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Clean Clay soil: environmental scanning electron micrograph (ESEM) with backscatter electron detection (BSED) and analysis using energy-dispersive X-ray spectroscopy; units on image are 250 µm.
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Realistic training is the cornerstone for a viable military, and should be conducted while responsibly minimizing potential adverse impacts on human health and the natural environment. Metals and metal alloys are used in bullet manufacture to satisfy ballistic performance requirements as well as environmental concerns related to target practice and...
Citations
... Vol:. (1234567890) the environmental contamination caused by shooting activity are, for example, copper (Cu), zinc (Zn), arsenic (As), antimony (Sb), nickel (Ni), cadmium (Cd), mercury (Hg), tungsten (W), and chromium (Cr) (ITRC, 2005;Sorvari, 2007;Bannon et al., 2009;O'Connor et al., 2009;Rodríguez-Seijo et al., 2016a;Stauffer et al., 2017). The environmental contamination in shooting ranges can cause significant risks to groundwater resources, aquatic ecosystems, and terrestrial biota. ...
Activities in shooting ranges can cause chemical disturbances in the soil due to the constituents of ammunition, such as lead (Pb). Ecological and human risks are expected in these sites due to the high toxicity, abundance, and persistency of Pb in the soil. Effects in growth, reproducibility, and water absorption are examples of how Pb can affect terrestrial plants. Ingestion or inhalation of Pb-contaminated soil particles can cause respiratory problems, infertility or convulsion, for example, depending on the level of exposure. Children are the most susceptible to adverse health effects, such as behavioral and neurological disturbances. A systematic literature review (SLR) study was conducted to evaluate and discuss the main subjects involving soil contamination by Pb in outdoor shooting ranges. Based on the 31 papers selected, relevant aspects of the risk assessment methodologies and remediation options were presented. To the best of our knowledge, this is the first time this topic has been approached through a SLR. 23 documents were used as support literature. Overall, studies that perform speciation analyses of Pb in soil are more indicated to assess ecological and human risk since the contaminant bioavailability is better evaluated. However, only laboratory studies were conducted in the papers analyzed in this SLR to investigate the remediation options for shooting range contamination. There is a lack of pilot-scale data in the literature.
... traffic run-off) (Shen et al., 2017;Huber et al., 2016;Marrugo-Negrete et al., 2017;KabataPendias, 2010). Shooting ranges are amongst sources of heavy metal pollution due to deposition of bullets, which are weathered over time and the metals/metalloids from bullets can be mobilised and dispersed into the environment via pore, surface or ground water (O'Connor et al., 2009;Duggan & Dhawan, 2007). The main concern at shooting range sites has historically been Pb, and elevated soil concentrations of minor components of bullets such as As, Cu, Ni, Sb and Zn, have also been observed ( Sanderson et al., 2012). ...
Electrodialytic remediation was applied for remediation of shooting range soils from two sites in Norway for which the targeted metals were As, Cu, Pb and Sb. Up to 75% Cu and 78% Pb was removed in the treatment, while low removal of As (<3%) and Sb (14%) was observed suggesting low mobility and bioavailability of these two metals in the studied soils. Removal of metals from the natural soil matrix (Al, Fe, K, Mg and Mn) were with the exception of Mn generally low (<20%) making it possible to target the removal of Cu and Pb while limiting the disturbance to the natural soil matrix. Multivariate design and analysis was applied for assessing the efficiency of electrodialytic remediation treatment and variable importance varied for each of the studied metals. In general, applying a stirred set-up improved the metal removal, acidification time and reduced the energy consumption. The placement of the anode directly in the soil did not significantly influence the removal of Al, Mg, Mn, As and Pb, while moderately influencing the removal of Cu. Multivariate analysis (projections onto latent structures) revealed similar variable importance and optimal settings for removal of Cu and Pb. It is hence possible to simultaneously optimise the removal by applying a stirred set-up, placement of the anode directly in the soil suspension, sieving the soil (<2 mm fraction) and long treatment time (35 days). The study showed that multivariate analysis is a valuable tool for evaluating remediation measures depending soil characteristics and this way be used for selection of site-specific best available remediation methods.
