J Soils Sediments (2010) 10:11421158 DOI 10.

1007/s11368-010-0248-9

SEDIMENTS, SEC 1 SEDIMENT QUALITY AND IMPACT ASSESSMENT RESEARCH ARTICLE

Geochemical studies on the contamination and dispersion of trace metals in intertidal sediments around a military air weapons shooting range
Hyun-Suk Jung & Seong-Taek Yun & Byoung-Young Choi & Hyang-Mi Kim & Myungchae Jung & Soon-Oh Kim & Kyoung-Ho Kim

Received: 4 March 2010 / Accepted: 29 April 2010 / Published online: 16 May 2010 # Springer-Verlag 2010

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
Responsible editor: Kevin G. Taylor H.-S. Jung : S.-T. Yun (*) : B.-Y. Choi : K.-H. Kim Department of Earth and Environmental Sciences, Korea University, Seoul 136-701, Republic of Korea e-mail: styun@korea.ac.kr H.-S. Jung Korea Environment Corporation, Incheon 404-708, Republic of Korea H.-M. Kim Department of Mathematics and Statistics, University of Calgary, Calgary, Canada T2N 1N4 M. Jung Department of Energy and Mineral Resources Engineering, Sejong University, Seoul 143-747, Republic of Korea S.-O. Kim Department of Earth and Environmental Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea

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 HFHNO3HClO4 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 kg1) are: Cd, 0.53.7; Co, 1622; Cr, 4671; Cu, 1051; Mn, 340998; Ni, 1228; Pb, 18277; and Zn, 5089. 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 FeMn (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 FeMn (hydro-)oxides and carbonates (typically for Pb, Cu, and Zn) or cation exchange with clays (especially Cd). These geochemical processes of trace metal immobilization

J Soils Sediments (2010) 10:11421158

1143

would rapidly occur with an increase in pH (up to 8.08.6) in the intertidal environment. However, we recommend a better isolation of metal-contaminated island soils from seaward movement. Keywords Geochemical dispersion . Intertidal sediments . Li normalization . Military air weapons shooting . Principal component analysis . Sequential extraction . Trace metals

1 Introduction Heavy metals are generally considered as serious inorganic pollutants due to their toxic effects, surface enrichment, and slow removal rates. Potentially toxic heavy metals can be inadvertently released from diverse sources into aquatic environments and living habitats by human activity. Once metal contaminants are released into ecosystems, they accumulate in soil, water, sediment, and biota, and accelerate pollution (e.g., Salomons and Frstner 1984; Kabata-Pendias and Pendias 1985; Salomons and Stigliani 1995). Trace metals move through aquatic environments via two mediums, i.e., as particulate matter and as dissolved forms such as free metal ions and soluble complexes. Once the transported trace metals are deposited in marine sediments, binding by diverse mineral phases such as FeMn hydroxides, sulfides, carbonates, and clay minerals immobilizes them until a change in ambient redox or pH conditions occurs (e.g., Adams et al. 1992; Jeong et al. 2006). Therefore, surficial marine sediments, particularly of fine sizes, easily accumulate trace metals before remobilization (e.g., Kennicutt et al. 1993; Lager et al. 2005). Although there have been numerous studies on trace metal pollution and its effects, only a limited number of publications have investigated trace metal contamination (and its effects on biota) in soils, water, and sediments within and around shooting ranges used for sport or military training (Jrgensen and Willems 1987; Stansley et al. 1992; Lin et al. 1995; Murray et al. 1997; Rooney et al. 1999, 2007; Lee et al. 2002; Darling and Thomas 2003; Migliorini et al. 2004; Rantalainen et al. 2006; Sorvari et al. 2006; Bordeleau et al. 2008; Heier et al. 2009; Sneddon et al. 2009). In some countries, the use of ammunition (pellets and bullets) for hunting and sport is a significant source of trace metal pollution because ammunitions generally contain Pb, Cu, Zn, Sb, As, Ni, and Mn (Tanskanen et al. 1991; Lin 1995; Rooney et al. 1999; Hardison et al. 2004; Migliorini et al. 2004). Jrgensen and Willems (1987) estimated the annual use of Pb in shotgun ammunition in Denmark to be about 800 tons, which is about three times larger than the annual use of Pb (250 tons) as additives in automobile fuel. In USA, about 3 million tons of Pb was

released as munitions in hunting and recreational shooting in the 20th century, resulting in the increase of Pb discharge at a rate of approximately 60,000 metric tons per year (Craig et al. 1999). Sorvari et al. (2006) demonstrated that among 2,000 to 2,500 outdoor shooting ranges in Finland, 50 to 60 ranges should be investigated in detail because of their high risk of groundwater pollution. High contents of Pb, Cd, and Cu were also observed in the training field of NATO in Germany (Schaefer 1997). To our knowledge, however, there is no publication on the contamination of soils and sediments derived from military shooting ranges in a marine environment. Recently, in South Korea where there are a great number of military or recreational shooting ranges, the pollution of soils, sediments, and groundwater by trace metals released from ammunitions have become a social issue. However, only a few studies have been made (Lee et al. 2002; Park et al. 2003; Bae and Kim 2006; Ryu et al. 2007). During the past one and a half decades, sociopolitical concerns have been raised as to the pollution of soil and groundwater by heavy metals and petroleum hydrocarbons in areas used by US military forces in South Korea. In particular, an air weapons shooting range located in the N island of this study has been the subject of special concern. The US Air Force has used the N island as an air weapons shooting target since 1951 and the Korean War. The N island is located in an intertidal flat in the central part of the west coast of South Korea (Fig. 1). Like in many other places, potential heavy metal contamination of the island soils and adjacent intertidal sediments has been of concern. Even so, coastal mollusks such as oysters and mussels in the vicinity of the island have been collected and sold without any environmental assessment for human health. Therefore, it was crucial to determine the degree of heavy metals pollution. This study was thus initiated to assess both the degree of contamination and the process and extent of dispersion of trace metals in the intertidal sediments around the N island, and to compare the occurrences (fractionation) of trace metals between contaminated and non-contaminated sediments. The results of this study are the first reporting on the dispersion and geochemical behavior of ammunition-derived trace metals in an intertidal environment.

