Environmental Science and Pollution Research

, Volume 24, Issue 11, pp 10182–10196 | Cite as

Distribution and mobility of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb) from ammunition residues on shooting ranges for small arms located on mires

  • Espen MariussenEmail author
  • Ida Vaa Johnsen
  • Arnljot Einride Strømseng
Research Article


An environmental survey was performed on shooting ranges for small arms located on minerotrophic mires. The highest mean concentrations of Pb (13 g/kg), Cu (5.2 g/kg), Zn (1.1 g/kg), and Sb (0.83 g/kg) in the top soil were from a range located on a poor minerotrophic and acidic mire. This range had also the highest concentrations of Pb, Cu, Zn, and Sb in discharge water (0.18 mg/L Pb, 0.42 mg/L Cu, 0.63 mg/L Zn, and 65 μg/L Sb) and subsurface soil water (2.5 mg/L Pb, 0.9 mg/L Cu, 1.6 mg/L Zn, and 0.15 mg/L Sb). No clear differences in the discharge of ammunition residues between the mires were observed based on the characteristics of the mires. In surface water with high pH (pH ~7), there was a trend with high concentrations of Sb and lower relative concentrations of Cu and Pb. The relatively low concentrations of ammunition residues both in the soil and soil water, 20 cm below the top soil, indicates limited vertical migration in the soil. Channels in the mires, made by plant roots or soil layer of less decomposed materials, may increase the rate of transport of contaminated surface water into deeper soil layers and ground water. A large portion of both Cu and Sb were associated to the oxidizable components in the peat, which may imply that these elements form inner-sphere complexes with organic matter. The largest portion of Pb and Zn were associated with the exchangeable and pH-sensitive components in the peat, which may imply that these elements form outer-sphere complexes with the peat.


Shooting ranges Mires Peat Heavy metals Antimony Sequential extractions 



We are indebted to our colleague, Ms. Marita Ljønes, and the students Ms. Ingvild Gudim (MSc), Ms. Sigurbjørg Hjartardottir (BSc), Ms. Anne Mari Herfindal (BSc), and Ms. Frøya Homlong (BSc) for participating in the field work and laboratory experiments. The authors also wish to acknowledge the anonymous reviewers of the manuscript and the editor of the journal. The work was supported by grants from the Norwegian Defense Estates Agency (Project Nos. 108901 and 360301).

Supplementary material

11356_2017_8647_MOESM1_ESM.docx (9.1 mb)
ESM 1 (DOCX 9362 kb)


