Skip to main content

Advertisement

Log in

Geochemical studies on the contamination and dispersion of trace metals in intertidal sediments around a military air weapons shooting range

  • SEDIMENTS, SEC 1 • SEDIMENT QUALITY AND IMPACT ASSESSMENT • RESEARCH ARTICLE
  • Published:
Journal of Soils and Sediments Aims and scope Submit manuscript

Abstract

Purpose

A number of publications have raised trace metal contamination of soils and sediments within and around shooting ranges used for sport or military training. To our knowledge, however, there is no publication on the contamination of sediments derived from military shooting ranges in a marine environment. Therefore, this work was purposed to assess the dispersion and fractionation of ammunition- and bomb-derived trace metals in intertidal sediment.

Materials and methods

Intertidal sediments (n = 32) were collected around a small island that has been used as a target for military air weapons shooting training for more than 50 years in the west coast area of South Korea and were analyzed for size distribution, pH, organic/inorganic carbon contents, and trace metals concentrations. Three kinds of the chemical extraction were used for trace metals analysis: 1) total extraction with a 4:4:1 mixture of HF–HNO3–HClO4 acid, 2) partial extraction with 0.1 N HCl, and 3) sequential extraction by a modified Community Bureau of Reference (BCR) method. We also compared our total concentration data with values reported for shallow marine sediments off South Korea and worldwide. Principal component analysis (PCA) was also used to identify shooting-related anthropogenic inputs for some trace metals.

Results and discussion

Ranges of total trace metals concentrations (mg kg−1) are: Cd, 0.5–3.7; Co, 16–22; Cr, 46–71; Cu, 10–51; Mn, 340–998; Ni, 12–28; Pb, 18–277; and Zn, 50–89. Using Li as a geochemical normalizer suggests that significant enrichments of Pb and Cd and moderate enrichments of Cu and Zn occur restrictedly in the immediate vicinity (<150 m) of the shooting range. This is also supported by the results of PCA analysis. Sequential extraction shows that Fe–Mn (hydro-)oxides play an important role in controlling (immobilizing) anthropogenic trace metals (Pb, Cd, Cu, and Zn). Pb and Cu are also bound to carbonate minerals, while Cd is also present in the exchangeable fraction.

Conclusions

Trace metals (Cd, Cu, Pb, and Zn) derived from weathering of ammunitions and bombs have not been dispersed extensively to marine environment from the target island, due to either adsorption onto and/or coprecipitation with Fe–Mn (hydro-)oxides and carbonates (typically for Pb, Cu, and Zn) or cation exchange with clays (especially Cd). These geochemical processes of trace metal immobilization would rapidly occur with an increase in pH (up to 8.0–8.6) in the intertidal environment. However, we recommend a better isolation of metal-contaminated island soils from seaward movement.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Adams WJ, Kimerle RA, Barnett JW Jr (1992) Sediment quality and aquatic life assessment. Environ Sci Technol 26:1864–1875

    Article  CAS  Google Scholar 

  • Ahn IY, Choi JW (1998) Macrobenthic communities impacted by antropogenic actives in an intertidal sand flat on the west coast (Yellow Sea) of Korea. Mar Poll Bull 36:808–817

    Article  CAS  Google Scholar 

  • Ahn IY, Kang YC, Choi JW (1995) The influence of industrial effluents on intertidal benthic communities in Panweol, Kyeonggi Bay (Yellow Sea) on the West Coast of Korea. Mar Poll Bull 30:200–206

    Article  CAS  Google Scholar 

  • Alloway BJ (1995) Heavy metals in soils, 2nd edn. Blackie Academic and Professional, London

    Google Scholar 

  • Aloupi M, Angelidis MO (2001) Geochemistry of natural and anthropogenic metals in the coastal sediments of the island of Lesvos, Aegean Sea. Environ Poll 113:211–219

    Article  CAS  Google Scholar 

  • Bacon JR, Davidson CM (2008) Is there a future for sequential chemical extraction? Analyst 133:25–46

    Article  CAS  Google Scholar 

  • Bae BH, Kim MK (2006) Distribution and transport of contaminants (heavy metals and explosives) in military gunnery range in Korea. In: Proceedings of 2006 Autumn Conference. Korean Society of Soil and Groundwater Environment, pp. 53–56 (in Korean)

  • Balistrieri LS, Murray JW (1986) The surface chemistry of sediments from the Panama Basin: the influence of Mn oxides on metal adsorption. Geochim Cosmochim Acta 50:2235–2243

    Article  CAS  Google Scholar 

  • Bordeleau G, Martel R, Ampleman G, Thiboutot S (2008) Environmental impacts of training activities at an air weapons range. J Environ Qual 37:308–317