2 Study area The N island in this study is small with a length of about 250 m and has been used as an air weapons shooting target by the US Air Force stationed in Okinawa (Japan), Guam, Philippines, and Korea. The N island, together with the G and U islands in the study area, is situated in

1144 Fig. 1 Sampling localities of intertidal sediments in the study area, Asan Bay, South Korea. The N island (a shooting target), G island and U island are also shown

J Soils Sediments (2010) 10:11421158

the central part of the west coast of South Korea (see Fig. 1). During surveys in 2000 and 2001, flat land of the target island was free of vegetation and covered with sandy soils where numerous fragments of weathered bombs and bullets were observed. Only about 40% of the forest remains on marginal slopes of the island. Remediation of contaminated soils in the target island was started after early 2010. The west coast of South Korea is the eastern part of the semi-enclosed Yellow (West) Sea which contains a shallow body of water (<100 m deep, average water depth=55 m) with a typical epicontinental shelf (Yang et al. 2003). An intertidal flat within Asan Bay surrounds the N, G, and U islands (see Fig. 1) and is subaerially exposed during ebb tide, being as much as 7 km wide. The intertidal flat forms a habitat of diverse organisms including mussels and oysters. In the study area, a crescent-shaped sand bar is developed from the N to the U islands (see Fig. 1). This sand bar is exposed during ebb tide. Tides in the area are semidiurnal with a mean tidal range of 8.3 m. Seawater generally flows north to west during high tide with a current velocity of 1.3 to 1.8 m s1 (Kim 1978). However, local regressive flow

during low tide is generally directed toward the south from the N island along the sand bar and locally also flows westward at the middle part of the sand bar (see Fig. 1). The geology of the mainland adjacent to the study area is mainly composed of banded biotite gneiss of the Precambrian Kyounggi metamorphic complex. Compared to intertidal sediments in the other areas of the Yellow Sea, the Asan Bay sediments are more feldspar-rich with a quartz:feldspar ratio of ca. 3:2 (Kim 1978).

3 Materials and methods 3.1 Sampling Thirty-two samples of surface intertidal sediments were collected around the N island between December 2000 and March 2001 (see Fig. 1). A representative sample at each locality was prepared by mixing ten subsamples. The samples were taken from the surface to a depth of 5 cm using a stainless steel auger and were immediately transferred to plastic bags and stored at 4C until laboratory analyses.

J Soils Sediments (2010) 10:11421158

1145

3.2 Sediment characterization The grain size distribution of the sediment samples was measured by wet sieving, and the following fractions were determined: silt + clay (<0.05 mm), very fine to fine sand (0.050.18 mm), and medium to coarse sand (>0.18 mm). Organic carbon (OC), carbonate, and trace metal content as well as pH were measured for the <0.18-mm (i.e., <80 mesh) fraction. Three kinds of chemical extraction (i.e., total, partial, and sequential) were performed to determine metal concentrations in the <80 mesh samples, as described below. The pH of sediments was measured using a slurry of sediment (5 g) + deionized water (12.5 ml). Organic carbon content was semi-quantitatively determined from the loss-on-ignition (LOI) value obtained after heating at 600C for 16 h (Nelson and Sommers 1982). The inorganic carbon content (expressed as the percentage CaCO3) was determined by the following procedure: 1.0 g of accurately weighed powder sample was shaken with an appropriate volume of 1 M HCl for 4 h; the residue was dried, and the weight loss measured to obtain the carbonate content (wt.%). 3.3 Chemical extraction of trace metals Total concentrations of trace metals in the sediment samples were analyzed via the following steps: 0.2 g of each sample was totally digested in Teflon vessels with a 4:4:1 mixture of HFHNO3HClO4 acid on a hot plate, evaporated completely, and the residue again dissolved in 5% nitric acid. This procedure was repeated until the sample was completely dissolved, after which the dissolved solution was analyzed. Metal analysis after partial extraction with 0.1 N HCl was also carried out for all samples. This partial extraction technique has been used in South Korea for evaluating metal contamination of soils (Ministry of Environment of Korea 1996) and consists of several steps: 10 g of each sample was transferred into Pyrex glass flasks in a chamber and leached with 50 ml of 0.1 N HCl for 1 h at 30C while shaking. Leachates were analyzed after being filtered with 5B filter paper. It should be noted that soilmetal concentrations determined by the Korean Standard Method are generally lower than those determined by strong acid digestion such as the US EPA 3050 method and the Canadian method (Environment Canada 1979). According to Kim (1998) and Kim and Kim (1998), Cd, Cr, Cu, Pb, and Zn contents determined by the Korean Standard Method are about three times lower than those by the US EPA method. Nevertheless, the weak acid extraction method used in this study provides useful information for evaluating the remobilization potential and bioavailability of metals (cf. Luoma and Bryan 1981;

Bryan and Langston 1992; Sutherland 2002b; Jung et al. 2005). 3.4 Sequential extraction of trace metals and chemical analysis The sequential extraction scheme (SES) has been used to identify and evaluate the mobility and bioavailability of trace metals in soils and sediments (Legret 1993; Krishanamurty et al. 1995; Izquierdo et al. 1997). One of the first SES schemes was proposed as a five-step procedure by Tessier et al. (1979). Several authors have modified this scheme with respect to the soil:extractant ratio, kinds and concentration of extractants, and extraction time (e.g., Maher 1984; Gmez-Ariza et al. 2000). Even so, the lack of uniformity between extraction schemes does not allow the analytical results to be compared worldwide (cf. Bacon and Davidson 2008). To overcome such problems, another sequential extraction scheme was proposed to harmonize and standardize the determination of extractable trace metals in soils and sediments by the Measurement and Testing Program [formerly, the Community Bureau of Reference (BCR)] within the European Community (Ure et al. 1993; Quevauviller et al. 1997). The BCR procedure initially consisted of three extraction steps to sequentially dissolve three operationally defined fractions (i.e., exchangeable + acidic phase, reducible phase, oxidizable phase) and an additional step (if necessary) to determine the residual fraction (cf. Rauret et al. 1999; Maiz et al. 2000; Sutherland and Tack 2000, 2003; Tokalioglu et al. 2000). Although the BCR sequential extraction procedure was slightly modified to overcome poor reproducibility of the second and third fractions (Rauret et al. 1999), we used an original BCR procedure in this study that was initiated at 2000. However, a slight modification of the original BCR procedure was performed to divide the exchangeable + acidic phase fraction into an exchangeable fraction and acid-extractable (carbonate) fraction in the intertidal sediments, as we intended to obtain more detailed information on the major chemical fractions and factors affecting the mobility of trace metals in the marine (intertidal) environment. The extraction procedures used in this study are summarized as follows: 1) Step 1 (exchangeable ions): 8 ml of 1 M MgCl2 solution initially at pH 7 was added to 0.5 g of each dried sample. The sample was shaken for 1 h in an end-overend shaker at room temperature. Then, the supernatant for chemical analysis was separated from the residue by centrifuging at 3,000 rpm for 10 min. 2) Step 2 (acid extractable; carbonates): separately, 20 ml of 0.11 M acetic acid (HOAc) was added to each 0.5-g

1146

J Soils Sediments (2010) 10:11421158

sample. The sample was shaken overnight for 16 h in an end-over-end shaker at room temperature. Then, the supernatant for analysis was separated from the residue by centrifuging at 3,000 rpm for 10 min. 3) Step 3 (reducible; Fe/Mn (hydr-)oxides): 20 ml of 0.1 M hydroxylamine hydrochloride (HA-HCl) adjusted to pH 2 with 2 M HNO3 was added to the rinsed residue from Step 2. The remaining procedure and analysis were the same with those for HOAc in Step 2. 4) Step 4 (oxidizable; sulfides and organic matter): Residue from Step 3 was initially rinsed with 5 ml of 30% H2O2 adjusted to pH 2 with HNO3. For this reaction, the reaction tube was covered with a watch glass and left at room temperature for 1 h with periodic manual shaking (each 15 min). The procedure was continued for an additional 1 h in an 85C water bath without the watch glass cover until the volume was reduced to a few milliliters. A further aliquot of 5 ml of 30% H2O2 was then added to the residue. The tube was covered again and heated to 85C for 1 h. Then, the cover was removed, and the volume was reduced almost to dryness. After cooling to room temperature, the residue was extracted with 25 ml of 1 M NH4OAc (adjusted to pH 2 with HNO3) for 16 h with shaking. The extraction solution was analyzed for metals. 5) Step 5 (residual; silicates and well-crystallized oxides): Residue from Step 3 was completely digested with 14 ml of a 10:3:1 HFHNO3HCl mixture in Teflon bombs on a heating plate for 1 h.