  1. Ackermann S, Giere R, Newville M, Majzlan J (2009) Antimony sinks in the weathering crust of bullets from Swiss shooting ranges. Sci. Tot. Environ. 407:1669–1682CrossRefGoogle Scholar
  2. Ambe S (1987) Adsorption-kinetics of antimony(v) ions onto alpha-fe2o3 surfaces from an aqueous-solution. Langmuir 3:489–493CrossRefGoogle Scholar
  3. Ash C, Tejnecky V, Sebek O, Nemecek K, Zahourova-Dubova L, Bakardjieva S, Drahota P, Drabek O (2013) Fractionation and distribution of risk elements in soil profiles at a Czech shooting range. Plant Soil Environ 59:121–129Google Scholar
  4. Braun U, Pusterla N, Ossent P (1997) Lead poisoning of calves pastured in the target area of a military shooting range. Schweiz Arch Tierheilkd 139:403–407Google Scholar
  5. Broder T, Biester H (2015) Hydrologic controls on DOC, As and Pb export from a polluted peatland—the importance of heavy rain events, antecedent moisture conditions and hydrological connectivity. Biogeosciences 12:4651–4664CrossRefGoogle Scholar
  6. Buschmann J, Sigg L (2004) Antimony(III) binding to humic substances: influence of pH and type of humic acid. Environ. Sci. Technol. 38:4535–4541CrossRefGoogle Scholar
  7. Byrne P, Reid I, Wood PJ (2013) Stormflow hydrochemistry of a river draining an abandoned metal mine: the Afon Twymyn, Central Wales. Environ Mon Ass 185:2817–2832CrossRefGoogle Scholar
  8. Cao XD, Ma LQ, Chen M, Hardison DW, Harris WG (2003) Weathering of lead bullets and their environmental effects at outdoor shooting ranges. J Environ Qual 32:526–534CrossRefGoogle Scholar
  9. Chambers FM, Beilman DW, Yu Z (2011) Methods for determining peat humification and for quantifying peat bulk density, organic matter and carbon content for palaeostudies of climate and peatland carbon dynamics. Mires Peat 7: Article no 7Google Scholar
  10. Christl I, Milne CJ, Kinniburgh DG, Kretzschmar R (2001) Relating ion binding by fulvic and humic acids to chemical composition and molecular size. 2. Metal binding. Environ. Sci. Technol. 35:2512–2517CrossRefGoogle Scholar
  11. Christl I, Metzger A, Heidmann I, Kretzschmar R (2005) Effect of humic and fulvic acid concentrations and ionic strength on copper and lead binding. Environ. Sci. Technol. 39:5319–5326CrossRefGoogle Scholar
  12. Clausen J, Korte N (2009) The distribution of metals in soils and pore water at three US military training facilities. Soil Sediment Contam 18:546–563CrossRefGoogle Scholar
  13. Cloy JA, Farmer JG, Graham MC, Mackenzie AB (2009) Retention of As and Sb I ombrotrophic peat bogs: records of As, Sb, and Pb deposition at four Scottish sites. Environ. Sci. Technol. 43:1756–1762CrossRefGoogle Scholar
  14. Craig JR, Rimstidt JD, Bonnaffon CA, Collind TK, Scanlon PF (1999) Surface water transport of lead at a shooting range. Bull Environ Contam Toxicol 63:312–319CrossRefGoogle Scholar
  15. Czarnezki JM (1987) Use of the pocketbook mussel, Lampsilis ventricosa, for monitoring heavy metal pollution in an Ozark stream. Bull Environ Contam Toxicol 38:641–646CrossRefGoogle Scholar
  16. Duggam J, Dhawan A (2007) Speciation and vertical distribution of lead and lead shot in soil at a recreational firing range. Soil Sediment Contam 16:351–369CrossRefGoogle Scholar
  17. Ettler V, Vanek A, Mihaljevic M, Bezdicka P (2005) Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy. Chemosphere 58:1449–1459CrossRefGoogle Scholar
  18. Ettler V, Mihaljevic M, Sebek O, Nechutny Z (2007) Antimony availability in highly polluted soils and sediments—a comparison of single extractions. Chemosphere 68:455–463CrossRefGoogle Scholar
  19. Filella M, Belzile N, Chen YW (2002) Antimony in the environment: a review focused on natural waters. I. Occurrence. Earth-Sci Rev 57:125–176CrossRefGoogle Scholar
  20. Forsvarsbygg (2012) Monitoring of metal contamination in runoff water from closed shooting ranges. [Norwegian]. Technical report SE 2012/08Google Scholar
  21. Gorham E, Rochefort L (2003) Peatland restoration: a brief assessment with special reference to sphagnum bogs. Wetl Ecol Manag 11:109–119CrossRefGoogle Scholar
  22. Gundersen P, Steinnes E (2003) Influence of pH and TOC concentration on Cu, Zn, Cd, and Al speciation in rivers. Water Res 37:307–318CrossRefGoogle Scholar