    Article  CAS  Google Scholar 

  • Bryan GW, Langston WJ (1992) Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries: a review. Environ Poll 76:89–131

    Article  CAS  Google Scholar 

  • Burdige DJ (1993) The biogeochemistry of manganese and iron reduction in marine sediments. Earth-Sci Rev 35:249–284

    Article  CAS  Google Scholar 

  • Cantillo AY, O’Connor TP (1992) Trace element contaminants in sediments from the NOAA National Status and Trends Programme compared to data from throughout the world. Chem Ecol 7:31–50

    Article  CAS  Google Scholar 

  • Cho YG, Lee CB, Choi MS (1999) Geochemistry of surface sediments off the southern and western coasts of Korea. Mar Geol 159:111–129

    Article  CAS  Google Scholar 

  • Craig JR, Rimstidt JD, Bonnaffon CA, Collins TK, Scanlon PF (1999) Surface water transport of lead at shooting range. Bull Environ Contam Toxicol 63:312–319

    Article  CAS  Google Scholar 

  • Darling CTR, Thomas VG (2003) The distribution of outdoor shooting ranges in Ontario and the potential for lead pollution of soil and water. Sci Total Environ 313:235–243

    Article  CAS  Google Scholar 

  • Environment Canada (1979) Inland waters directorate. In: Analytical method manual. Water Quality Branch, Ottawa

  • Gómez-Ariza JL, Giráldez I, Sánchez-Rodas D, Morales E (2000) Comparison of the feasibility of three extraction procedures for trace metal partitioning in sediments from south-west Spain. Sci Total Environ 246:271–283

    Article  Google Scholar 

  • Hardison DW Jr, Ma LQ, Luongo T, Harris WG (2004) Lead contamination in shooting range soils from abrasion of lead bullets and subsequent weathering. Sci Total Environ 328:175–183

    Article  CAS  Google Scholar 

  • 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 Total Environ 407:4047–4055

    Article  CAS  Google Scholar 

  • Izquierdo C, Usero J, Gracia I (1997) Speciation of heavy metals in sediments from Salt Marshes on the southern Atlantic coast of Spain. Mar Poll Bull 34:123–128

    Article  CAS  Google Scholar 

  • Jeong KS, Cho JH, Lee JH, Kim KH (2006) Accumulation history of anthropogenic heavy metals (Cu, Zn, and Pb) in Masan Bay sediments, southeastern Korea: a role of chemical front in the water column. Geosci J 10:445–455

    Article  CAS  Google Scholar 

  • Jørgensen SS, Willems M (1987) The fate of lead in soils: the transformation of lead pellets in shooting range soil. Ambio 16:11–15

    Google Scholar 

  • Jung HB, Yun ST, Mayer B, Kim SO, Park SS, Lee PK (2005) Transport and sediment-water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, Korea. Environ Geol 48:437–449

    Article  CAS  Google Scholar 

  • Kabata-Pendias A, Pendias H (1985) Trace elements in soils and plants. CRC, Boca Raton

    Google Scholar 

  • Kennicutt MC, Wade TL, Presley BJ, Requejo AG, Brooks JM, Denoux GJ (1993) Sediment contaminants in Casci Bay, Maine: inventories, sources and potential for biological impacts. Environ Sci Technol 28:1–15

    Article  Google Scholar 

  • Kim SW (1978) Bottom sediments of the Asan bay, west coast of Korea. J Kor Inst Mining Geol 11:81–88 (in Korean)

    Google Scholar 

  • Kim KH (1998) A comparative analysis of soil metal concentrations in terms of differences in sampling and analytical approaches. J Kor Inst Min Energy Resour Eng 35:582–587 (in Korean)

    Google Scholar 

  • Kim KH, Kim SH (1998) A comparative analysis of different pretreatment methods in the determinations of soil-metal concentrations and some causes to their data interpretation. J Kor Inst Min Energy Resour Eng 35:59–67 (in Korean)

    Google Scholar 

  • Krishanamurty GSR, Huang PM, van Rees KCJ, Kozac LM, Posted HPW (1995) Speciation of particulate-bound cadmium of soil and its bioavailability. Analyst 120:659–665

    Article  Google Scholar 

  • Kwon YT, Lee CW, Ahn BY (2001) Sedimentation pattern and sediments bioavailability in a wastewater discharging area by sequential metal analysis. Microchem J 68:135–141

    Article  CAS  Google Scholar 

  • Kwon MJ, Yun ST, Doh SJ, Son BK, Choi K, Kim W (2010) Metal enrichment and magnetic properties of core sediment from the eastern Yellow Sea: implication to paleo-depositional change during the late Pleistocene/Holocene transition. Quat Intl. doi:10.1016/j.quaint.2009.07.027

