry were implemented as a tool for improving molecular identification. We demonstrate that the specific lines in the mass spectra of several chemical warfare simulants are sensitive to the phase characteristics of the incident laser field. The deviation in the relative yield of fragment ions observed upon pulse shaping (enhancement or suppression) adds a new dimension to mass spectrometry that improves molecular identification and can be used to quantitatively analyze mixtures of isomers.     

Reagentless detection of Mycobacteria tuberculosis H37Ra in respiratory effluents in minutes

Two similar mycobacteria, Mycobacteria tuberculosis H37Ra and Mycobacteria smegmatis are rapidly detected and identified within samples containing a complex background of respiratory effluents using single-particle aerosol mass spectrometry (SPAMS). M. tuberculosis H37Ra (TBa), an avirulent strain, is used as a surrogate for virulent tuberculosis; M. smegmatis (MSm) is utilized as a near-neighbor confounder for TBa. Bovine lung surfactant and human exhaled breath condensate are used as first-order surrogates for infected human lung expirations from patients with pulmonary tuberculosis. This simulated background sputum is mixed with TBa or MSm and nebulized to produce conglomerate aerosol particles, single particles that contain a bacterium embedded within a background respiratory matrix. Mass spectra of single conglomerate particles exhibit ions associated with both respiratory effluents and mycobacteria. Spectral features distinguishing TBa from MSm in pure and conglomerate particles are shown. SPAMS pattern matching alarm algorithms are able to distinguish TBa-containing particles from background matrix and MSm for >50% of the test particles, which is sufficient to enable a high probability of detection and a low false alarm rate if an adequate number of such particles are present. These results indicate the potential usefulness of SPAMS for rapid, reagentless tuberculosis screening.     

Surface-enhanced Raman scattering detection of chemical and biological agent simulants

Surface-enhanced Raman scattering spectra of chemical and biological agent simulants, such as dimethyl methylphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, 2-chloroethyl ethylsulfide, bacillus globigii, erwinia herbicola, and bacillus thuringiensis were obtained from silver-oxide film-deposited substrates. Thin AgO films ranging in thickness from 50 to 250 nm were produced by chemical bath deposition onto glass slides. Further Raman intensity enhancements were noticed in UV irradiated surfaces due to photo-induced Ag nanocluster formation, which may provide a possible route to producing highly useful plasmonic sensors for the detection of chemical and biological agents upon visible-light illumination.     

Laser-induced breakdown spectroscopy (LIBS): a promising versatile chemical sensor technology for hazardous material detection

A series of laboratory experiments have been performed highlighting the potential of laser-induced breakdown spectroscopy (LIBS) as a versatile sensor for the detection of terrorist threats. LIBS has multiple attributes that provide the promise of unprecedented performance for hazardous material detection and identification. These include: 1) real-time analysis, 2) high sensitivity, 3) no sample preparation, and 4) the ability to detect all elements and virtually all hazards, both molecular and biological. We have used LIBS to interrogate a variety of different target samples, including explosives, chemical warfare simulants, biological agent simulants, and landmine casings. We have used the acquired spectra to demonstrate discrimination between different chemical warfare simulants, including those on soil backgrounds. A linear correlation technique permits discrimination between an anthrax surrogate and several other biomaterials such as molds and pollens. We also use broadband LIBS to identify landmine casings versus other plastics and environmental clutter materials. A new man-portable LIBS system developed as a collaborative effort between the U.S. Army Research Laboratory and Ocean Optics, Inc., is described and several other schemes for implementing LIBS sensors for homeland security and force protection are discussed.     

In Situ, Real-Time Identification of Biological Tissues by Ultraviolet and Infrared Laser Desorption Ionization Mass Spectrometry

Laser desorption ionization-mass spectrometric (LDI-MS) analysis of vital biological tissues and native, ex vivo tissue specimens is described. It was found that LDI-MS analysis yields tissue specific data using lasers both in the ultraviolet and far-infrared wavelength regimes, while visible and near IR lasers did not produce informative MS data. LDI mass spectra feature predominantly phospholipid-type molecular ions both in positive and negative ion modes, similar to other desorption ionization methods. Spectra were practically identical to rapid evaporative ionization MS (REIMS) spectra of corresponding tissues, indicating a similar ion formation mechanism. LDI-MS analysis of intact tissues was characterized in detail. The effect of laser fluence on the spectral characteristics (intensity and pattern) was investigated in the case of both continuous wave and pulsed lasers at various wavelengths. Since lasers are utilized in various fields of surgery, a surgical laser system was combined with a mass spectrometer in order to develop an intraoperative tissue identification device. A surgical CO(2) laser was found to yield sufficiently high ion current during normal use. The principal component analysis-based real-time data analysis method was developed for the quasi real-time identification of mass spectra. Performance of the system was demonstrated in the case of various malignant tumors of the gastrointestinal tract.     

