Lead-free ammunition is becoming increasingly popular because of the environmental and human health issues associated with the use of leaded ammunition. However, there is a lack of data on the emissions produced by firing such ammunition. We report emission factors for toxic gases and particle-bound compounds produced by firing lead-free ammunition in a test chamber. Carbon monoxide, ammonia, and hydrogen cyanide levels within the chamber were analysed by Fourier transform infrared spectroscopy, while total suspended particles and respirable particles were determined gravimetrically. The metal content of the particulate emissions was determined and the associated organic compounds were characterized in detail using a method based on thermal desorption coupled to gas chromatography and mass spectrometry. The particulate matter (∼30 mg/round) consisted primarily of metals such as Cu, Zn, and Fe along with soot arising from incomplete combustion. Nitrogen-containing heterocyclic aromatic compounds such as carbazole, quinolone, and phenazine were responsible for some of the 25 most significant chromatographic peaks, together with PAHs, diphenylamine, and phthalates. Emission factors were determined for PAHs and oxygenated PAHs; the latter were less abundant in the gun smoke particles than in domestic dust and diesel combustion smoke. This may be due to the oxygen-deficient conditions that occur when the gun is fired. By using an electrical low pressure impactor, it was demonstrated that more than 90% of the particles produced immediately after firing the weapon had diameters of less than 30 nm, and so most of the gun smoke particles belonged to the nanoparticle regime.

Numerous studies demonstrated that the use of lead (Pb)-containing ammunition is associated with mainly chronic health problems and also is a burden on the environment and wildlife. Recently, a number of reports showed evidence of undesirable acute health effects related to the use of newly developed Pb-free small-caliber ammunition. In this study, particles from leaded and Pb-free ammunition were collected in liquid collection medium, in a highly controlled chamber, while firing a pistol (9 mm) or a rifle (7.62 × 51 mm). The emitted particles were typically smaller than 4 μm, with the great majority in even smaller size ranges, as shown by gravimetrical analysis and a multistage impactor. Chemical analysis revealed significant differences in content and concentration of several metals in the particles. After administration of the liquids to alveolar and bronchial in vitro cell systems, particles were taken up by the cells; the Pb-free particles displayed higher cytotoxicity (EC50 = 2 μg/cm(2)) than particles from Pb ammunition. High correlation factors (>0.9) were found between cell death and content of copper and zinc. Particles from both Pb-containing and Pb-free ammunition were able to induce oxidative stress and the proinflammatory marker interleukin (IL)-8 in both in vitro systems. These results support previous findings that indicate an association between gunshot emissions and metal fume fever. This study demonstrates the usefulness of combining chemical data with biological in vitro responses in assessing acute toxicological effects from emissions from firing both Pb and Pb-free ammunition.

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