  23. Gustafsson Ö, Gschwend PM (1997) Aquatic colloids: concepts, definitions, and current challenges. Limnol Oceanogr 42:519–528CrossRefGoogle Scholar
  24. Hardison DW, Ma LQ, Luongo T, Harris WG (2004) Lead contamination in shooting range soils from abrasion of lead bullets and subsequent weathering. Sci. Tot. Environ. 328:175–183CrossRefGoogle Scholar
  25. Hartikainen H, Kerko E (2009) Lead in various chemical pools in soil depth profiles on two shooting ranges of different age. Boreal Environ Res 14:61–69Google Scholar
  26. Haux C, Larsson A, Lithner G, Sjobeck M (1986) A field-study of physiological-effects on fish in lead-contaminated lakes. Environ Toxicol Chem 5:283–288CrossRefGoogle Scholar
  27. Heier LS, Lien IB, Strømseng AE, Ljønes M, Rosseland BO, Tollefsen KE, Salbu B (2009) Speciation of lead, copper, zinc and antimony in water draining a shooting range-time dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.) Sci Tot Environ 407:4047–4055CrossRefGoogle Scholar
  28. Hjortenkrans DST, Mansson NS, Bergback BG, Haggerud AV (2009) Problems with Sb analysis of environmentally relevant samples. Environ Chem 6:153–159CrossRefGoogle Scholar
  29. Hockmann K, Tandy 2, Lenz M, Reiser R, Conesa HM, Keller M, Studer B, Schulin R (2015) Antimony retention and release from drained and waterlogged shooting range soil under field conditions. Chemosphere 134:536–543CrossRefGoogle Scholar
  30. Ilgen AG, Majs F, Barker AJ, Douglas YA, Trainor TP (2014) Oxidation and mobilization of metallic antimony in aqueous systems with simulated groundwater. Geochim Cosmochim Acta 132:16–30CrossRefGoogle Scholar
  31. Johnson CA, Moench H, Wersin P, Kugler P, Wenger V (2005) Solubility of antimony and other elements in samples taken from shooting ranges. J Environ Qual 34:248–254Google Scholar
  32. Jörgensen SS, Willems M (1987) The fate of lead in soils—the transformation of lead pellets in shooting-range soils. Ambio 16:11–15Google Scholar
  33. Klavins M, Purmalis O (2013) Properties and structure of raised bog peat humic acids. J Mol Struct 1050:103–113CrossRefGoogle Scholar
  34. Knechtenhofer LA, Xifra IO, Scheinost AC, Fluhler H, Kretzschmar R (2003) Fate of heavy metals in a strongly acidic shooting-range soil: small scale metal distribution and its relation to preferential water flow. J Plant Nutr Soil Sci 166:84–92CrossRefGoogle Scholar
  35. Kosmulski M (2016) Isoelectric points and points of zero charge of metal (hydr)oxides: 50 years after Parksʼ review Adv. Coll Inter Sci 238:1–61CrossRefGoogle Scholar
  36. Labare MP, Butkus MA, Riegner D, Schommer N, Atkinson J (2004) Evaluation of lead movement from the abiotic to biotic at a small-arms firing range. Environ Geol 46:750–754CrossRefGoogle Scholar
  37. 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 7-8:767–781CrossRefGoogle Scholar
  38. Lee YH (1985) Aluminium speciation in different water types. Ecol Bull 37:109–119Google Scholar
  39. Leverett P, Reynolds K, Roper AJ, Williams PA (2012) Tripuhyite and scharzikite: two of the ultimate sinks for antimony in the natural environment. Mineralog Mag 76:891–902CrossRefGoogle Scholar
  40. Lewis LA, Poppenga RK, Davidson WR, Fischer JR, Morgan KA (2001) Lead toxicosis and trace element levels in wild birds and mammals at a firearms training facility. Arch Environ Contam Toxicol 41:208–214CrossRefGoogle Scholar
  41. Lieb DA, Carline RF (2000) Effects of urban runoff from a detention pond on water quality, temperature and caged Gammarus minus (Say) (Amphipoda) in a headwater stream. Hydrobiologia 441:107–116CrossRefGoogle Scholar
  42. Logan EM, Pulford ID, Cook GT, MacKenzie AB (1997) Complexation of Cu2+ and Pb2+ by peat and humic acid. Europe J Soil Sci 48:685–696CrossRefGoogle Scholar
  43. Manunza B, Deiana S, Maddau V, Gessa C, Seeber R (1995) Stability-constants of metal-humate complexes—titration data analyzed by bimodal gaussian distribution. Soil Sci Soc Amer J 59:1570–1574CrossRefGoogle Scholar
  44. Mariussen E (2012) Analysis of antimony (Sb) in environmental samples FFI-rapport 2012/00347. ISBN: 978–82–464-2049-3Google Scholar
  45. Mariussen E, Ljønes M, Nazari B, Løkke M, Voie OA (2009) Analyses of lead (Pb) and copper (Cu) in perch (Perca fluviatilis) from Steinsjøen small arms shooting range. [Norwegian] Technical report FFI-2009/01925. ISBN: 978–82–464-1666-3Google Scholar