4 Results and discussion 4.1 Size distribution, mineralogy, pH, and carbon contents XRD analysis of a bulk composite sample from the study area showed the mineralogical composition of intertidal sediments to consist of quartz (33.8%), plagioclase (22.2%), potassium feldspar (15.9%), micas (20.1%), chlorite (3.7%), amphibole (2.0%), kaolinite (0.9%), and smectite (1.2%). The quartz:feldspar ratio is ca.1:1, which is slightly lower that the value (about 3:2) reported for Asan Bay sediment (Kim 1978). Physicochemical properties and metal concentrations of collected intertidal sediments (n=32) are summarized in Table 1. The pH of the sediments is slightly alkaline with a narrow range (8.08.6), which is coincident with that of seawater. Thus, we can consider that seawater pH largely controls the solubility, mobility, and fractionation of trace metals in intertidal sediments of the study area. Proportions of the silt + clay fraction (<0.05 mm) in sediments are variable, ranging from 38 to 77 wt.% (average, 52%). Organic carbon contents range from 1.51 to 4.37 wt.% (average, 3.06%), while measured inorganic carbon (CaCO3) contents are low and variable (0.254.87 wt.%; average, 1.01%) (see Table 1). 4.2 Total concentrations For a potential baseline metal inventory, one composite sample of surface soil (<5 cm deep) in the N island (a target of shooting) was collected during the initial stage of our study focused on intertidal sediments and was totally extracted by a 4:4:1 mixture of HFHNO3HClO4. As expected, the soil sample showed severe contamination by Pb (2,510 mg kg 1 ), Cu (167 mg kg 1 ), and Cd (11.3 mg kg1), indicating their substantial release from weathered ammunition (Schaefer 1997). The ranges and average values of total metal concentrations (mg kg1) in intertidal sediments of this study are as follows (Table 2): Cd, 0.53.7 (0.8); Co, 1622 (18); Cr, 4671 (59); Cu, 1051 (18); Li, 4278 (55); Mn, 340998 (533); Ni, 1228 (20); Pb, 18277 (36); and Zn, 5089 (65). Aluminum (Al) and Fe concentrations are very uniform, respectively, having the ranges and averages of 5.37.0 wt.% (5.9%) and 1.82.6 wt.% (2.1%) (see Table 2). To estimate enrichments of measured trace metals in intertidal sediments, we compared our total concentration data with values reported for shallow marine sediments off South Korea and worldwide (Table 3). Trace metal concentrations of intertidal sediments in this study are mostly comparable to the world averages of coastal and estuarine sediments but are significantly lower than the

Chemical analysis of the metal concentrations was performed using an inductively-coupled plasma atomic emission spectrometer (ICP-AES, Optima 3000XL) at the Center for Mineral Resources Research of Korea University. The detection limits of analysis were 27 ppb (Al), 24 ppb (Zn), 21 ppb (Pb), 6 ppb (Cu), 2 ppb (Cr and Ni), and 1 ppb (Cd, Co, Fe, and Mn). Duplicate analysis of the samples indicated relative deviations of data (i.e., precision) to be <5% for Al, Co, Cr, Cu, Fe, Li, Mn, Ni, and Pb and about 10% for Cd. Standard materials including the PACS-2 Certified Reference Materials (marine sediment; for the total digestion procedure) and blanks were also analyzed for the QA/QC of analysis. The accuracy of the laboratory results on total concentrations of trace metals was better than 95% compared with the stated reference values for all metals. The overall quality of data from BCR sequential extraction procedure was also evaluated by comparing the sum of metal concentrations in individual fractions with total metal concentration. The differences in metal concentrations determined by both procedures were usually <15%.

Table 1 Size fraction, pH, contents of organic carbon and carbonate, and total metal concentrations of intertidal sediments pH Cd 8.2 8.2 8.1 8.0 8.3 8.0 8.4 8.1 8.1 8.6 8.0 8.5 8.2 8.4 8.2 8.2 8.2 8.3 8.5 8.3 8.3 8.4 8.2 8.2 8.2 8.4 8.2 8.0 8.3 8.2 8.2 8.2 3.60 3.47 2.91 4.10 3.45 2.69 3.86 2.03 2.73 0.89 0.55 3.16 0.86 1.83 0.91 0.60 0.30 0.61 5.88 6.06 5.42 6.53 6.46 5.37 6.18 5.49 5.58 2.03 2.21 1.95 2.55 2.32 2.09 2.38 1.93 1.96 0.70 0.70 0.61 1.29 3.67 1.22 0.98 0.60 0.57 19.34 17.90 16.58 20.98 19.37 17.37 18.56 17.27 17.02 65.82 61.02 58.53 69.58 68.64 59.27 63.61 50.56 53.66 16.52 17.65 15.24 22.12 39.73 50.57 24.07 13.48 14.58 62.84 59.43 55.33 67.42 58.95 47.88 66.38 41.50 45.94 2.35 3.09 3.28 2.91 2.87 2.83 3.07 1.51 2.87 3.03 3.29 3.46 3.34 2.43 2.51 3.53 2.98 4.18 0.58 0.29 0.60 0.61 0.59 0.59 0.88 0.61 0.51 4.87 1.80 0.25 0.30 0.59 0.53 0.30 0.90 0.56 5.94 5.84 6.34 5.79 6.45 5.94 6.33 5.74 5.53 5.89 5.47 5.58 5.97 5.94 5.74 5.79 6.10 6.84 2.02 2.20 2.25 2.06 2.02 2.16 2.02 1.91 1.97 2.06 1.90 2.00 2.07 1.94 1.95 2.10 2.03 2.08 0.63 0.58 0.79 0.67 0.60 0.71 0.70 0.58 0.76 0.66 0.55 0.71 0.65 0.72 0.54 0.62 0.72 0.71 17.07 18.28 18.20 16.91 16.56 17.35 17.83 15.66 16.26 16.41 15.73 16.26 16.83 16.62 16.30 17.91 18.86 19.36 55.52 63.99 62.31 57.41 55.67 61.50 59.72 51.86 55.36 56.06 55.69 58.24 60.50 55.66 52.77 57.22 59.03 66.08 16.43 17.43 18.28 16.18 13.27 16.77 15.79 12.92 14.12 14.27 13.22 14.79 14.98 15.24 13.18 15.70 14.57 15.84 49.89 58.32 60.18 54.60 51.58 56.43 61.22 44.97 54.12 49.68 43.92 46.45 48.41 52.38 46.99 59.46 55.20 68.96 536.26 575.90 668.13 636.92 493.75 544.58 481.82 454.16 529.06 641.63 483.01 502.79 509.52 460.97 434.76 456.20 460.09 467.76 575.45 563.45 428.25 674.74 442.98 450.76 658.13 479.05 429.64 16.42 23.54 21.61 19.61 17.64 27.81 22.42 15.45 19.92 15.89 12.96 16.19 20.35 18.66 12.19 24.29 19.43 26.81 22.65 24.02 20.82 26.47 26.75 19.11 28.24 13.90 11.61 2.87 3.09 2.22 4.37 3.12 0.29 1.45 1.22 0.87 3.51 5.29 6.45 5.69 7.04 5.83 1.77 2.25 1.92 2.49 2.11 0.52 0.78 0.56 0.85 0.61 15.65 19.01 17.13 21.64 17.89 46.40 63.95 53.63 70.63 61.43 10.14 17.56 14.31 19.72 18.57 43.70 65.21 45.30 77.53 54.65 339.71 671.33 435.15 997.91 580.12 18.75 25.76 15.17 28.31 20.79 Co Cr Cu Li Mn Ni Pb 18.13 24.13 19.60 28.45 25.61 18.54 20.79 22.12 20.71 22.24 21.67 23.89 18.01 20.40 20.00 18.60 20.32 22.52 22.71 17.60 23.86 22.66 22.91 25.28 22.39 22.00 103.38 105.73 277.03 50.04 29.20 22.84 Org. C (wt.%) CaCO3 (wt.%) Al (wt.%) Fe (wt.%) Trace metals (mgkg1) Zn 52.07 80.25 55.03 88.77 71.55 56.51 67.03 75.57 66.71 58.64 69.14 63.94 52.37 55.79 57.70 52.49 57.89 57.70 56.59 59.19 67.58 62.18 71.02 67.50 69.44 61.50 82.15 86.23 74.03 81.60 49.84 55.64