... Dynamic loading occurs over the lifetime of a SAFR berm when new bullets strike the berm impact medium, which also contains bullet residues, with high kinetic energy. These high-speed impacts continually fragment the residual bullets into smaller and smaller particles (Martin et al. 2014;O'Connor et al. 2009). More than 96 percent of the Pb-Sb alloy from bullets fired into impact areas is present in metallic form as intact or fragmented bullets or shot (ITRC 2003;Martin et al. 2014). ...
Migration potential of metal(loids) associated with small-arms ammunition fired into range berms under dynamic loading conditions was assessed using pilot-scale and field-scale live-fire lysimeters. Experimental impact media at both scales was sand or sand plus a commercial heavy metal sorption amendment. After firing, artificial rainwater was applied weekly to the pilot-scale system; the field-scale system received natural rainfall. Leachate collected from both systems was analyzed for total suspended solids, hydrogen ion concentration, antimony, and lead. In pilot-scale lysimeters, antimony constituted 0.52% of the total bullet mass, but comprised 91.5 and 17% of the dissolved leachate metal from control and amended lysimeters, respectively. Lead constituted 52% of the total bullet mass but made up only 8.5 and 5% of the total dissolved leachate metal from the control and amended lysimeters, respectively. Use of the live-fire lysimeters under dynamic loading conditions provided support for range design recommendations. Impact areas should be constructed using pure sand (low fines) along with antimony and lead sorbing amendment(s) in order to provide maximum protection from heavy metal transport off range.
... Ultimately, range maintenance and weathering conditions dictate the longevity of the metal in the berm soil . Bullet corrosion depends on weathering effects associated with local climate, the physical form (i.e., fragmented or intact bullets), the alloy components of the bullet, and the soil conditions, where the more fragmented bullets can potentially release the components more rapidly into the environment (Ackermann et al., 2009;O'Connor et al., 2009;Larson et al., 2011). Soil analysis using X-ray Diffraction (XRD) and micro-Raman techniques were not a definitive identifier of Sb minerals in the samples analyzed from Swiss small arms range soils, but the use of an electron microprobe (EMP) suggests that Sb was concentrated near iron (Fe)-oxides as confirmed by extended X-ray absorption fine structure (EXAFS) (Ackermann et al., 2009). ...
Small arms firing ranges (SAFRs) contain a mixed amount of bullets and bullet fragments accumulated throughout their designed lifetime. Lead-antimony (Pb-Sb) alloy copper (Cu) jacketed bullets are a common modern ammunition used at SAFRs. The impact of bullets with berm material (i.e., soil) generates a heterogeneous distribution of bullets and bullet fragments in the surrounding soil. As bullets and bullet fragments corrode in the berm soil, the migration potential for antimony compared to other metals is quite high. The goal of this study was to evaluate the spatial Sb migration potential from an SAFR as compared to lead, copper, and zinc (Zn) migration from the same SAFR. Berm soil samples were collected along with surface and ground water samples for a preliminary investigation of the Sb migration from an active SAFR. In addition, different aqueous sample preservation techniques were used and evaluated. Soil sample analysis results show the presence of the metals (i.e., Pb, Sb, Cu, and Zn) in the range floor soil samples, indicating the migration of these metals from the berm to the range floor. The groundwater samples indicate that Sb was migrating from the SAFR more readily than the other metals based on the concentration of Sb in the monitoring well farthest from the SAFR berm.
... Normal operation of small arms ranges can result in the accumulation within the backstop berm soils of Pb at concentrations of several weight percent, in addition to other metals. Bullets are commonly fragmented and pulverized upon impact with the range floor, backstop, berms, or bullet traps (O'Connor et al., 2007(O'Connor et al., , 2009). This research compares the weathering and dissolution of lead in contaminated soils from antique and modern small arms ammunition ranges. ...
... As noted previously, the enhanced dissolution of lead can result in surface water or, more rarely, groundwater contamination. Soil type can also have an effect on lead dissolution by affecting the degree of bullet fragmentation (O'Connor et al., 2009). The authors evaluated impact fragmentation of modern lead alloy ammunition in five different soil types (ranging from a muck to a glacial till) using ESEM and X-ray diffraction (XRD) analysis. ...