  46. Mariussen E, Ljønes M, Strømseng AE (2012) Use of sorbents for purification of lead, cupper and antimony in runoff water from a small arms shooting range. J. Haz. Mat. 243:95–104CrossRefGoogle Scholar
  47. Mariussen E, Johnsen IV, Strømseng A (2016) Metal pollution at small arm shooting ranges located on mires and the effect of a sedimentation pond on contaminated discharge water containing high concentrations of humic acid. [Norwegian] FFI-report 16/00057. ISBN 978–82–464-2710-2Google Scholar
  48. Mariussen E, Heier LS, Teien HC, Pettersen MN, Holth TF, Salbu B, Rosseland BO (2017) Accumulation of lead (Pb) in brown trout (Salmo trutta) from a lake downstream a former shooting range. Ecotoxicol Environ Safe 135:327–336CrossRefGoogle Scholar
  49. Martin WA, Lee LS, Schwab P (2013) Antimony migration trends from a small arms firing range compared to lead, copper, and zinc. Sci. Tot. Env. 463:222–228CrossRefGoogle Scholar
  50. Murray K, Bazzi A, Carter C, Ehlert A, Harris A, Kopec M, Richardson J, Sokol H (1997) Distribution and mobility of lead in soils at an outdoor shooting range. J Soil Contam 6:79–93CrossRefGoogle Scholar
  51. Nakamaru YM, Altansuvd J (2014) Speciation and bioavailability of selenium and antimony in non-flooded and wetland soils: a review. Chemosphere 111:366–371CrossRefGoogle Scholar
  52. Nash MJ, Maskall JE, Hill SJ (2000) Methodologies for determination of antimony in terrestrial environmental samples. J Environ Monit 2:97–109CrossRefGoogle Scholar
  53. Nieminen TM, Ukonmaanaho L, Shotyk W (2002) Enrichment of Cu, Ni, Zn, Pb and as in an ombrotrophic peat bog near a Cu-Ni smelter in Southwest Finland. Sci. Tot. Env. 292:81–89CrossRefGoogle Scholar
  54. Novak M, Pacherova P (2008) Mobility of trace metals in pore waters of two central European peat bogs. Sci Total Environ 394:331–337CrossRefGoogle Scholar
  55. Novak M, Zemanova L, Voldrichova P, Stepanova M, Adamova M, Pacherova P, Komarek A, Krachler M, Prechova E (2011) Experimental evidence for mobility/immobility of metals in peat. Env Sci Technol 45:7180–7187CrossRefGoogle Scholar
  56. Okkenhaug G, Amstatter K, Bue HL, Cornelissen G, Breedveld GD, Henriksen T, Mulder J (2013) Antimony (Sb) contaminated shooting range soil: Sb mobility and immobilization by soil amendments. Environ. Sci. Technol. 47:6431–6439Google Scholar
  57. Okkenhaug G, Gebhardt KA, Amstätter K, Bue HL, Herzel H, Mariussen E, Almås ÅR, Cornelissen G, Breedveld G, Rasmussen G, Mulder M (2016) Immobilization of antimony (Sb) and lead (Pb) in shooting range soils with iron based sorbents, a field study. J Haz Mat 307:336–343CrossRefGoogle Scholar
  58. Oughton MI, Salbu B, Riise G, Lien H, Østby G, Noren A (1992) Radionucleide mobility and bioavailability in Norwegian and soviet soils. Analyst 117:481–486CrossRefGoogle Scholar
  59. Peddicord RK, LaKind JS (2000) Ecological and human health risks at an outdoor firing range. Environ Toxicol Chem 19:2602–2613CrossRefGoogle Scholar
  60. Pilarski J, Waller P, Pickering W (1995) Sorption of antimony species by humic-acid. Wat Air Soil Pol 84:51–59CrossRefGoogle Scholar
  61. Qiu P, Leygraf C (2011) Initial oxidation of brass induced by humidified air. Appl Surface Sci 258:1235–1241CrossRefGoogle Scholar
  62. Randich E, Duerfeldt W, McLendon W, Tobin W (2002) A metallurgical review of the interpretation of bullet lead compositional analysis. Forensic Sci Int 127:174–191CrossRefGoogle Scholar
  63. Roberts DA, Poore AGB, Johnston EL (2007) BACI sampling of an episodic disturbance: Stormwater effects on algal epifauna. Mar Environ Res 64:514–523CrossRefGoogle Scholar
  64. Rothwell JJ, Evans MG, Daniels SM, Allott THE (2007) Baseflow and stormflow metal concentrations in streams draining contaminated peat moorlands in the Peak District National Park (UK). J Hydrol 341:90–104CrossRefGoogle Scholar
  65. Rydin H, Jeglum J (2006) The biology of peatlands. Oxford University press, Oxford ISBN 0-19-852871-XCrossRefGoogle Scholar
  66. Sanderson P, Naidu R, Bolan N, Bowman M, Mclure S (2012) Effect of soil type on distribution and bioaccessibility of metal contaminants in shooting range soils. Sci Tot Env 438:452–462CrossRefGoogle Scholar