Sample site

Size fraction (%)

>0.18mm

<0.05mm

J Soils Sediments (2010) 10:11421158

1 2 3 4 5

35 30 18 6 10

38 57 43 77 58

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

18 2 3 4 4 0 13 3 16 4 9 4 2 11 6 19 31 5

45 66 64 50 45 61 53 44 50 50 40 39 44 44 43 49 56 71

24 25 26 27 28 29 30 31 32

12 6 21 25 41 34 7 14 18

52 63 51 67 48 46 67 40 50

1147

1148 Table 2 Total and partial (i.e., extractable with 0.1 N HCl) concentrations of metals in intertidal sediments (n=32) (Unit in mg kg1, except the data indicated by * in wt.%) Elements Total concentration Range Al Fe Cd Co Cr Cu Li Mn Ni Pb Zn 5.37.0* 1.82.6* 0.53.7 1622 4671 1051 4278 340998 1228 18277 5089 Mean1 5.90.4* 2.10.2* 0.80.6 182 596 188 559 533121 205 3649 6511

J Soils Sediments (2010) 10:11421158 Partial concentrationa Range 286665 2781043 01.8 0.91.7 0.20.6 1.720.2 1.02.2 144349 0.51.2 4192 5.213.3 Mean1 46281 683196 0.20.3 1.00.2 0.30.1 3.63.9 1.70.3 22958 0.70.2 1635 6.81.9 0.8 3.3 17.3 5.8 0.5 18.2 3.1 43.5 3.5 43.0 10.4 Relative percentageb

Concentration determined after weak acid (0.1 N HCl) digestion

b Ratio of partial concentration to total concentration

worldwide averages of hot (polluted) shallow marine sediments (Cantillo and O'Connor 1992). However, compared with values for worldwide clastic sedimentary rocks such as shales and sandstones (Turekian and Wedepohl 1961; Alloway 1995), our sandy to silty intertidal sediments are enriched in Pb and possibly Cd (see Table 3). Compared to marine surface sediments (n=51) collected from a wide area off the west coast of Korea (Cho et al. 1999), our intertidal sediments are about one and half to two times higher in most metals such as Co, Cr, Cu, and Zn (Cd and Pb were not reported by Cho et al.). Compared to intertidal flat sediments (n=10) off Songdo (Ahn and Choi 1998), located in Kyounggi Bay (see Fig. 1 for locality) and at the mouth of the Han River flowing westward via Seoul, average concentrations of trace metals in our sediments are at least two or three times higher. These two comparisons indicate trace metals enrichment in our studied sediments. On the other hand, compared to intertidal sediments (n=30) off Panweol (Ahn et al. 1995), a typical heavily industrialized city adjacent to the southern part of the Kyounggi Bay, average concentrations of trace metals in our sediments are significantly lower, except for Co (see Table 3). Many factories of machinery, metallurgy, chemistry, rubber industry, and others have been concentrated in the industrial complex of Panweol since 1979, and effluents from a wastewater treatment plant have been discharged directly into the mudflat. Thus, several signs of severe trace metal pollution (especially of Cu, Ni, Cr, and Zn) in intertidal sediments off Panweol undoubtedly originate from industrial sources (Ahn et al. 1995). Similar trace metals pollution (especially Zn, Cd and Pb) was also reported in surface sediments of Jinhae Bay of the South Sea that receives metal-contaminated wastewater (see Table 3; Kwon et al. 2001). Intertidal sediments of this study are significantly lower in most trace metals compared with off-shore sediments near industrialized

cities such as Panweol and Jinhae (see Table 3). However, it should be noted that maximum concentrations of Pb (277 mg kg1), Cd (3.7 mg kg1), and Cu (51 mg kg1) of our sediments are relatively very high. This suggests a local but strong influence of Pb, Cd, and Cu originating from a military air weapons shooting in the study area. 4.3 Partial concentrations The ranges and average values of acid-extractable metal contents (mg kg1) of tidal sediments in this study are as follows (see Table 2): Cd, 0.18.0 (0.2); Co, 0.91.7 (1.0); Cr, 0.20.6 (0.3); Cu, 1.720.2 (3.6); Li, 1.02.2 (1.7); Mn, 144349 (229); Ni, 0.51.2 (0.7); Pb, 4192 (16); and Zn, 5.213.3 (6.8). As described above, the Korean Standard Method of extraction yields preferentially and effectively the weakly bound metals that exist (or are partitioned) mainly in exchangeable sites and in carbonate or Fe-hydroxide minerals. Weakly bonded metals are easily extractable and available in surface water during changes of physicochemical conditions, e.g., acidic rainfall events, and hence can be considered as labile and bioavailable fractions (Luoma and Bryan 1981; Bryan and Langston 1992; Yun et al. 2000; Jung et al. 2005; Lee et al. 2005; Kwon et al. 2010). There are some advantages of the partial extraction; it is cost-effective and rapid, and it requires minimal technical expertise and dangerous acids like HClO4 and HF (Sutherland 2002a, b). Examination of acid-extractable contents of trace metals indicates that intertidal sediments of this study are contaminated especially with Cd and Pb, locally exceeding the Korean guidelines for soils. In addition, the ratio of the 0.1 M HCl extraction to the total extraction contents for each metal reflects both the relative proportion of bioavailable forms and possibly its origin [i.e., anthropogenic (shooting-related) or not]. Average values of

