Pollution and risk assessment of potential hazardous elements in a shooting range soils (NW Spain)

Supplementary Files

Sin título


Pollution at shooting ranges is an issue of growing importance. Accumulation in soils of potentially harmful elements (PHEs) from ammunitions used is a major environmental risk. The total and available (extraction with 0.01 M CaCl2 and DTPA) content of As, Cd, Cu, Ni, Pb, Sb and Zn were evaluated in 10 soils from a shooting range for military use (León, Spain). The results showed that, among the studied pollutants, Pb is the element present in highest concentration (13.83-4451.57 mg kg-1), followed by Sb (1.80-96.10 mg kg-1), Cu (4.50-88.52 mg kg-1), As (13.24-62.47 mg kg-1), Zn (13.31-46.19 mg kg-1), Ni (11.53-46.30 mg kg-1) and Cd (0.30-1.00 mg kg-1). The strong soil acidity, its medium organic matter content and low proportion of clay, favor a high availability of these PHEs, particularly Pb and Cu. Although impact mitigation measures, such as collecting cartridges whenever a round of shots is fired in the shooting range, the pollution assessment indicates that performances should improve in the berm. The application of organic amendments, or nanomaterials, could help reduce the PHEs availability and avoid the contamination of adjacent areas.



Acevedo-Figueroa D, Jiménez BD, Rodríguez-Sierra CJ. 2006. Trace metals in sediments of two estuarine lagoons from Puerto Rico. Environ Pollut. 141:336-342.

Alloway BJ. 2013. Heavy Metals in Soils. Trace Metals and Metalloids in Soils and their Bioavailability. Amsterdam, The Netherlands: Springer.

Althoff DP, Althoff PS, Lambrecht ND, Gipson PS, Pontius JS, Woodford, PB. 2007. Soil properties and perceived disturbance of grasslands subjected to mechanized military training: Evaluation of an index. Land Degrad Dev. 18:269-288.

Anjos C, Magalhães MCF, Abreu MM. 2012. Metal (Al, Mn, Pb and Zn) soils extractable reagents for available fraction assessment: Comparison using plants, and dry and moist soils from the Braçal abandoned lead mine area, Portugal. J Geochem Explor. 113:45-55.

Arenas-Lago D, Rodríguez-Seijo A, Cerqueira B, Andrade ML, Vega FA. 2015. Cd2+, Cu2+, and Pb2+ sorption, desorption and migration in fluvisols. Span J Soil Sci. 5(3):276-295.

Bannon DI, Drexler JW, Fent GM, Casteel SW, Hunter PJ, Brattin WJ, Major MA. 2009. Evaluation of Small Arms Range Soils for Metal Contamination and Lead Bioavailability. Environ Sci Technol. 43:9071-9076.

BOE. 2005. Royal Decree 9/2005, dated January 14, where a list of potentially soil polluting activities and the criteria and standards for the declaration of contaminated soils are established. BOE, January 18, num. 15. p. 1833-1843.

Bremner JM, Mulvaney CS. 1982. Nitrogen-total. In: Page AL, Miller RH, Keeney RS, editors. Methods of soil analysis: Part 2. Chemical and microbiological properties. Agronomy Monographs no. 9, 2nd edition. Madison, WI, USA: American Society of Agronomy and Soil Science Society of America. p. 595-624.

Brevik EC, Cerdà A, Mataix-Solera J, Pereg L, Quinton JN, Six J, Van Oost K. 2015. The interdisciplinary nature of soil. SOIL 1:117-129.

Cao X, Ma LQ, Chen M, Hardison DW Jr, Harris WG. 2003. Weathering of Lead Bullets and Their Environmental Effects at Outdoor Shooting Ranges. J Environ Qual. 32(2):526-534.

CCME. 2007. Recommandations canadiennes pour la qualité des sols: Environnement et santé humaine – tableaux sommaires, mis à jour, in Recommandations Canadiennes pour la Qualité de l’Environnement. Winnipeg: Canadian Council of Ministers of the Environment.

Chen M, Daroub SH, Ma LQ, Harris WG, Cao X. 2002. Characterization of lead in soils of a rifle/pistol shooting range in central Florida, USA. Soil Sediment Contam. 11:1-17.

