Attenuation of Pb and Sb in shooting range soils by Fe amendments.

Lead (Pb) and antimony (Sb) contamination pose a major environmental risk at firing ranges and threaten land sustainability. Methods for the stabilization of metal (loid) contaminants are necessary to prevent off-site migration of metals in surface and ground water or from soil erosion. In the present study, two remediation treatments (ferric chloride/calcium carbonate and nanoscale zero-valent iron (nZVI)) were applied to flow-through soil columns containing four types of soils (sand, sandy loam, loamy sand, and silty loam) to study Pb and Sb behavior. Water runoff was continuously monitored for three months prior to amendment addition and for the following ten months. Soils were characterized before and after reaction. We found Sb was more mobile than Pb in all soil systems and was primarily present in the dissolved fraction whereas Pb was associated with both soil organic matter (SOM) and Fe colloids. Dominant Pb solid phase species were comprised of Pb0, PbO, PbCO3, and Pb sorbed to Fe(III) oxides while Sb was present as fully oxidized Sb(V) in soil and soil solution. The nZVI addition had minimal impact on Pb and Sb immobilization compared to control soil. The FeCl2 and CaCO3 amendment decreased pore water Sb concentrations by >80% for all soil types and >96% reduction in the fine- and coarse-grained soil types (silt loam and sand). Lead was initially mobilized coinciding with a decrease in pH from the hydrolysis of Fe(II) in solution. Additional soil treatments have the potential to be effective for system-wide immobilization with adequate additions of CaCO3 buffer. Though this study focused on bullet fragment weathering as a source of Pb and Sb the results have application to environmental monitoring and remediation efforts at mining or industrial runoff sites.

Environmental impact of metals resulting from military training activities: A review.

The deposition of metals into the environment as a result of military training activities remains a long-term concern for Defense organizations across the globe. Of particular concern for deposition and potential mobilization are antimony (Sb), arsenic (As), copper (Cu), lead (Pb), and tungsten (W), which are the focus of this review article. The fate, transport, and mobilization of these metals are complicated and depend on a variety of environmental factors that are often convoluted, heterogeneous, and site-dependent. While there have been many studies investigating contaminant mobilization on military training lands there exists a lack of cohesiveness surrounding the current state of knowledge for these five metals. The focus of this review article is to compile the current knowledge of the fate, transport, and ultimate risks presented by metals associated with different military training activities particularly as a result of small arms training activities, artillery/mortar ranges, battleruns, rocket ranges, and grenade courts. From there, we discuss emerging research results and finish with suggestions of where future research efforts and training range designs could be focused toward further reducing the deposition, limiting the migration, and decreasing risks presented by metals in the environment. Additionally, information presented here may offer insights into Sb, As, Cu, Pb, and W in other environmental settings.

Lead and antimony from bullet weathering in newly constructed target berms: Chemical speciation, mobilization, and remediation strategies.

Understanding lead (Pb) and antimony (Sb) speciation associated with the weathering of bullets at shooting ranges is essential for identifying species migration potential to local watersheds and for assessing the overall toxicity of shooting range soils. In the present study, we fired 2000 5.56 mm bullets into newly constructed and instrumented target berms composed of well-characterized test soils (sand, sandy loam, loamy sand, silt loam) and collected berm pore water runoff and soil samples over five summers (2011 to 2015). We tracked the chemical transformations of Pb and Sb released during bullet weathering as a function of time and soil properties. During 2014 summer, an amendment of ferrous chloride (FeCl2) with a calcium carbonate (CaCO3) buffer was added to a subset of the berms of each soil type to test this remediation strategy. Bulk speciation analysis coupled with micro-scale spectroscopic methods show that both Sb(III) and Sb(V) species are present in soil solution depending on the soil matrix type, but Sb(III) was not observed after 9 months of weathering. In general, Sb was found to be more mobile than Pb, attributable to the relatively low solubility of the dominant Pb phases present in the crust forming around bullet fragments and within soil. The oxidation of Pb(0) resulted in a mixture of lead oxide, lead carbonate, and lead sorbed onto iron(III) oxides. We found a higher degree of metal(loid) mobilization (higher dissolved metal concentrations) in the berms made from the sandy soils. In contrast, silt loam soil was found to be more effective at immobilizing metal(loid)s. Furthermore, we observed that an iron-oxide type amendment may be effective at further reducing Pb and Sb runoff. Results from this study provide insight into the fate and transport of metal(loid)s within small arms target ranges and address a potential method for metal(loid) immobilization.