... The authors evaluated impact fragmentation of modern lead alloy ammunition in five different soil types (ranging from a muck to a glacial till) using ESEM and X-ray diffraction (XRD) analysis. O'Connor et al., (2009) showed that, using modern 5.56 mm military rounds, some metals softened on contact with the soil producing "smears" of copper and zinc on the soil particles. In the Pb/Sb alloy, lead was always observed to be present as a discrete particle in sizes ranging from 3 microns to nearly complete rounds. ...
Through space revitalization, small arms firing ranges of older bases have and may become incorporated into residential areas of active bases with possible human exposure to lead. Bullet dissolution and scanning electron microscopy studies compared weathering of lead from antique small arms ammunition (the 45/70-405 Government) and modern ammunition (5.56 mm). The almost pure lead in the 45/70 bullet resulted in a round that has a lower corrosion and dissolution rate than the lead/antimony alloy of modern ammunition. It is less likely that lead will migrate from the older ranges into the surrounding environment either with suspended solids carried by surface water runoff or through leaching into the underlying soil and groundwater.
... Bullets are fragmented, pulverized, and can smear onto soil particles upon impact with the ground, backstop, berms, or bullet traps (O'Connor et al., 2009). The severity of fragmentation depends on the distance traveled, the soil type, bullet velocity and force of impact. ...
... The severity of fragmentation depends on the distance traveled, the soil type, bullet velocity and force of impact. The formation of mobile metal species on SAFRs is dependent on the types of bullet components, the extent of fragmentation of the rounds upon impact, the biogeochemistry of the soil into which the rounds are fired, and the degree of weathering to which the fragments are exposed (Griggs et al., 2010;O'Connor et al., 2009). Particle size distribution for Sb in post-fired soils is similar to that of Pb, indicating that the particles of the core retain their Pb-Sb alloy nature (O'Connor et al., 2007(O'Connor et al., , 2009. ...
... The formation of mobile metal species on SAFRs is dependent on the types of bullet components, the extent of fragmentation of the rounds upon impact, the biogeochemistry of the soil into which the rounds are fired, and the degree of weathering to which the fragments are exposed (Griggs et al., 2010;O'Connor et al., 2009). Particle size distribution for Sb in post-fired soils is similar to that of Pb, indicating that the particles of the core retain their Pb-Sb alloy nature (O'Connor et al., 2007(O'Connor et al., , 2009. Recent data collected from active SAFRs indicates that Sb may be leaving the range in pore and surface waters in higher concentrations than previously thought (Johnson et al., 2005; Aberdeen Test Center (ATC), 2009). ...
Chemical and biogenic sources of phosphate are commonly accepted in situ treatment methods for immobilization of lead (Pb) in soil. The metalloid antimony (Sb), commonly associated with Pb in the environment, exists as either a neutral species or a negatively charged oxyanion. Antimony is used in the manufacture of bullets as a hardening agent, constituting approximately 3% of the bullet mass. Technological solutions to reduce the migration of metals from small arms firing range (SAFR) soils for environmental compliance purposes must be robust with respect to multi-component systems containing both cationic and anionic contaminants. The effect of varying physico-chemical soil properties on Sb mobility post-firing was assessed in this study for six soil types using common analytical protocols and methods related to regulatory criteria. The sands (SM and SP) demonstrated the greatest Sb solubility in post-firing leachate samples and therefore were selected to evaluate the effects of five commercially available stabilization amendments on Sb mobility. Enhanced Sb leaching was experimentally confirmed in the phosphate-treated soils compared to both the untreated control soil and the sulfur-based amendment, and thus suggests competition for negative sorption sites between Sb and phosphate. However, the 5% Buffer Block® calcium phosphate amendment did not exhibit the same enhanced Sb release. This can be attributed to the inclusion of aluminum hydroxide in the amendment composition. Technologies are needed that will adequately immobilize Pb without mobilizing oxyanions such as Sb. Further research will be required to elucidate binding mechanisms and redox conditions that govern the mobility of Sb on SAFRs.
