Peter Sanderson

Effect of soil type on distribution and bioaccessibility of metal contaminants in shooting range soils.

Shooting ranges from Department of Defence sites around Australia were investigated for extent of metal contamination. Shooting range soils contained concentrations ranging from 399 to 10,403 mg/kg Pb, 6.57 to 252 mg/kg Sb, 28.7 to 1250 mg/kg Cu, 5.63 to 153 mg/kg Zn, 1.35 to 8.8 mg/kg Ni and 3.08 to 15.8 mg/kg As. Metal(loid)s were primarily concentrated in the stop butt and the surface soil (0-10 cm). The distribution of contamination reflected firing activity, soil properties, climate and management practices. Climatic variations among sites in Australia are significant, with a temperate climate in the south and tropical climate with high rainfall in the north. Up to 8% of total Pb resided in soil fines (<0.075 mm), due to the fragmentation of bullets on impact. Distribution and bioaccessibility varied between each site. Acidic Townsville soil had the highest proportion of water extractable Pb at 10%, compared to the alkaline Murray Bridge with only 2% Pb water extractable. Soil properties such as CEC, pH and dissolved organic carbon influence mobility. This is reflected in the subsoil concentrations of Pb in Townsville and Darwin which are up to 30 and 46% of surface concentration in the subsoil respectively. Similarly bioaccessibility is influenced by soil properties and ranges from 46% in Townsville to 70% in Perth. Acidic pH promotes dissolution of secondary minerals and the downward movement of Pb in the profile. The secondary Pb minerals formed as a result of weathering in these soils were cerussite, hydrocerussite, pyromorphite, galena and anglesite. Copper oxide was also reported on fragments from bullet jackets. These results have implications for range management.

Ecotoxicity of chemically stabilised metal(loid)s in shooting range soils

Five chemical amendments (soft rock phosphate, lime, commercial phosphate amendment, red mud and magnesium oxide) were applied across four different shooting range soils to chemically stabilise metal(loid)s in the soils. Soils were contaminated with Pb between 2330 and 12,167 mg/kg, Sb from 7.4 to 325 mg/kg and soil pH ranged from 5.43 to 9.29. Amendments were tested for their ability to reduce the bioavailability of Pb, Sb, Zn, Ni, Cu and As in the soils to soil organisms after one year of aging, by measuring a series of ecotoxicological endpoints for earthworms and plants and soil microbial activity. Growth-based endpoints for earthworms and plants were not significantly affected by amendment addition, except in the most contaminated soil. Per cent survival and weight-loss reduction of earthworms was enhanced by amendment addition in only the most contaminated soil. Plant biomass and root elongation was not significantly affected by amendment addition (p=<0.05). Red mud and magnesium oxide appeared toxic to plants and earthworms, probably due to highly alkaline pH (9-12). Lead in soil organisms was relatively low despite the high concentrations of Pb in the soils, suggesting low bioavailability of Pb. Uptake of Pb by earthworms was reduced by between 40 and 96 per cent by amendments, but not across all soils. Amendments reduced Sb in earthworms in Townsville soil by up to 92 per cent. For lettuce the average uptake of Pb was reduced by 40 to 70 per cent with amendment addition in Townsville, Darwin and Perth soil. The effect of amendments on the uptake of Sb, Zn, Ni, Cu and As was variable between soils and amendments. Microbial activity was increased by greater than 50 per cent with amendments addition, with soft rock phosphate and lime being the most effective in Murray Bridge and TV soils and commercial phosphate and MgO being the most effective in Darwin and Perth soils.

Chemical stabilisation of lead in shooting range soils with phosphate and magnesium oxide: Synchrotron investigation.

