Chemistry and lung toxicity of particulate matter emitted from firearms.

Smoke emissions produced by firearms contain hazardous chemicals, but little is known if their properties change depending on firearm and ammunition type and whether such changes affect toxicity outcomes. Pulmonary toxicity was assessed in mice exposed by oropharyngeal aspiration to six different types of smoke-related particulate matter (PM) samples; (1) handgun PM, (2) rifle PM, (3) copper (Cu) particles (a surrogate for Cu in the rifle PM) with and without the Cu chelator penicillamine, (4) water-soluble components of the rifle PM, (5) soluble components with removal of metal ions, and (6) insoluble components of the rifle PM. Gun firing smoke PM was in the respirable size range but the chemical composition varied with high levels of Pb in the handgun and Cu in the rifle smoke. The handgun PM did not induce appreciable lung toxicity at 4 and 24 h post-exposure while the rifle PM significantly increased lung inflammation and reduced lung function. The same levels of pure Cu particles alone and the soluble components from the rifle fire PM increased neutrophil numbers but did not cause appreciable cellular damage or lung function changes when compared to the negative (saline) control. Penicillamine treated rifle PM or Cu, slightly reduced lung inflammation and injury but did not improve the lung function decrements. Chelation of the soluble metal ions from the rifle fire PM neutralized the lung toxicity while the insoluble components induced the lung toxicity to the same degree as the rifle PM. The results show that different firearm types can generate contrasting chemical spectra in their emissions and that the rifle PM effects were mostly driven by water-insoluble components containing high levels of Cu. These findings provide better knowledge of hazardous substances in gun firing smoke and their potential toxicological profile.

Invited Article: Quantitative imaging of explosions with high-speed cameras.

The techniques presented in this paper allow for mapping of temperature, pressure, chemical species, and energy deposition during and following detonations of explosives, using high speed cameras as the main diagnostic tool. This work provides measurement in the explosive near to far-field (0-500 charge diameters) of surface temperatures, peak air-shock pressures, some chemical species signatures, shock energy deposition, and air shock formation.

High-speed two-camera imaging pyrometer for mapping fireball temperatures.

A high-speed imaging pyrometer was developed to investigate the behavior of flames and explosive events. The instrument consists of two monochrome high-speed Phantom v7.3 m cameras made by Vision Research Inc. arranged so that one lens assembly collects light for both cameras. The cameras are filtered at 700 or 900 nm with a 10 nm bandpass. The high irradiance produced by blackbody emission combined with variable shutter time and f-stop produces properly exposed images. The wavelengths were chosen with the expected temperatures in mind, and also to avoid any molecular or atomic gas phase emission. Temperatures measured using this pyrometer of exploded TNT charges are presented.

High-speed digital color imaging pyrometry.

Temperature measurements of high-explosive and combustion processes are difficult to obtain due to the speed and environment of the events. To overcome these challenges, we have characterized and calibrated a digital high-speed color camera that may be used to measure the temperature of such events. A two-color ratio method is used to calculate a temperature using the color filter array raw image data and a graybody assumption. If the raw image data are not available, temperatures may be calculated from the processed images or movies, depending on proper analysis of the digital color imaging pipeline. We analyze three transformations within the pipeline (demosaicing, white balance, and gamma correction) to determine their effect on the calculated temperature. Using this technique with a Phantom color camera, we have measured the temperature of exploded C-4 charges. The surface temperature of the resulting fireball was found to rapidly increase after detonation, and subsequently decayed to a constant value of approximately 1980 K.

Acetylene measurement in flames by chirp-based quantum cascade laser spectrometry.

We have designed and characterized a mid-IR spectrometer built around a pulsed distributed-feedback quantum cascade laser using the characteristic frequency down-chirp to scan through the spectral region 6.5 cm(-1) spectral region. The behavior of this chirp is extensively measured. The accuracy and detection limits of the system as an absorption spectrometer are demonstrated first by measuring spectra of acetylene through a single pass 16 cm absorption cell in real time at low concentrations and atmospheric pressure. The smallest detectable peak is measured to be approximately 1.5 x 10(-4) absorbance units, yielding a minimum detectable concentration length product of 2.4 parts per million meter at standard temperature and pressure. This system is then used to detect acetylene within an ethylene-air opposed flow flame. Measurements of acetylene content as a function of height above the fuel source are presented, as well as measurements of acetylene produced in fuel breakdown as a function of preinjection fuel temperature.

Temporal evolution of the laser-induced breakdown spectroscopy spectrum of aluminum metal in different bath gases.

The spectral emission of gas-phase aluminum and aluminum oxide was measured during and immediately after exposure of a bulk-aluminum sample to a laser-induced spark produced by a focused, pulsed laser beam (Nd:YAG, 10-ns pulse duration, 35 mJ/pulse, lambda = 1064 nm). The spectral emission was measured as a function of time after the onset of the laser pulse, and it was also measured in different bath gases (air, nitrogen, oxygen, and helium).

Laser-induced breakdown spectroscopy analysis of energetic materials.

A number of energetic materials and explosives have been studied by laser-induced breakdown spectroscopy (LIBS). They include black powder, neat explosives such as TNT, PETN, HMX, and RDX (in various forms), propellants such as M43 and JA2, and military explosives such as C4 and LX-14. Each of these materials gives a unique spectrum, and generally the spectra are reproducible shot to shot. We observed that the laser-produced microplasma did not initiate any of the energetic materials studied. Extensive studies of black powder and its ingredients by use of a reference spectral library have demonstrated excellent accuracy for unknown identification. Finally, we observed that these nitrogen- and oxygen-rich materials yield LIBS spectra in air that have correspondingly different O:N peak ratios compared with air. This difference can help in the detection and identification of such energetic materials.

Laser-induced breakdown spectroscopy of bacterial spores, molds, pollens, and protein: initial studies of discrimination potential.

Laser-induced breakdown spectroscopy (LIBS) has been used to study bacterial spores, molds, pollens, and proteins. Biosamples were prepared and deposited onto porous silver substrates. LIBS data from the individual laser shots were analyzed by principal-components analysis and were found to contain adequate information to afford discrimination among the different biomaterials. Additional discrimination within the three bacilli studied appears feasible.

Fourier-transform laser spectroscopy.

The development of microphotonic sensors based on Fourier-transform laser spectroscopy (FT-LS) is discussed. The application demonstrated is for measurement of vapors from the hydrocarbon fuels JP-8, diesel fuel, and gasoline. The two-laser prototype FT-LS sensor used for our research employs distributed-feedback lasers in the near-infrared spectral region (1.3- and 1.7-microm wavelength). An extension of this research to multilaser arrays is discussed. We believe that this is the first measurement of middle-distillate fuel-vapor concentrations using this optical mixing technique.