... rates depending on the local environment and individual metal properties. Previous work has addressed tungsten distribution in post-fired range soils and concluded that extent of weathering may be attributed to a ratio of the resulting surface area to mass ratio produced after impact (O'Connor et al., 2009). ...
In this study, a series of chemical extractions was used as a low-level, solid-phase tungsten speciation technique and correlated with XRD results. In addition to qualitative speciation, these efforts, which utilize the varying solubilities of WO−2 4, WO3, and W, provide statistically representative quantitative data at environmentally relevant levels. The selective nature of the digestion procedures allowed calculation of each individual species concentration by subtracting recoveries of the composite matrices from the total tungsten determinations. The results of this method exceed the sensitivity limitations of non-destructive techniques and may provide a valuable tool in environmental forensic investigations regarding the source of tungsten contamination.
... Over the last decade tungsten toxicological and environmental effects have received significant attention in relation to different research programs. Tungsten has been intensively investigated in connection with the US Army's Green Ammunition Program that included fate and transport, toxicological and ecotoxicological studies (Dermatas et al., 2004;Strigul et al., 2005;Bednar et al., 2009aBednar et al., , 2009bButler et al., 2009;Clausen and Korte, 2009;Griggs et al., 2009;Felt et al., 2009;Johnson et al., 2009;O'Connor et al., 2009, Ringelberg et al., 2009and others). Toxicity of tungstenbased shots used for hunting ammunition was also investigated (Kelly et al., 1998;Mitchell et al., 2001;Brewer et al., 2003;Thomas et al., 2007Thomas et al., , 2009). ...
... Typically, more than 96% of the lead is present as intact bullets/fragments (Interstate Technology Regulatory Council (ITRC) 2003). Lead bullets striking an impact berm at high speeds may vitrify on impact forming "melts" on individual soil particles (O'Connor et al. 2009). Several investigators have shown that fragments of lead ammunition weathered in surface soils will oxidize to a soluble ionic form (Lin et al. 1995, Murray et al. 1997). ...
The extent of bullet fragmentation, among other factors, affects the formation of mobile metal species on small arms firing ranges. Impact fragmentation produces an increase in the surface area to mass ratio of the metal alloys in the soil. This study examined the results of this increase in six soil types. Larger percentages of the average mass of metal particulates passing through a 1.68 mm sieve were observed for rocky and sandy soils than for softer, less compressible soils. Soil particle size separation by wet sieve analysis demonstrated that <1.8 of the total amount of lead introduced by ammunition was present in the <0.45 micron (soluble) size fraction. Bullet fragmentation patterns indicate that fragmentation at a firing distance of 25 m is greater than that at 98.5 m. The particulate nature of metals, such as lead, results in extensive sample heterogeneity and a consequent broad range of metal concentrations.
... This situation, combined with damage from bullet impacts, can lead to soil erosion of the berm. Annual training at rifle ranges can deliver millions of pounds of lead (Pb) into impact target areas along the berm in sizes ranging from fragments to intact projectiles (ITRC 2003) and/or "smears" of metal on soil particles (O'Connor et al. 2009). The metals of concern generated from small arms ammunition are principally Pb, alloyed with antimony (Sb), a hardening agent, along with copper (Cu) and zinc (Zn), which are the primary components of shell casings and jackets (HQDA 1996). ...
Bullet impact can significantly erode berm soils on small arms firing ranges. A study was conducted using mesoscale rainfall lysimeters to evaluate the effects of vegetation and liming on transport of heavy metals in the surface (runoff) and subsurface (leachate) waters. Runoff water and leachate were collected and analyzed for metals, pH, dissolved organic matter, and total suspended solids. Treatment with lime alone decreased the concentration of metals in the leachate from the firing range berm soil by five to eight times compared to the unlimed berm soil. Treatment with grass alone decreased the concentration of metals in the runoff water by almost nine times compared to the control. The addition of lime to the vegetated cells also decreased the amount of soluble lead released into the leachate. The engineered solution to metals contamination on range lands needs to be based on the specific environmental issues present on the range.
