The Release of Incidental Nanoparticles During the Weathering of Gunshot Residue in Soils of a Shooting Range in Ontario, Canada

Gunshot residue is emitted as fine particulate matter upon the ignition of percussion-sensitive explosives among other additives in a firearm barrel. The particulates condense from a vapor phase and contain material from the Pb-Sb-Ba-bearing primer, S-bearing gunpowder, and the Pb-bearing bullet fragments. Shooters can inhale or ingest the fine particulates which also attach to their hands, clothing, and other surfaces. Estimation of the bioavailability of the emitted toxic Pb- and Sb-bearing particulates requires detailed knowledge of their mineralogical composition and those of their weathering products. For this purpose, gunshot residue particulates have been collected from soils in front of a firing line of a shooting range in Ontario, Canada. Bulk mineralogical and chemical features of the soils have been characterized using X-ray powder diffraction, inductively coupled plasma-mass spectrometry, and scanning electron microscopy. The focused ion-beam technique has been used to extract a section containing numerous altered gunshot residue particulates from a soil grain. Subsequent transmission electron microscopy shows for the first time that gunshot residue particulates are composed of metallic δ-Pb, α-Sb, galena (PbS), and an unidentified Ba-bearing phase. Weathering of the gunshot residue particulates results in the formation of incidental nanoparticles (i.e., not purposely engineered to occur at the nanometer scale) in the form of δ-Pb, massicot, PbO, and galena. The formation and mobilization of some of these nanoparticles within the soil grain suggest that their release during the weathering of bullets and gunshot residue contributes to the release of Pb into the environment. Hydrocerussite, Pb3(CO3)2(OH)2, cerussite, PbCO3, and massicot and anglesite, PbSO4, are the major secondary Pb-phases in and around altered GSR particulates. These phases form during the weathering of metallic Pb, massicot, and galena nanoparticles in a Ca-carbonate rich environment. Secondary Sb-bearing phases are valentinite, Sb2O3, and amorphous Sb-Pb phases (Sb:Pb ratio = 2:1–4:1). The latter phases have partially replaced large proportions of the Ca-carbonates surrounding the gunshot residue particulates. The larger abundance of the amorphous Sb-Pb phases relative to valentinite suggests that their solubility most likely controls the release of Sb into the bulk soil. The SEM and TEM characterizations and chemical analyses of mineral surface coatings and the colloidal fraction of a leachate from the collected surficial soils indicate that Pb occurs predominantly in the colloidal fraction, is often associated with sulfate-bearing colloids, and is sequestered in sulfate and carbonate/hydroxide coatings.