    Google Scholar 

  • Lager T, Hamer K, Schulz HD (2005) Mobility of heavy metals in harbor sediments: an environmental aspect for the reuse of contaminated dredged sediments. Environ Geol 48:92–100

    Article  CAS  Google Scholar 

  • Lee IS, Kim OK, Chang YY, Bae BH, Kim HH, Baek KH (2002) Heavy metal concentrations and enzyme activities in soil from a contaminated Korean shooting range. J Biosci Bioeng 94:406–411

    CAS  Google Scholar 

  • Lee PK, Yu YH, Yun ST, Mayer B (2005) Metal contamination and solid phase partitioning of metals in urban roadside sediments. Chemosphere 60:672–689

    Article  CAS  Google Scholar 

  • Legret M (1993) Speciation of heavy metals in sewage sludge and sludge-amended soil. Intl J Environ Anal Chem 51:161–165

    Article  CAS  Google Scholar 

  • Lin Z (1995) Secondary mineral phases of metallic lead in soils of shooting ranges from Örebro County, Sweden. Environ Geol 27:370–375

    Article  Google Scholar 

  • Lin Z, Comet B, Qvarfort U, Herbert R (1995) The chemical and mineralogical behaviour of Pb in shooting range soils from central Sweden. Environ Poll 89:303–309

    Article  CAS  Google Scholar 

  • Loring DH (1993) Regional mineralogical variability in Eastern Canadian Marine Sediments. Nantes, France, ICES WG/MS

    Google Scholar 

  • Loring DH, Rantala RTT (1992) Manual for the geochemical analysis of marine sediments and suspended particulate matter. Earth-Sci Rev 32:235–283

    Article  CAS  Google Scholar 

  • Luoma SN, Bryan GW (1981) A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants. Sci Total Environ 17:165–196

    Article  CAS  Google Scholar 

  • Maher WA (1984) Evaluation of a sequential extraction scheme to study associations of trace elements in estuarine and oceanic sediments. Bull Environ Contam Toxicol 32:339–344

    Article  CAS  Google Scholar 

  • Maiz I, Arambarri I, Garcia R, Millan E (2000) Evaluation of heavy metal availability in polluted soils by two sequential extraction procedures using factor analysis. Environ Poll 110:3–9

    Article  CAS  Google Scholar 

  • Migliorini M, Pigino G, Bianchi N, Bernini F, Leonzio C (2004) The effects of heavy metal contamination on the soil arthropod community of a shooting range. Environ Poll 129:331–340

    Article  CAS  Google Scholar 

  • Ministry of Environment of Korea (1996) Korean Standard Treatment Method

  • 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 6:79–93

    CAS  Google Scholar 

  • Nelson DW, Sommers LE (1982) Total carbon, organic carbon, and organic matter. In: Page AL, Miller RH, Keeney DR (eds) Methods of soil analysis, part 2 (Agronomy Monograph 9). American Society of Agronomy, Madison, pp 539–580

    Google Scholar 

  • Park JS, Chang YY, Bae BH, Kim OK, Cho KS, Lee IS (2003) Low heavy metal bioavailability in soil at contaminated Korean shooting sites. J Environ Sci Health A38:1285–1297

    Article  CAS  Google Scholar 

  • Quevauviller Ph, Rauret G, López-Sánchez JF, Rubio R, Ure A, Muntuau H (1997) Certification of trace metal extractable contents in a sediment reference material (CRM 601) following a three-step sequential extraction procedure. Sci Total Environ 205:223–234

    Article  CAS  Google Scholar 

  • Rantalainen ML, Torkkeli M, Strömmer R, Setälä H (2006) Lead contamination of an old shooting range affecting the local ecosystem—a case study with a holistic approach. Sci Total Environ 369:99–108

    Article  CAS  Google Scholar 

  • Rauret G, López-Sánchez JF, Sahuquillo A, Rubio R, Davidson C, Ure A, Quevauviller Ph (1999) Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. J Environ Monit 1:57–61

    Article  CAS  Google Scholar 

  • Rooney CP, McLaren RG, Cresswell RJ (1999) Distribution and phytoavailability of lead in a soil contaminated with lead shot. Water, Air Soil Poll 116:535–548

    Article  CAS  Google Scholar 

  • Rooney CP, McLaren RG, Condron LM (2007) Control of lead solubility in soil contaminated with lead shot: effect of soil pH. Environ Poll 149:149–157

    Article  CAS  Google Scholar 

  • Ryu H, Han JK, Jung JW, Bae B, Nam K (2007) Human health risk assessment of explosives and heavy metals at a military gunnery range. Environ Geochem Health 29:259–269