J Soils Sediments (2010) 10:11421158 Table 3 Comparison of total concentration of heavy metals (mg kg1) in shallow marine sediments off South Korea and elsewhere. Data from worldwide clastic sediments are also listed for comparison
Cantillo and OConnor (1992) Turekian and Wedepohl (1961)

1149

Ahn and Choi (1998)

Cho et al. (1999)

Ahn et al. (1995)

Kwon et al. (2001)

This study

Reference

Alloway (1995)

Alloway (1995)

the ratios decrease in the following order (see Table 2): Mn (43.5%), Pb (43.0%), Cu (18.2%), Cd (17.3%), Zn (10.4%), Co (5.8%), Ni (3.5%), Li (3.1%), and Cr (0.5%). These results suggest that in addition to Pb and Cd, Cu, Zn, and possibly Mn with high ratios likely reflect their influences from military shooting. 4.4 Spatial distribution of trace metals The spatial distribution pattern of trace metals in sediment can be helpful in identifying their source. The distribution of trace metals in our intertidal sediments is shown in Fig. 2. The results of both total and partial extractions show the occurrence of high concentrations of Pb, Cd, and Cu restricted to the area adjacent (<150 m) the N island (i.e., sampling points 27, 28, 29, and 30), while other analyzed metals do not show any distinct spatial anomaly. Concentrations of Pb, Cd, and Cu dramatically decrease at the other sampling points including two localities (i.e., 31, 32) at the northeast of the N island (see Fig. 2). As stated above, Pb, Cd, and Cu are the major elements of bullets; thus, these metals were obviously dispersed from the N island (shooting target), influencing nearby intertidal sediments. In addition, Zn concentrations determined by weak acid extraction show moderate enrichments in the immediate vicinity (i.e., sampling points 27, 28, 29, and 30) of the target area (see Fig. 2). Zn is a trace component in bullets used for military training. Figure 2 also shows that the sand fraction of intertidal sediments increases near the N island, indicating that coarser particles in intertidal sediments were derived from weathered rocks and soils of the island. Thus, it is also likely that transportation of sediment particles from the island was enhanced by physical fragmentation of rocks by shooting. Some metals such as Pb, Cd, Cu, and Zn were also transported from the shooting area and restrictedly deposited in intertidal sediments with higher sand proportions within a short distance from the island (<150 m). Thereafter, secondary chemical transformation of those shooting-derived metals occurred in the intertidal environment (see below). 4.5 Normalization of total metal concentrations with lithium: assessment of shooting-related contamination To determine the degree of anthropogenic contamination of sediments, i.e., the concentrations above which would naturally occur, it is necessary to estimate the natural component of total concentration. Natural trace metal concentrations and their variability in sediments are determined not only by grain size distribution but also fundamentally by the composition of minerals and secondary compounds. Trace metal concentrations in

40 (15106)

n.a. (80120) 68 (20250) 50 (30150) 120 (30590) n.a. (1050) 23

65 (5089)

290

170

182

Zn

91

32

58.4

11.1

36 (18277)

110

Pb

20 68 90 19 45

34

17 (650)

187.8

10.9

26

20 (1228)

92

Ni

48

18 (1051)

9 (329)

207

Cu

93

28

37 (1293)

123

59 (4671)

170

46

61

17

7 (316)

11.2

6.3

18 (1622)

Co

13

Cr

35 5) Worldwide sandstones and conglomerates

a

n.a. (520)

10

n.a. (1030)

95

2) Mcarine surface sediments of South Korea

1) Worldwide coasts and estuaries

Asan Bay sediment: intertidal flat of this study (n=32)a Surface sediment of the Jinhae Bay, South Sea (n=10) 3) Worldwide shales

Locality and source

4) Worldwide shales and clays

Ranges of concentrations are shown in parentheses. n.a. = not analyzed

<0.02

0.8 (0.53.7)

4.3

1.1

Surface sediment off the West Coast (n=51)

1) Intertidal flat off Panweol (n=30)

1.7

Cd

Kyounggi Bay sediment

Hot (polluted) sediment

Average

2) Intertidal flat off Songdo (n=10)

3.8

0.3

n.a. (0.01711)

n.a. (0.0190.4)

1150 Fig. 2 Histograms showing spatial distributions of the concentrations of heavy metals (determined by total extraction and 0.1 N HCl extraction) and grain size of intertidal sediments

J Soils Sediments (2010) 10:11421158

sediments usually increase with decreasing grain size. However, the granulometric approach cannot successfully compensate for metal variability. Thus, normalization to the grain size difference should be performed to detect and quantify the anomalous metal concentrations (Loring 1993; Aloupi and Angelidis 2001). Aluminum (Al) has been frequently used as a grain size proxy in marine and estuarine sediments, because it is a major constituent of fine-grained aluminosilicates with which the bulk of trace metals are associated in those sediments (Aloupi and Angelidis 2001). However, Al cannot be successfully used for the sediments containing abundant immature physically weathered materials,

such as feldspars, of variable grain size, as is the case in this study. This is due to poor or insignificant correlations between trace metals and Al because roughly the same amounts of Al are present in the coarse and fine fractions (Aloupi and Angelidis 2001). For such surface sediments, lithium (Li) can be successfully used as a geochemical proxy because trace metals are mostly associated in the same mineralogical components as Li, e.g., micas, ferromagnesian minerals, and secondary clay minerals, but not feldspars (Loring and Rantala 1992). Hence, we examined the usefulness of Li as a geochemical normalizer for evaluating the degree of anthropogenic (i.e., shooting-related) contamination.

J Soils Sediments (2010) 10:11421158

1151

Table 4 summarizes Spearman correlation coefficients between textural and geochemical parameters of our intertidal sediments. The silt + clay content showed good correlations with most parameters except Cd, Cu, and Pb (see Table 4). It is notable that Li shows the highest correlation (r=0.87; see Table 4) with silt + clay content. In addition, Li concentration showed good correlations with most of the measured transition elements such as Co, Cr, Ni, and Zn (r>0.82; see Table 4). These observations reflect the ability of Li to geochemically normalize the metal concentrations in relation to the textural variability of our sediments (Aloupi and Angelidis 2001). Therefore, by using Li as a geochemical normalizer with a natural origin whose concentration is controlled by texture, it is possible to evaluate the anthropogenic influences of trace metals in our sediments (n=32). Figure 3 shows good positive correlations between silt + clay content and concentrations of total Al, total Fe, and OC. Table 4 shows poor correlations between Li and some metals such as Cd (r=0.66), Cu (r=0.72), and Pb (r=0.55). Zinc (Zn) has the Spearman's r value of 0.85. As described above, it is noteworthy that these metals are restrictedly enriched in the sediments adjacent to the N island (see Fig. 2). Hence, we scrutinized the concentration relationships between total Li and total Cd, Cu, Pb, and Zn (Fig. 4). Figure 4 clearly shows a few anomalous samples whose chemical composition was affected by shooting-related metal contamination. If we exclude the anomalous data from a few sampling points, the correlations are excellent: =0.733 for Cd, =0.833 for Cu, =0.784 for Pb, and =0.920 for Zn. The numbers of such sampling points are 27, 28, and 29 (and possibly 30) for Cd; 27, 28, 29, and 30 for Cd and Cu; 27,