Three Australian shooting range soils were treated with phosphate and magnesium oxide, or a combination of both to chemically stabilize Pb. Lead speciation was determined after 1 month ageing by X-ray absorption spectroscopy combined with linear combination fitting in control and treated soils. The predominant Pb species in untreated soils were iron oxide bound Pb, humic acid bound Pb and the mineral litharge. Treatment with phosphate resulted in substantial pyromorphite formation in two of the soils (TV and PE), accounting for up to 38% of Pb species present, despite the addition of excess phosphate. In MgO treated soils only, up to 43% of Pb was associated with MgO. Litharge and Pb hydroxide also formed as a result of MgO addition in the soils. Application of MgO after P treatment increased hydroxypyromorphite/pyromorphite formation relative to soils teated with phosphate only. X-ray diffraction and Scanning electron microscopy revealed PbO precipitate on the surface of MgO. Soil pH, (5.3-9.3) was an important parameter, as was the solubility of existing Pb species. The use of direct means of determination of the stabilisation of metals such as by X-ray absorption spectroscopy is desirable, particularly in relation to understanding long term stability of the immobilised contaminants.

Critical Review on Chemical Stabilization of Metal Contaminants in Shooting Range Soils

Abstract Shooting ranges have come under increased scrutiny in recent years as a potential source of contamination owing to the high loading of lead in the soil. Stabilization by the addition of chemical amendments has been examined as a viable risk-based approach to managing shooting range contamination. Amendments have been shown to immobilize metals to varying degrees, determined by the target contaminant, the amendment used, soil properties, and the reaction kinetics in the contaminated soil and amendment system. Field scale evaluation of the effectiveness of chemical amendments for the stabilization of metal contaminants in shooting range soil is limited. Doubt remains over effectiveness and long-term stability under the varying conditions found in the field, which affect the kinetics of immobilization and dissolution in amended soil.

Potential value of phosphate compounds in enhancing immobilization and reducing bioavailability of mixed heavy metal contaminants in shooting range soil

Shooting range soils contain mixed heavy metal contaminants including lead (Pb), cadmium (Cd), and zinc (Zn). Phosphate (P) compounds have been used to immobilize these metals, particularly Pb, thereby reducing their bioavailability. However, research on immobilization of Pbs co-contaminants showed the relative importance of soluble and insoluble P compounds, which is critical in evaluating the overall success of in situ stabilization practice in the sustainable remediation of mixed heavy metal contaminated soils. Soluble synthetic P fertilizer (diammonium phosphate; DAP) and reactive (Sechura; SPR) and unreactive (Christmas Island; CPR) natural phosphate rocks (PR) were tested for Cd, Pb and Zn immobilization and later their mobility and bioavailability in a shooting range soil. The addition of P compounds resulted in the immobilization of Cd, Pb and Zn by 1.56-76.2%, 3.21-83.56%, and 2.31-74.6%, respectively. The reactive SPR significantly reduced Cd, Pb and Zn leaching while soluble DAP increased their leachate concentrations. The SPR reduced the bioaccumulation of Cd, Pb and Zn in earthworms by 7.13-23.4% and 14.3-54.6% in comparison with earthworms in the DAP and control treatment, respectively. Bioaccessible Cd, Pb and Zn concentrations as determined using a simplified bioaccessibility extraction test showed higher long-term stability of P-immobilized Pb and Zn than Cd. The differential effect of P-induced immobilization between P compounds and metals is due to the variation in the solubility characteristics of P compounds and nature of metal phosphate compounds formed. Therefore, Pb and Zn immobilization by P compounds is an effective long-term remediation strategy for mixed heavy metal contaminated soils.

The effect of environmental conditions and soil physicochemistry on phosphate stabilisation of Pb in shooting range soils.