Daskalakis KD, O’Connor TP. 1995. Normalization and elemental sediment contamination in the coastal United States. Environ Sci Technol. 2(2):470-477.

De la Fuente C, Clemente R, Albuquerque JA, Vélez D, Bernal MP. 2010. Implications of the use of As-rich groundwater for agricultural purposes and the effects of soil amendments on as solubility. Environ Sci Technol. 44(24):9463-9469.

EEA. 2015. The European environment — state and outlook 2015: synthesis report. Copenhagen: European Environment Agency.

Etim EU, Onianwa PC. 2012. Lead contamination of soil in the vicinity of a military shooting range in Ibadan, Nigeria. Toxicol Environ Chem. 94:895-905.

Evangelou MWH, Hockman K, Pokharel R, Jakob A, Schulin R. 2012. Accumulation of Sb, Pb, Cu, Zn and Cd by various plants species on two different relocated military shooting range soils. J Environ Manage. 108:102-107.

FOREGS. 2005. Forum of the European Geological Survey Directors. Geochemical Atlas of Europe, Geological Survey of Finland, Espoo. [Cited 2016 Feb 3]. Available from http://weppi.gtk.fi/publ/foregsatlas/.

Forteza J, García Rodríguez A, Lorenzo Martin LF. 1982. Suelos forestales de la zona N.O. de la Región Castellano-Leonesa. Anuario 1981, Centro de Edafología Aplicada del CSIC 8:175-188.

Gee GW, Or D. 2002. Particle-size analysis: Pipette method. In: Dane JH, Topp GC, editors. Methods of Soil Analysis: Part 4: Physical Methods. Madison, WI, USA: Soil Science Society of America. p. 272-278.

Guemiza K, Mercier G, Blais JF. 2015. Pilot-Scale Decontamination of Small-Arms Shooting Range Soil Polluted with Copper, Lead, Antimony, and Zinc by Acid and Saline Leaching. J Environ Eng. 141(1). 10.1061/(ASCE)EE.1943-7870.0000887.

Hakanson L. 1980. An ecological risk index for aquatic pollution control. A sedimentological approach. Water Res. 14:975-1001.

Hendershot WH, Duquette M. 1986. A simple barium chloride method for determining cation exchange capacity and exchangeable cations. Soil Sci Soc Am J. 50:605-608.

Houba VJG, Temminghoff EJM, Gaikhorst GA, Van Vark W. 2000. Soil analysis procedures using 0.01 M calcium chloride as extraction reagent. Commun Soil Sci Plant Anal. 31:1299-1396.

Islam S, Ahmed K, Habibullah-Al-Mamun, Masunaga S. 2015. Potential ecological risk of hazardous elements in different land-use urban soils of Bangladesh. Sci Total Environ. 512-513:94-102.

Islam MN, Nguyen XP, Jung H-Y, Park J-H. 2016. Chemical Speciation and Quantitative Evaluation of Heavy Metal Pollution Hazards in Two Army Shooting Range Backstop Soils. Bull Environ Contam Toxicol. 96:179-185.

Jensen J, Mesman M. 2006. Ecological risk assessment of contaminated land–Decision support for site specific investigations. RIVM report 711701047. The Netherlands.

Kabata-Pendias A. 2010. Trace elements in soils and plants. 4th edn. New York: CRC Press.

Keesstra SD, Geissen V, Mosse K, Piiranen S, Scudiero E, Leistra M, van Schaik L. 2012. Soil as a filter for groundwater quality. Curr Opin Environ Sustain. 4:507-516.

Laporte-Saumure M, Martel R, Mercier G. 2011. Characterization and metal availability of copper, lead, antimony and zinc contamination at four Canadian small arms firing ranges. Environ Technol. 32(7):767-781.

Lindsay WL, Norwell WA. 1978. Development of a DTPA soil test for zinc, iron, manganese and copper. Soil Sci Soc Am J. 42:421-428.

Müller G. 1969. Index of geoaccumulation in sediments of the Rhine River. J Geol. 2:108-118.