    Article  CAS  Google Scholar 

  • Salomons W, Förstner U (1984) Metals in the hydrocycle. Springer-Verlag, New York

    Google Scholar 

  • Salomons W, Stigliani B (1995) Biogeodynamics of pollutants in soils and sediments: risk assessment of delayed and non-linear responses. Environmental Science Series, Springer, Berlin

    Google Scholar 

  • Schaefer KW (1997) International experiences and expertise in registration, investigation, assessment, and clean-up of contaminated military sites. Dames and Moore GmbH and Co

  • Sneddon J, Clemente R, Riby P, Lepp NW (2009) Source-pathway-receptor investigation of the fate of trace elements derived from shotgun pellets discharged in terrestrial ecosystems managed for game shooting. Environ Poll 157:2663–2669

    Article  CAS  Google Scholar 

  • Sorvari J, Antikainen R, Pyy O (2006) Environmental contamination at Finnish shooting ranges—the scope of the problem and management options. Sci Total Environ 366:21–31

    Article  CAS  Google Scholar 

  • Stansley W, Widjeskog L, Roscoe DE (1992) Lead contamination and mobility in surface water at trap and skeet ranges. Bull Environ Contam Toxicol 49:640–647

    Article  CAS  Google Scholar 

  • Sutherland RA (2002a) Comparison between non-residual Al, Co, Cu, Fe, Mn, Ni, Pb and Zn released by a three-step sequential extraction procedure and a dilute hydrochloric acid leach for soil and road deposited sediment. Appl Geochem 17:353–365

    Article  CAS  Google Scholar 

  • Sutherland RA (2002b) Multi-element removal from road-deposited sediments using weak hydrochloric acid. Environ Geol 42:937–944

    Article  CAS  Google Scholar 

  • Sutherland RA, Tack FMG (2000) Metal phase associations in soils from an urban watershed, Honolulu, Hawaii. Sci Total Environ 256:103–113

    Article  CAS  Google Scholar 

  • Sutherland RA, Tack FMG (2003) Fractionation of Cu, Pb and Zn in certified reference soils SRM 2710 and SRM 2711 using the optimized BCR sequential extraction procedure. Adv Environ Res 8:37–50

    Article  CAS  Google Scholar 

  • Tanskanen H, Kukkonen I, Kaija J (1991) Heavy metal pollution in the environment of a shooting range. In: Auto S (ed) Current Research 1989–1990. Geological Survey of Finland, Espoo, Finland, pp. 187–193

    Google Scholar 

  • Tokalioglu S, Kartal S, Elçi L (2000) Determination of heavy metals and their speciation in lake sediments by flame atomic absorption spectrometry after a four-stage sequential extraction procedure. Anal Chim Acta 413:33–40

    Article  CAS  Google Scholar 

  • Turekian KK, Wedepohl KH (1961) Distribution of the elements in some major units of the Earth’s crust. Geol Soc Am Bull 72:175–192

    Article  CAS  Google Scholar 

  • Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 51:844–851

    Article  CAS  Google Scholar 

  • Ure AM, Quevauvuller Ph, Muntau H, Griepink B (1993) Speciation of heavy metals in soils and sediment. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the Commission of the European Communities. Intl J Environ Anal Chem 51:135–151

    Article  CAS  Google Scholar 

  • Yang SY, Jung HS, Lim DI, Li CX (2003) A review on the provenance discrimination of sediments in the Yellow Sea. Earth-Sci Rev 63:93–120

    Article  CAS  Google Scholar 

  • Yun ST, Choi BY, Lee PK (2000) Distribution of heavy metals (Cr, Cu, Zn, Pb, Cd, As) in roadside sediments, Seoul metropolitan city, Korea. Environ Technol 21:989–1000

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The initiation of this study was supported by the Ministry of Defense of Korea. The preparation and completion of this manuscript were possible by the support from Korea Research Foundation (KRF) to the Environmental Geosphere Research Lab (EGRL) of Korea University (KU). Many graduate students at the Environmental Geochemistry Laboratory of KU helped field works and sampling. We thank Rodney H. Grapes (KU) for providing comments on the early draft version of this manuscript. Constructive comments provided by two anonymous reviewers are gratefully acknowledged since they helped to improve the final version of this manuscript.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Seong-Taek Yun.

Additional information

Responsible editor: Kevin G. Taylor

Rights and permissions

Reprints and permissions

About this article

Cite this article

Jung, HS., Yun, ST., Choi, BY. et al. Geochemical studies on the contamination and dispersion of trace metals in intertidal sediments around a military air weapons shooting range. J Soils Sediments 10, 1142–1158 (2010). https://doi.org/10.1007/s11368-010-0248-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11368-010-0248-9

Keywords

Navigation