The stabilisation of Pb in the soil by phosphate is influenced by environmental conditions and physicochemical properties of the soils to which it is applied. Stabilisation of Pb by phosphate was examined in four soils under different environmental conditions. The effect of soil moisture and temperature on stabilisation of Pb by phosphate was examined by measurement of water extractable and bioaccessible Pb, sequential fractionation and X-ray absorption spectroscopy. The addition of humic acid, ammonium nitrate and chloride was also examined for inhibition or improvement of Pb stability with phosphate treatment. The effect of moisture level varied between soils. In soil MB and DA a soil moisture level of 50% water holding capacity was sufficient to maximise stabilisation of Pb, but in soil TV and PE reduction in bioaccessible Pb was inhibited at this moisture level. Providing moisture at twice the soil water holding capacity did not enhance the effect of phosphate on Pb stabilisation. The difference of Pb stability as a result of incubating phosphate treated soils at 18 °C and 37 °C was relatively small. However wet-dry cycles decreased the effectiveness of phosphate treatment. The reduction in bioaccessible Pb obtained was between 20 and 40% with the most optimal treatment conditions. The reduction in water extractable Pb by phosphate was substantial regardless of incubation conditions and the effect of different temperature and soil moisture regimes was not significant. Selective sequential extraction showed phosphate treatment converted Pb in fraction 1 (exchangeable, acid and water soluble) to fraction 2 (reducible). There were small difference in fraction 4 (residual) Pb and fraction 1 as a result of treatment conditions. X-ray absorption spectroscopy of stabilised PE soil revealed small differences in Pb speciation under varying soil moisture and temperature treatments. The addition of humic acid and chloride produced the greatest effect on Pb speciation in phosphate treated soils.

Application of a biodegradable chelate to enhance subsequent chemical stabilisation of Pb in shooting range soils

PurposeA risk-based approach commonly applied for Pb-contaminated soil is stabilisation by phosphate amendment. However, the proportion of Pb present in a form that is readily immobilised by phosphate addition is often limited. Chelates were examined as a means to mobilise Pb prior to immobilisation to increase the proportion of Pb that could react with phosphate. Four contrasting shooting range soils from around Australia (Murray Bridge (MB), Townsville (TV), Darwin (DA) and Perth (PE)) were used for the study.Materials and methodsChelating agents such as ethylenediaminetetraacetic acid (EDTA) are able to extract Pb from existing species in the soil, forming complexes. By lowering soil pH or adding Fe3+ for the displacement of Pb from the complex, a greater proportion of Pb may be available for reaction with phosphate. The use of biodegradable ethylenediamine-N,N′-disuccinic acid (EDDS) minimises residual effects of chelate treatment in the soil.Results and discussionEDTA was not found to be suitable due to the stability of the chelate-Pb complex. The addition of EDDS had variable effect between the four shooting range soils. In the strongly weathered oxidic TV and DA soils, applying EDDS prior to phosphate amendment produced greater reduction in bioaccessible Pb, but in the less weathered MB and PE soil, bioaccessible Pb was increased. Water-extractable (WE) Pb increased in the soils by EDDS application, but this could be offset by lime application in DA soil, without negatively affecting Pb bioaccessibility; WE Pb also decreased over time when ammonium nitrate was added to the soil.ConclusionsApplication of EDDS may be able to increase the proportion of Pb that reacts with phosphate in the soil, providing greater reduction in bioaccessible Pb than phosphate-only treatments. Additional treatability studies are needed to test amendments that could manage the water-extractable portion of Pb and to optimise application of EDDS for the best outcome.

Contamination, Fate and Management of Metals in Shooting Range Soils—a Review

Pollution of shooting range soils by lead from bullets represents a widespread and potentially significant concern for impact on the environment. High concentrations of lead in particular are reported in bullet impact berms and shot fall zones. The other components of bullets used in shooting including antimony, copper and zinc may also be present at elevated concentrations. Antimony is a concern due to its mobility in the environment. It has been recognised that the status of contamination is important for the risk presented by shooting ranges. Lead bullets are subject to weathering in the soil, forming secondary minerals, which may be solubilised and may release lead and co-contaminants into the soil. The mobility and availability of contaminants in the soil affect their potential for spreading in the environment and for uptake and toxicity in organisms. Soil physicochemical properties affect bullet weathering and availability of contaminants in the soil. A number of strategies have been researched for management of shooting range pollution such as chemical stabilisation, phytoremediation and soil washing. This review considers the current state of knowledge and research of contamination and management of shooting ranges from recent literature (2014–2017) reflecting on new knowledge and novel management strategies for shooting range soil management. Ultimately, management of pollution in shooting range soils should seek to remove bullets from soil, reduce the weathering of bullets and reduce the mobility and bioavailability of contaminants. Adopted management practices should be based an understanding of site-specific condition, to achieve the most optimal outcome.