Naidu R, Bolan NS, Megharaj M, Juhasz AL, Gupta SK, Clothier BE, Schulin R. 2008. Chemical bioavailability in terrestrial environments. In: Hartemink AE, McBratney AB, Naidu R, editors. Developments in Soil Science, Vol. 32. Amsterdam: Elsevier. p. 1-6.

Pierart A, Shahid M, Séjaln-Delmas N, Dumat C. 2015. Antimony bioavailability: Knowledge and research perspectives for sustainable agricultures. J Hazard Mater. 289:219-234.

Pierce ML, Moore CB. 1982. Adsorption of arsenite and arsenate on amorphous iron hydroxide. Water Res. 16:1247-1253.

Rajapaksha AU, Ahmad M, Vithanage M, Kim KR, Chang JY, Lee SS, Ok YS. 2015. The role of biochar, natural iron oxides, and nanomaterials as soil amendments for immobilizing metals in shooting range soil. Environ Geochem Health 37:931-942.

Rodríguez-Seijo A, Alfaya MC, Andrade ML, Vega FA. 2016a. Copper, Chromium, Nickel, Lead and Zinc Levels and Pollution Degree in Firing Range Soils. Land Degrad Dev. in press. doi: 10.1002/ldr.2497.

Rodríguez-Seijo A, Lago-Vila M, Andrade ML, Vega FA. 2016b. Pb pollution in soils from a trap shooting range and the phytoremediation ability of Agrostis capillaris L. Environ Sci Pollut Res. 23:1312-1323.

Romero-Freire A, Martin-Peinado FJ, van Gestel CAM. 2015. Effect of soil properties on the toxicity of Pb: Assessment of the appropriateness of guideline values. J Hazard Mater. 289:46-53.

Sanderson P, Naidu R, Bolan N, Bowman M. 2012a. Critical review on chemical stabilization of metal contaminants in shooting range soils. J Hazard Toxic Radioact Waste 16:258-272.

Sanderson P, Naidu R, Bolan N, Bowman M, Mclure S. 2012b. Effect of soil type on distribution and bioaccessibility of metal contaminants in shooting range soils. Sci Total Environ. 438:452-462.

Sherdrick BH, McKeague JA. 1975. A comparison of extractable Fe and Al data using methods followed in the USA and Canada. Can J Soil Sci. 55:77-78.

Spanish Ministry of Defence. 2007. Centros de Adiestramiento y Campos de Maniobras y Tiro. Revista Ejército 800:64-73.

US Soil Conservation Service. 1972. Soil survey laboratory methods and procedures for collecting soil samples. Soil Survey Investigations Report No. 1. Washington, DC: U.S. Government Printing Office.

USEPA. 2005. Best management practices for lead outdoor shooting ranges. EPA-902-B-01-001, Revised June 2005.

VROM. 2000. Circular on Target Values and Intervention Values for Soil Remediation. Annex A. The Hague, The Netherlands: Dutch Ministry of Housing Spatial Planning and Environment.

Walkley A, Black IA. 1934. An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method. Soil Sci. 34:29-38.

Wang G, Murphy D, Oller A, Howard H, Anderson AB, Rijal S, Myers NR, Woodford P. 2014. Spatial and Temporal Assessment of Cumulative Disturbance Impacts Due to Military Training, Burning, Haying, and Their Interactions on Land Condition of Fort Riley. Environ Manage. 54:51-66.

Wilson SC, Lockwood PV, Ashley PM, Tighe M. 2010. The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review. Environ Pollut. 158:1169-1181.

Wu J, Teng Y, Lu S, Wang Y, Jiao X. 2014. Evaluation of Soil Contamination Indices in a Mining Area of Jiangxi, China. PLoS ONE 9(11):e112917.

Yang J, Wang W, Zhao M, Chen B, Dada OA, Chu Z. 2015. Spatial distribution and historical trends of heavy metals in the sediments of petroleum producing regions of the Beibu Gulf, China. Mar Pollut Bull. 91:87-95.

Zhou J, Feng K, Pei Z, Meng F, Sun J. 2016. Multivariate analysis combined with GIS to source identification of heavy metals in soils around an abandoned industrial area, Eastern China. Ecotoxicology 25:380-388.