28, 29, 30, and 31 for Pb; and 28 and 29 for Zn. Furthermore, it is evident that environmental impacts of trace metals on intertidal sediments are spatially restricted to the area adjacent to the N island. Figure 4 also shows correlations between total Cd, Cu, Pb, and Zn. Good correlations are observed for the following pairs (see Table 4): PbCu (r=0.69), CuCd, (r=0.72), CuZn, (r=0.88), and ZnCd, (r=0.72). This indicates their identical source (i.e., shooting-related contamination). As described above, Pb, Cu, Cd, and Zn are the constituents of bullets and bombs of air weapons. Principal components analysis (PCA) was applied to refine the qualitative designation of sample sites for trace metals more precisely. The PCA is used to describe the variation in a set of correlated variables in terms of a new set of uncorrelated variables with decreasing order of importance. Component 1 accounts for much of the variation in the original data, and component 2 accounts for as much as possible of the remaining variation, and so on. The results of PCA for this study are shown in Table 5. The first two components all have variances (eigenvalues) greater than one, 2.846 (component 1) and 1.547 (component 2), and together account for almost 81% of the variance of the original variables. The coefficients defining each component are scaled so that their sums of squares equal unity (blanks indicate near-zero values). The first component is regarded as an index of natural components. The second component is largely concerned with anthropogenic components, having positive coefficients for Cd (0.433), Cu (0.565), Pb (0.566), and Zn (0.124) (see Table 5). Thus, these two components are used as the basis for various graphical displays of the sites (Figs. 5, 6, and 7).

Table 4 Spearman correlation coefficients () among silt + clay, organic carbon, and total metal concentrations of intertidal sediments Silt + claya Silt +claya Org. C Al Cd Co Cr Cu Fe Li Mn Ni Pb Zn
a

Org. C

Al

Cd

Co

Cr

Cu

Fe

Li

Mn

Ni

Pb

Zn

1 0.58** 0.64** 0.54** 0.75** 0.79** 0.69** 0.78** 0.87** 0.61** 0.78** 0.47** 0.77**

1 0.53** 0.46** 0.60** 0.79** 0.52** 0.67** 0.72** 0.50** 0.70** 0.45** 0.67**

1 0.58** 0.69** 0.69** 0.51** 0.70** 0.76** 0.54** 0.64** 0.43* 0.65**

1 0.61** 0.68** 0.72** 0.70** 0.66** 0.47** 0.65** 0.62** 0.72**

1 0.83** 0.78** 0.80** 0.82** 0.43* 0.76** 0.75** 0.81** 1 0.83* 0.87** 0.85** 0.59** 0.86** 0.61** 0.89** 1 0.87* 0.72** 0.52** 0.75** 0.69** 0.88**

1 0.80** 0.67** 0.82** 0.60** 0.92**

1 0.56** 0.90** 0.55** 0.85**

1 0.49** 0.24 0.51**

1 0.56** 0.83**

1 0.65**

Size of silt+clay fraction is <0.05 mm

*Significant correlation at 95% confidence level, ** Significant correlation at 99% confidence level

1152 Fig. 3 Scatter plot matrix of four variables (silt + clay content, organic carbon content, and total concentrations of Al and Fe) of intertidal sediments

J Soils Sediments (2010) 10:11421158

Fig. 4 Scatter plot matrix of five variables (i.e., total concentrations of Li, Cd, Cu, Pb, and Zn) in intertidal sediments. Numbers denote samples potentially affected by shooting-related contamination

J Soils Sediments (2010) 10:11421158 Table 5 Results of principal component analysis (PCA) of silt + clay, organic carbon, and total metal concentrations of intertidal sediments Component 1 Component 2 Component 3 Standard deviation Proportion of Variance Cumulative Proportion Loadings silt+claya Org. C Al Cd Co Cr Cu Fe Li Mn Ni Pb Zn 2.846 0.623 0.623 0.300 0.278 0.283 0.158 0.322 0.333 0.153 0.328 0.327 0.251 0.306 0.334 1.547 0.184 0.807 0.203 0.105 0.163 0.433 0.835 0.054 0.861 0.205 0.121 0.283 0.597

1153

0.565 0.162 0.225 0.566 0.124

0.185

0.499 0.181 0.400

Figure 5 shows scatter plots of the data (samples) in the space of the first two principal components (PC 1 and PC 2) that demonstrate that sites 27, 28, 29, and 30 are highly exposed to trace metals. The levels of four trace metals (Cd, Cu, Pb, and Zn) plotted against the second principal component scores (see Fig. 6) also indicate that sites 28 and 29 are highly contaminated. Plots of lithium (Li) against the first two principal components are shown in Fig. 7. Sites 28 and 29 are anomalous on the Li versus second principal component scores diagram (see Fig. 7b), indicating their highest affection by shooting-related metal contamination. In summary, both the use of Li normalizer to examine geochemical correlations and the application of PCA to total concentration data are very successful in identifying the trace metal contamination of intertidal sediments caused by air weapons training, which is characterized by Pb, Cu, Cd, and Zn in the limited place near the shooting range. 4.6 Assessment of geochemical fractionation of metals The sequential extraction of intertidal sediments (n=32) was performed using a modified BCR procedure to understand the geochemical phases and processes potentially affecting the dispersion and mobility of trace metals (esp., Cd, Cu, Pb, and Zn) in an intertidal environment. The results of sequential extraction are summarized in Table 6. Comparison of the sum of metal concentrations in individual fractions with total metal concentration (determined by strong acid

digestion) suggests good recoveries of sequential extraction for most metals, approximately falling between 70 and 130% (average recovery percentage=86.6111.3%; see Table 6). Very small proportions of Al, Fe, and Cr (average 0.1 to 2.3%) were released in the steps for exchangeable and acidextractable (carbonate) fractions (see Table 6). These metals, together with Co and Ni, were largely found in the residual fraction (average, 73.896.6%). The residual fraction consists of the metals retained within the crystal lattice of minerals and well-crystallized oxides and is considered to be immobile (Tessier et al. 1979). In contrast, 34 to 65% of total Mn was released in the fractions of exchangeable (average, 10.4%) and acid-extractable (average, 41.3%) forms (see Table 6). This proportion range is comparable to the proportions of 0.1 N HCl extraction (average, 43.5%; see Table 2) and suggests that about one half of Mn occurs in weakly bound phases such as carbonates in our intertidal sediments. Large amounts of Cd, Cu, Pb, and Zn were recovered in the reducible fraction (in average, Cd 10.5%, Cu 24.8%, Pb 48.5%, and Zn 18.9%), while those in the oxidizable fraction were relatively low (<0.1% for Cd, 8.1% for Cu, 6.0% for Pb and 10.1% for Zn; see Table 6). For Cu and Zn, the concentrations in the acid-extractable fraction were comparable to those in the oxidizable fraction, while about twice as much Pb (average 13.6%) was released from the acidextractable fraction compared to the oxidizable fraction. Concentrations in the residual fraction were 32.9% Pb, 58.2% Cu, 60.4% Zn, and 81.4% Cd. These observations suggest that except for the metals in the residual fraction,