  67. Santillan-Medrano J, Jurinak JJ (1975) The chemistry of lead and cadmium in soil: solid phase formation. Soil Sci Soc Amer Proc 39:851–856CrossRefGoogle Scholar
  68. Scheinost AC, Rossberg A, Vantelon D, Xifra I, Kretzschmar R, Leuz AK, Funke H, Johnson CA (2006) Quantitative antimony speciation in shooting-range soils by EXAFS spectroscopy. Geochim Cosmochm Acta 70:3299–3312CrossRefGoogle Scholar
  69. Schmitt CJ, Finger SE (1982) The dynamics of metals from past and present mining activities in the Big and Black River watersheds, southeastern Missouri. Completion report. U.S. Army Corps of Engineers, St Louis District Proj. No. DACW43-80-A-0109Google Scholar
  70. Sekaly ALR, Mandal R, Hassan NM, Murimboh J, Chakrabarti CL, Back MH, Gregoire DC, Schroeder WH (1999) Effect of metal/fulvic acid mole ratios on the binding of Ni(II), Pb(II), Cu(II), Cd(II), and Al(III) by two well-characterized fulvic acids in aqueous model solutions. Anal Chim Acta 402:211–221CrossRefGoogle Scholar
  71. Shotyk W, Krachler M, Chen B (2004) Antimony in recent, ombrotrophic peat from Switzerland and Scotland: comparison with natural background values (5,320 to 8,020 14C yr BP) and implications for the global atmospheric Sb cycle. Glob Biogeochem Cycles 18:GB1016CrossRefGoogle Scholar
  72. Shotyk W, Rausch N, Nieminen TM, Ukonmaanaho L, Krachler M (2016) Isotopic composition of Pb in peat and Porewaters from three contrasting ombrotrophic bogs in Finland: evidence of chemical diagenesis in response to acidification. Environ. Sci. Technol. 50:9943–9951CrossRefGoogle Scholar
  73. Silamikele I, Nikodemus O, Kalnina L, Kuske E, Rodinovs V, Purmalis O, Klavins M (2010) Major and trace element distribution in the peat from ombrotrophic bogs in Latvia. In: Mires and Peat. (ed) M Klavins University of Latvia Press. ISBN 978–9984–45-163-3Google Scholar
  74. Sjörs H, Gunnarsson U (2002) Calcium and pH in north and central Swedish mire waters. J Ecol 90:650–657CrossRefGoogle Scholar
  75. Skjelkvåle BL, Borg H, Hindar A, Wilander A (2007) Large scale patterns of chemical recovery in lakes in Norway and Sweden: importance of sea salt episodes and changes in dissolved organic carbon. Appl Geochem 22:1174–1180CrossRefGoogle Scholar
  76. Strømseng AE, Ljønes M, Mariussen E (2009) Episodic discharge of lead, copper and antimony from a Norwegian small arm shooting range. J Environ Monit 11:1259–1267CrossRefGoogle Scholar
  77. Stumm W (1995) The inner-sphere surface complex. In: Huang CP, O’Melia CR, Morgan JJ (eds) Aquatic chemistry, interfacial and interspecies processes. Advances in chemistry, volume 244. ACS Publication, American Chemical Society, Washington, DCGoogle Scholar
  78. Syrovetnik K, Malmstrom ME, Neretnieks I (2007) Accumulation of heavy metals in the Oostriku peat bog, Estonia: determination of binding processes by means of sequential leaching. Environ Poll 147:291–300CrossRefGoogle Scholar
  79. Tella M, Pokrovski GS (2012) Stability and structure of pentavalent antimony complexes with aqueous organic ligands. Chem Geol 292-293:57–68CrossRefGoogle Scholar
  80. Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace-metals. Anal Chem 51:844–851CrossRefGoogle Scholar
  81. Tighe M, Lockwood P, Wilson S (2005) Adsorption of antimony(v) by floodplain soils, amorphous iron(III) oxidxide nd humic acid. J Environ Monit 7:1177–1185CrossRefGoogle Scholar
  82. Vantelon D, Lanzirotti A, Scheinost AC, Kretzschmar R (2005) Spatial distribution and speciation of lead around corroding bullets in a shooting range souil studied by Mcro-x-ray fluorescence and absorption spectroscopy. Environ Sci Technol 39:4808–4815CrossRefGoogle Scholar
  83. Violante A (2013) Elucidating mechanisms of competitive sorption at the mineral/water interface. Adv in Agron 118:111–176CrossRefGoogle Scholar
  84. Weng L, Temminghoff EJM, Van Riemsdijk WH (2002) Aluminum speciation in natural waters: measurement using Donnan membrane technique and modeling using NICA-Donnan. Water Res 36:4215–4226CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  1. 1.Norwegian Defence Research Establishment (FFI), Protection and Societal Security DivisionKjellerNorway
  2. 2.The Norwegian Water Resources and Energy DirectorateOsloNorway

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