Soot particle disintegration and detection by two-laser excimer laser fragmentation fluorescence spectroscopy

A two-laser technique is used to study laser-particle interactions and the disintegration of soot by high-power UV light. Two separate 20 ns laser pulses irradiate combustion-generated soot nanoparticles with 193 nm photons. The first laser pulse, from 0 to 14.7 J/cm2, photofragments the soot particles and electronically excites the liberated carbon atoms. The second laser pulse, held constant at 13 J/cm2, irradiates the remaining particle fragments and other products of the first laser pulse. The atomic carbon fluorescence at 248 nm produced by the first laser pulse increases linearly with laser fluence from 1 to 6 J/cm2. At higher fluences the signal from atomic carbon saturates. The carbon fluorescence from the second laser pulse decreases as the fluence from the first laser increases, suggesting that the particles fully disintegrate at high laser fluences. We use an energy balance parameter, called the photon/atom ratio, to aid in understanding laser-particle interactions. These results help define the regimes where photofragmentation fluorescence methods quantitatively measure total soot concentrations.     

Detection of pesticide residues on individual particles

An aerosol time-of-flight mass spectrometer (ATOFMS) is used to analyze the size and composition of individual particles containing pesticides. Pesticide residues are found in the atmosphere as a result of spray drift, volatilization, and suspension of coated soils. The ability of the ATOFMS to identify the presence of these contaminants on individual particles is assessed for particles created from pure solutions of several commonly used pesticides, as well as pesticides mixed with an organic matrix, and coated on soils. The common names of the pesticides studied are 2,4-D, atrazine, chlorpyrifos, malathion, permethrin, and propoxur. Analysis of the mass spectra produced by single- and two-step laser desorption/ionization of pesticide-containing particles allows for identification of peaks that can be used for detection of pesticide residues in the ambient aerosol. The identified marker peaks are used to approximate detection limits for the pesticides applied to soils, which are on the order of a fraction of a monolayer for individual particles. Results suggest that this technique may be useful for studying the real-time partitioning and distribution of pesticides in the atmosphere immediately following application in agricultural regions.     

Laser ablation and growth of Si and Ge

In this work, we investigated the laser ablation and deposition of Si and Ge at room temperature in vacuum by employing nanosecond lasers of 248 nm, 355 nm, 532 nm and 1064 nm. Time-integrated optical emission spectra were obtained for neutrals and ionized Ge and Si species in the plasma at laser fluences from 0.5 to 11 J/cm². The deposited films were characterized by using Raman spectroscopy, scanning electron microscopy and atomic force microscopy. Amorphous Si and Ge films, micron-sized crystalline droplets and nano-sized particles were deposited. The results suggested that ionized species in the plasma promote the process of subsurface implantation for both Si and Ge films while large droplets were produced from the superheated and melted layer of the target. The dependence of the properties of the materials on laser wavelength and fluence were discussed.     

Time-resolved laser-induced incandescence and laser elastic-scattering measurements in a propane diffusion flame

Laser-induced incandescence (LII) and laser elastic-scattering measurements have been obtained with subnanosecond time resolution from a propane diffusion flame. Results show that the peak and time-integrated values of the LII signal increase with increasing laser fluence to maxima at the time of the onset of significant vaporization, beyond which they both decrease rapidly with further increases in fluence. This latter behavior for the time-integrated value is known to be characteristic for a laser beam with a rectangular spatial profile and is attributed to soot mass loss from vaporization. However, there is no apparent explanation for the corresponding large decrease in the peak value. Analysis shows that the peak value occurs at the time in the laser pulse when the time-integrated fluence reaches approximately 0.2 J/cm(2) and that the magnitude of the peak value is strongly dependent on the rate of energy deposition. One possible explanation for this behavior is that, at high laser fluences, a cascade ionization phenomenon leads to the formation of an absorptive plasma that strongly perturbs the LII process.     

Synthesis of phosphonate-containing mesoporous silica spheres under basic condition

Phosphonate-containing mesoporous silica (PMPS) spheres were successfully synthesized using diethyl(2-bromoethyl)phosphonate and non-ionic and cationic surfactants. The spherical PMPS particles with the mesopores were effectively formed under the basic condition through the hydrolysis and condensation reactions of tetraethoxysilane, even though the BET surface area of the particles decreased with increasing the added phosphonate amount. The hollow structures with the mesopores were obtained in the preferential amount of the phosphonate.     