Fig. 5 Scatter plots of the data (for each sample) in the space of the first two principal components (i.e., PC 1 and PC 2)

1154

J Soils Sediments (2010) 10:11421158

Fig. 6 Plots of four variables (i.e., total Cd, Cu, Pb, and Zn) against the second principal component (PC 2)

FeMn (hydro-)oxides play an important role in fractionation of Cd, Cu, Pb, and Zn in our sediments. FeMn (hydro-) oxides in sediments can scavenge trace metals in water by coprecipitation and adsorption if the water is geochemically reduced and/or the pH increases, and the opposite process (i.e., metals remobilization) is also plausible (Balistrieri and Murray 1986; Burdige 1993; Kwon et al. 2010). The difference of fractionation of Cd, Cu, Pb, and Zn in sediments was further examined according to the sample groups described above (Fig. 8). Group A represents sediment samples that were affected by shooting-related contamination in the vicinity of the shooting range (i.e., sites 27, 28, 29, and 30), while Group B denotes uncontaminated samples. Figure 8 shows that trace metal fractionation is clearly distinct between the two groups. The percentages of Cd, Cu, Pb, and Zn that were released from the residual fraction (i.e., step 5) were significantly lower for Group A samples (see Table 6),

indicating that these metals are preferentially bound to the fractions of steps 1 to 4. Percentages of Cd, Cu, and Pb in the reducible fraction (i.e., step 3) remarkably increased for Group A samples to average values of Cd 23%, Cu 36%, and Pb 60% (see Table 6). These values are about 1.5 to 2 times higher than those for Group B samples, which suggests that anthropogenic Cd, Cu, and Pb are preferentially partitioned to FeMn (hydro-)oxides in the intertidal environment. For Pb, Cu, and Zn, the percentages of the carbonate fraction (i.e., step 2) were also much higher for Group A samples (Pb 27%, Cu 20%, and Zn 19%). In the case of Cd in Group A samples, 33% was released in the exchangeable fraction (see Table 6). In summary, the geochemical behavior and fate of trace metals (Cd, Cu, Pb, and Zn) transported to an intertidal environment from the shooting range (i.e., N island) are mainly controlled by either adsorption onto and/or coprecipitation with FeMn (hydro-)oxides and carbonates

J Soils Sediments (2010) 10:11421158

1155

Fig. 7 Scatter plots of the data (for each sample) on total Li versus principal component scores diagrams

Table 6 Average values of sequential extraction of elements from intertidal sediments (n=32) (Concentration units in mg kg1, except the data indicated by * in wt.%) Metal Fractions Exchangeable Al Cd Co Cr Cu Fe Mn Ni Pb Zn Concentration % Concentration % Concentration % Concentration % Concentration % Concentration % Concentration % Concentration % Concentration % Concentration % 29.74 0.05 0.06 7.21 0.04 0.22 <0.002 <0.003 0.17 0.94 1.92 0.01 55.29 10.37 0.01 0.06 <0.02 <0.04 0.01 0.02 Acid extractable 34.74 0.06 0.01 1.24 1.36 7.73 0.08 0.14 1.43 8.09 473 2.27 220.38 41.33 1.07 5.23 4.88 13.55 6.84 10.50 Reducible 1128 1.90 0.08 10.48 1.75 9.94 2.83 4.79 4.39 24.77 2894 13.89 86.16 16.16 1.76 8.64 17.49 48.52 12.32 18.92 Oxidizable 852 1.43 <0.001 <0.12 1.46 8.28 4.04 6.84 1.43 8.05 1970 9.45 33.57 6.29 1.76 8.63 2.15 5.96 6.60 10.14 Residual 5.75* 96.56 0.65 81.38 13.01 73.82 52.14 88.22 10.31 58.16 1.55* 74.38 137.85 25.85 15.82 77.45 11.86 32.92 39.36 60.44 Sum 5.95* 100.00 0.80 100.00 17.63 100.00 100.00 100.00 17.73 100.00 2.08* 100.00 533.25 100.00 20.42 100.00 36.04 100.00 65.11 100.00 Recovery (%)a Range Mean

80117 70123 83111 80104 80120 84130 83120 81109 82111 80115

95.2 91.2 94.3 86.6 89.2 111.3 98.9 90.7 91.2 92.2

Percentage of the sum concentration of stepwise results to the total concentration determined separately by strong acid digestion

1156 Fig. 8 The results of modified BCR sequential extraction of intertidal sediments (n=32), showing geochemical fractionation of Cd, Cu, Pb, and Zn (represented as the recovery percentages of each metal in each extraction step). Averaged total concentrations of each metal and error bars are also shown. Samples of Group A represent shooting-related contamination in the vicinity of N island and include sites 27, 28, 29 and 30, while those of Group B are not affected by heavy metal contamination

J Soils Sediments (2010) 10:11421158

(typically for Pb, Cu and Zn) or cation exchange with clays (especially Cd). These geochemical processes resulting in immobilization of trace metals would rapidly occur with an increase in pH (up to 8.08.6) during transport to the intertidal environment. Therefore, we consider that shooting-related trace metal contamination in the studied intertidal environment is restricted to only a short distance (<150 m) from the N island.

Cu, Li, Mn, Ni, Pb, and Zn) in a total of 32 intertidal sediments that were collected around a >50-year-old military air weapons shooting range in an island (N island), Yellow (West) Sea of Korea. The major findings of this study can be summarized as follows: (1) Sampled sediments are variable in texture (sandy to silty) and elemental chemistry. Total concentrations of sediments showed substantial contamination by Pb (max. 277 mg kg1), Cd (max. 3.7 mg kg1), Cu (max. 51 mg kg1) and Zn (max. 89 mg kg1). Weak acid (0.1 N HCl) solubilized relatively higher proportions for Pb (43.0% of the total concentration), Cd (17.3%), Cu (18.2%), and Zn (10.4%), suggesting that these metals are mainly of anthropogenic origin.

