Application of sorbents in different soil types from small arms shooting ranges for immobilization of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb)
Soil contamination of ammunition residues at shooting ranges for small arms may be followed by leaching of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb). Mixing stabilizing agents into the soil may reduce the mobility of the contaminants. To avoid risk of unexpected effects of a stabilizing agent in large-scale measures, the effect of an amendment should be tested on a small scale in advance. Two different amendments, ferric oxyhydroxide powder (CFH-12 from a commercial provider) and zerovalent iron (powder or grit), were mixed into different soil types in order to test their generic effects as stabilizing agents in contaminated soil from shooting ranges. Factors that were considered for their effects were soil water pH, limestone addition, soil chemical composition, and content of organic matter.
Materials and methods
The stabilizing agents (2–4% weight basis) were mixed into four different soil types contaminated with ammunition residues. The effects of the amendments were elucidated in two column experiments, one small-scale and one larger-scale experiment. Leaching of Pb, Cu, Zn, and Sb from the soil mixed with stabilizing agents was compared with reference soil with no amendments added.
Results and discussion
Best performance was achieved on leaching of Sb irrespective of the type of iron amendment and soil type. The Sb concentrations in the soil leachates were 55–94% less than in the leachates from the reference soils. Both amendments mixed into an acidic soil reduced the Pb, Cu, and Zn concentrations in the soil leachates in the range of 79–99%. The ability of the amendment to reduce leaching of Pb, Cu, and Zn from the other soil types was highly dependent on soil pH. CFH-12 was acidic and pH had to be balanced with limestone. The general trend was that the iron amendments reduced leaching of the elements in the order Sb>>Cu > Pb ≥ Zn.
Iron amendment may be suitable as stabilizing agents for Pb, Cu, Zn, and Sb in soil. The soil pH appeared to be the most important factor governing the mobility of the ammunition residues in the soils. Overall, best effect was achieved with zerovalent iron, which can be purchased at low cost and appeared to have minor influence on the properties of the soils.
KeywordsAntimony Heavy metals Iron oxyhydroxide Soil amendments Soil stabilization Zerovalent iron
Dr. Gudny Okkenhaug from NGI, Norway, kindly provided the CFH-12 Fe oxyhydroxide powder and the limestone used in the study. MSc Elisabeth Elje from FFI helped in preparing and sampling in the lysimeter-2 experiment. The authors also wish to acknowledge Dr. Gudny Okkenhaug and MSc Helga Lassen Bue from NGI for helping in preparing the columns in the lysimeter-2 experiment.
This study received funding from The Norwegian Defence Estates Agency (Project nr. 108901 and 360301).
- Armbruster DA, Tillman MD, Hubbs LM (1994) Limit of detection (LOD)/limit of quantification (LOQ): comparison of the empirical and the statistical methods exemplified with GC-MS assays of abused drugs. Clin Chem 40(7 Pt 1):1233–1238Google Scholar
- 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 and Peat 7, Article no 7Google Scholar
- Essington ME (2004) Soil and water chemistry: an integrative approach. CRC, Boca Raton ISBN 0-8493-1258-2Google Scholar
- Johnson CA, Moench H, Wersin P, Kugler P, Wenger C (2005) Solubility of antimony and other elements in samples taken from shooting ranges. J Environ Qual 34(1):248–254Google Scholar
- Krogstad T. (1992): Methods for soil analyses [Norwegian] Report no. 6/92, Institute for Soil Sciences, Norwegian University of Life Sciences. ISSN 0803-1304Google Scholar
- 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 Am J 59(6):1570–1574. https://doi.org/10.2136/sssaj1995.03615995005900060009x CrossRefGoogle Scholar
- Mariussen E (2012) Analysis of antimony (Sb) in environmental samples FFI-report 2012/00347. ISBN: 978-82-464-2049-3Google Scholar
- McBride MB, Blasiak JJ (1979) Zinc and copper solubility as a function of ph in an acid soil. Soil Sci Soc Am J 43(5):866–870. https://doi.org/10.2136/sssaj1979.03615995004300050009x CrossRefGoogle Scholar
- Myhre O, Fjellheim K, Ringnes H, Reistad T, Longva KS, Ramos TB (2013) Development of environmental performance indicators supported by an environmental information system: application to the Norwegian defence sector. Ecol Indic 29:293–306. https://doi.org/10.1016/j.ecolind.2013.01.005 CrossRefGoogle Scholar
- 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 Hazard Mater 307:336–343. https://doi.org/10.1016/j.jhazmat.2016.01.005 CrossRefGoogle Scholar
- Okkenhaug G, Smebye AB, Pabst T, Amundsen CE, Sævarsson H, Breedveld GD (2017) Shooting range contamination: mobility and transport of lead (Pb), copper (Cu) and antimony (Sb) in contaminated peatland. J Soils Sediments. https://doi.org/10.1007/s11368-017-1739-8
- Santillan-Medrano J, Jurinak JJ (1975) The chemistry of lead and cadmium in soil: solid phase formation. Soil Sci Soc Am Proc 39(5):851–856. https://doi.org/10.2136/sssaj1975.03615995003900050020x CrossRefGoogle Scholar
- 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, vol 244. ACS Publication, American Chemical Society, Washington, DCGoogle Scholar
- 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 micro-X-ray fluorescence and absorption spectroscopy. Environ Sci Technol 39(13):4808–4815. https://doi.org/10.1021/es0482740 CrossRefGoogle Scholar
- Violante A (2013) Elucidating mechanisms of competitive sorption at the mineral/water interface. Adv Agron 118:111–176. https://doi.org/10.1016/B978-0-12-405942-9.00003-7 CrossRefGoogle Scholar
- Voie Ø, Strømseng A (2000). Risk assessment of the heavy metal pollution at an outdoor shooting range. (Norwegian) FFI/rapport 2000/06166 ISBN 82-464-0468-7Google Scholar