Effects of Laser Repetition Rate and Fluence on Micromachining of TiC Ceramic

Micromachining of titanium carbide (TiC) ceramic is very difficult because of its high hardness and brittleness. Femtosecond pulsed laser was employed to process circular rings on the surface of TiC ceramic. The interaction area between femtosecond laser pulses and TiC at different laser repetition rates and fluences was studied. Morphology and composition of irradiated area were analyzed by scanning electron microscope, energy dispersive spectroscopy, and Raman spectrum. The results indicated that the radius of outer circle was close to the intended radius. Laser fluence had obvious effects on the radius and width of circular rings, compared to laser repetition rate. The width of circular rings increased rapidly with increasing laser fluence from 2.55 × 10^?2 to 1.27 × 10^?1 J/mm², and then stabilized at around 40 µm when laser fluence was above 7.64 × 10^?1 J/mm². The surface of circular rings was characterized by ripples at the lower laser fluence. With increasing laser fluence, four kinds of typical morphology were observed, including ripples, cauliflower-like particles, ball-like particles, and deposited oxide layer. Ball-like particles contained high concentration of titanium, which came from melt ball splashing from ablation area. The others came from the different oxidation stages occurred on the surface of TiC sample.     

Laser-induced incandescence: excitation intensity

Assumptions of theoretical laser-induced incandescence (LII) models along with possible effects of high-intensity laser light on soot aggregates and the constituent primary particles are discussed in relation to selection of excitation laser fluence. Ex situ visualization of laser-heated soot by use of transmission electron microscopy reveals significant morphological changes (graphitization) induced by pulsed laser heating. Pulsed laser transmission measurements within a premixed laminar sooting flame suggest that soot vaporization occurs for laser fluences greater than 0.5 J/cm(2) at 1064 nm. Radial LII intensity profiles at different axial heights in a laminar ethylene gas jet diffusion flame reveal a wide range of signal levels depending on the laser fluence that is varied over an eight fold range. Results of double-pulse excitation experiments in which a second laser pulse heats in situ the same soot that was heated by a prior laser pulse are detailed. These two-pulse measurements suggest varying degrees of soot structural change for fluences below and above a vaporization threshold of 0.5 J/cm(2) at 1064 nm. Normalization of the radial-resolved LII signals based on integrated intensities, however, yields self-similar profiles. The self-similarity suggests robustness of LII for accurate relative measurement of soot volume fraction despite the morphological changes induced in the soot, variations in soot aggregate and primary particle size, and local gas temperature. Comparison of LII intensity profiles with soot volume fractions (f(v)) derived by light extinction validates LII for quantitative determination of f(v) upon calibration for laser fluences ranging from 0.09 to 0.73 J/cm(2).     

Beam-profile modulation of thulium laser radiation applied with multimode fibers and its effect on the threshold fluence to vaporize water

The threshold fluences at which vaporization is initiated at the tip of a multimode fiber that is submerged in water were investigated when free-running and Q-switched thulium laser pulses (lambda = 2.01 mum) were applied with different pulse energies. We focused on the quantification of temporal and spatial fluence modulations of the beam profile at the tip of a 400-mum fiber. The spatial and the temporal fluence peaks over the average fluence were measured to as high as 1.5 and 4 in the Q-switched mode, respectively, and 2.5 and 40 in the free-running mode, respectively. The fluence peaks significantly influence the vaporization process. An increase in the threshold fluence with increasing pulse energy was found for the Q-switched mode, but there was a decrease for the free-running mode. Pressure transients of the order of 1 kbar and temperatures higher than 200 degrees C were calculated for a 30-mJ Q-switched laser pulse at the onset of vaporization. Collecting all the data allowed us to trace the thermodynamic path of rapid heating and vaporization in a phase diagram of water.     

Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames

Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence. For larger fluences, distortions in the profile are attributed to photodissociation of H2O, CH3, and/or other combustion intermediates, and stimulated emission. In comparison with the nanosecond laser, excitation with the picosecond laser can effectively reduce the photolytic interference and produces approximately an order of magnitude larger interference-free signal in CH4/O2/N2 flames with equivalence ratios in the range of 0.5< or =Phi< or =1.4, and in H2/O2 flames with 0.3< or =Phi< or =1.2. Although photolytic interference limits the nanosecond laser fluence in all flames, stimulated emission, occurring between the laser-excited level, H(n=3), and H(n=2), is the limiting factor for picosecond excitation in the flames with the highest H atom concentration. Nanosecond excitation is advantageous in the richest (Phi=1.64) CH4/O2/N2 flame and in H2/O2/N2 flames. The optimal excitation pulse width for interference-free H atom detection depends on the relative concentrations of hydrogen atoms and photolytic precursors, the flame temperature, and the laser path length within the flame.