5 Summary In this study, we examined both total and 0.1 N HClextractable concentrations of 11 metals (Al, Fe, Cd, Co, Cr,

J Soils Sediments (2010) 10:11421158

1157 In: Proceedings of 2006 Autumn Conference. Korean Society of Soil and Groundwater Environment, pp. 5356 (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 50:22352243 Bordeleau G, Martel R, Ampleman G, Thiboutot S (2008) Environmental impacts of training activities at an air weapons range. J Environ Qual 37:308317 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 76:89131 Burdige DJ (1993) The biogeochemistry of manganese and iron reduction in marine sediments. Earth-Sci Rev 35:249284 Cantillo AY, OConnor TP (1992) Trace element contaminants in sediments from the NOAA National Status and Trends Programme compared to data from throughout the world. Chem Ecol 7:3150 Cho YG, Lee CB, Choi MS (1999) Geochemistry of surface sediments off the southern and western coasts of Korea. Mar Geol 159:111129 Craig JR, Rimstidt JD, Bonnaffon CA, Collins TK, Scanlon PF (1999) Surface water transport of lead at shooting range. Bull Environ Contam Toxicol 63:312319 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 313:235243 Environment Canada (1979) Inland waters directorate. In: Analytical method manual. Water Quality Branch, Ottawa Gmez-Ariza JL, Girldez I, Snchez-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 246:271283 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 328:175183 Heier LS, Lien IB, Strmseng AE, Ljnes M, Rosseland BO, Tollefsen KE, Salbu B (2009) Speciation of lead, copper, zinc and antimony in water draining a shooting rangetime dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.). Sci Total Environ 407:40474055 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 34:123128 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 10:445455 Jrgensen SS, Willems M (1987) The fate of lead in soils: the transformation of lead pellets in shooting range soil. Ambio 16:1115 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 48:437449 Kabata-Pendias A, Pendias H (1985) Trace elements in soils and plants. CRC, Boca Raton 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 28:115 Kim SW (1978) Bottom sediments of the Asan bay, west coast of Korea. J Kor Inst Mining Geol 11:8188 (in Korean) 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 35:582587 (in Korean) 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 35:5967 (in Korean)

(2) The degree and spatial extent of shooting-related trace metal contamination could be recognized by careful examination of total concentration data using Li as a geochemical normalizer. Combined with PCA analysis of total concentration data, the results showed that sediment contamination is characteristic for Pb, Cd, Cu, and Zn and is spatially restricted to the vicinity area (<150 m) from the N island used as a shooting target. (3) Sequential extraction of intertidal sediments using a modified BCR method indicated that trace metals in contaminated sediments are more abundant in weakly bound fractions such as exchangeable, acid-extractable, and reducible forms than those in non-contaminated sediments in which trace metals are largely bound in residual form. Anthropogenic Pb, Cd, Cu, and Zn that were transported from the shooting range seem to be readily immobilized by either adsorption onto and/or coprecipitation with FeMn (hydro-)oxides and carbonates (typically for Pb, Cu, and Zn) or cation exchange with clays (especially for Cd), due to an increase in pH in intertidal environment. (4) Even though dispersion of trace metals is not pervasive and significant in the studied intertidal environment, better isolation of metals-contaminated island soils from seaward movement is recommended.
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.

References
Adams WJ, Kimerle RA, Barnett JW Jr (1992) Sediment quality and aquatic life assessment. Environ Sci Technol 26:18641875 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 36:808817 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 30:200206 Alloway BJ (1995) Heavy metals in soils, 2nd edn. Blackie Academic and Professional, London Aloupi M, Angelidis MO (2001) Geochemistry of natural and anthropogenic metals in the coastal sediments of the island of Lesvos, Aegean Sea. Environ Poll 113:211219 Bacon JR, Davidson CM (2008) Is there a future for sequential chemical extraction? Analyst 133:2546 Bae BH, Kim MK (2006) Distribution and transport of contaminants (heavy metals and explosives) in military gunnery range in Korea.

1158 Krishanamurty GSR, Huang PM, van Rees KCJ, Kozac LM, Posted HPW (1995) Speciation of particulate-bound cadmium of soil and its bioavailability. Analyst 120:659665 Kwon YT, Lee CW, Ahn BY (2001) Sedimentation pattern and sediments bioavailability in a wastewater discharging area by sequential metal analysis. Microchem J 68:135141 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 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 48:92100 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 94:406411 Lee PK, Yu YH, Yun ST, Mayer B (2005) Metal contamination and solid phase partitioning of metals in urban roadside sediments. Chemosphere 60:672689 Legret M (1993) Speciation of heavy metals in sewage sludge and sludge-amended soil. Intl J Environ Anal Chem 51:161165 Lin Z (1995) Secondary mineral phases of metallic lead in soils of shooting ranges from rebro County, Sweden. Environ Geol 27:370375 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 89:303309 Loring DH (1993) Regional mineralogical variability in Eastern Canadian Marine Sediments. Nantes, France, ICES WG/MS Loring DH, Rantala RTT (1992) Manual for the geochemical analysis of marine sediments and suspended particulate matter. Earth-Sci Rev 32:235283 Luoma SN, Bryan GW (1981) A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants. Sci Total Environ 17:165196 Maher WA (1984) Evaluation of a sequential extraction scheme to study associations of trace elements in estuarine and oceanic sediments. Bull Environ Contam Toxicol 32:339344 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 110:39 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 129:331340 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 6:7993 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 539580 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 A38:12851297 Quevauviller Ph, Rauret G, Lpez-Snchez 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 205:223234 Rantalainen ML, Torkkeli M, Strmmer R, Setl H (2006) Lead contamination of an old shooting range affecting the local ecosystema case study with a holistic approach. Sci Total Environ 369:99108

J Soils Sediments (2010) 10:11421158 Rauret G, Lpez-Snchez 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 1:5761 Rooney CP, McLaren RG, Cresswell RJ (1999) Distribution and phytoavailability of lead in a soil contaminated with lead shot. Water, Air Soil Poll 116:535548 Rooney CP, McLaren RG, Condron LM (2007) Control of lead solubility in soil contaminated with lead shot: effect of soil pH. Environ Poll 149:149157 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 29:259269 Salomons W, Frstner U (1984) Metals in the hydrocycle. SpringerVerlag, New York 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 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-pathwayreceptor investigation of the fate of trace elements derived from shotgun pellets discharged in terrestrial ecosystems managed for game shooting. Environ Poll 157:26632669 Sorvari J, Antikainen R, Pyy O (2006) Environmental contamination at Finnish shooting rangesthe scope of the problem and management options. Sci Total Environ 366:2131 Stansley W, Widjeskog L, Roscoe DE (1992) Lead contamination and mobility in surface water at trap and skeet ranges. Bull Environ Contam Toxicol 49:640647 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 17:353365 Sutherland RA (2002b) Multi-element removal from road-deposited sediments using weak hydrochloric acid. Environ Geol 42:937944 Sutherland RA, Tack FMG (2000) Metal phase associations in soils from an urban watershed, Honolulu, Hawaii. Sci Total Environ 256:103113 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 8:3750 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. 187193 Tokalioglu S, Kartal S, Eli 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 413:3340 Turekian KK, Wedepohl KH (1961) Distribution of the elements in some major units of the Earths crust. Geol Soc Am Bull 72:175192 Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 51:844851 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 51:135151 Yang SY, Jung HS, Lim DI, Li CX (2003) A review on the provenance discrimination of sediments in the Yellow Sea. Earth-Sci Rev 63:93120 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 21:9891000