environmental protection strategies for sustainable development || a review of environmental...

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Contents

14.1 Shooting Ranges: A Menace to the Environment .......................................................... 43814.1.1 Backgrounds ...................................................................................................... 43814.1.2 Environmental Concerns .................................................................................... 43914.1.3 Environmental Management Practices (EMPs) ................................................. 441

14.2 Remediation of Shooting Ranges Soil ........................................................................... 44214.2.1 Soil Characteristics and Remediation Technologies .......................................... 442

14.3 Remediation of Shooting Range Soils Using Lime-Based Waste Materials ................. 44414.3.1 Lead Immobilization Using Waste Materials ..................................................... 44514.3.2 Use of Lime-Based Waste Materials .................................................................. 446

14.4 Conclusion ..................................................................................................................... 446References ................................................................................................................................. 447

Abstract Many shooting ranges are contaminated by heavy metals and the used bullets have been known as a primary source. Once the bullets perch on soils, toxic metals such as lead (Pb), copper (Cu), nickel (Ni), antimony (Sb), and zinc (Zn) can be released into the soils and further transformed into available forms threat-ening the surrounding environment. In this review, we evaluated different sources of waste materials as soil amendments to stabilize heavy metals in soils. Amend-ments such as red mud, sugar foam, poultry waste, and dolomitic residue have been used to stabilize Pb at shooting ranges. Among various amendments, lime-based waste materials such as oyster shell and eggshell can effectively immobilize heavy metals, thereby reducing their bioavailability in soils. The main mechanism of Pb immobilization is closely associated with sorption and precipitation at high soil pH. Calcium aluminate hydrate (CAH) and calcium silicate hydrate (CSH) also can be formed to retain the metals in hardened soils. Overall, the use of lime-based wastes is applicable to immobilize toxic metals at shooting range soils.

A. Malik, E. Grohmann (eds.), Environmental Protection Strategies for Sustainable Development, Strategies for Sustainability, DOI 10.1007/978-94-007-1591-2_14, © Springer Science+Business Media B.V. 2012

Chapter 14A Review of Environmental Contamination and Remediation Strategies for Heavy Metals at Shooting Range Soils

Mahtab Ahmad, Sang Soo Lee, Deok Hyun Moon, Jae E. Yang and Yong Sik Ok

Y. S. Ok ()Department of Biological Environment, Kangwon National University, Chuncheon 200-701, Koreae-mail: [email protected]

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Keywords Heavy metals • Environmental contamination • Shooting range • Remediation • Immobilization

14.1 Shooting Ranges: A Menace to the Environment

14.1.1 Backgrounds

Shooting ranges, which are also known as firing ranges, are designed to use firearms for purposes of military training or public recreation (Scheetz and Rimstidt 2009). To secure a sufficient distance or to reduce noise pollution, most shooting ranges are constructed as outdoor facilities and are located in desolate areas. In some cases, the indoor shooting ranges are situated at urban areas for public recreation purpose. All firearms such as rifles, pistols, shot guns, and machine guns must be used at properly designed shooting ranges as shown in Fig. 14.1 (Tardy et al. 2003; USEPA 2003). Depending on types of firearm and capacity of firing station, a sufficient distance and width in shooting ranges vary. Moveable or fixed target is made of paper, plastic or metal, and lead (Pb) is mostly used as a bullet material because of its versatility and performance. A backstop with heights from 5 to 8 m is distinguished by building ma-terials that consist of earthen berms, sand traps, steel traps, or rubber traps behind a target to gather bullets and bullet fragments (ITRC 2005). However, absorbed bullets and their fragments can be weathered over time by process in metal transformation, thereby contaminating soils and surrounding environments.

Fig. 14.1 A typical shooting range (modified from Tardy et al. 2003)

Impact Berm

Target

Range Floor

Firing Line

5 – 8 m

25 – 600 m

30 m

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14.1.2 Environmental Concerns

14.1.2.1 Heavy Metal Contamination

Used bullets at shooting ranges are regarded as a source of soil pollution due to the release of metals and metalloids into surrounding environments (Cao et al. 2003a; Dermatas et al. 2006a; Sorvari et al. 2006). A bullet pellet typically consists of lead (Pb; > 90%), antimony (Sb; 2–7%), arsenic (As; 0.5–2%), nickel (Ni; < 0.5%), and traces of bismuth (Bi) and silver (Ag) (Chrastný et al. 2010; Dermatas et al. 2006a; Robinson et al. 2008; Sorvari et al. 2006), and a bullet jacket is mainly made of copper (Cu; 89–95%), and zinc (Zn; 5–10%) (Robinson et al. 2008; USEPA 2003). Once a bullet and its fragments perch on the soil, these materials can be dissolved by chemical reactions such as oxidation, carbonation, and hydration (Ma et al. 2007). Soils at military shooting ranges are also contaminated with energetic compounds such as trinitrotoluene (TNT; C6H2[NO2]3CH3), dinitrotoluene (DNT; C6H3[CH3][NO2]2), trinitrobenzene (TNB; C6H3N3O6), nitroglycerin (NG; C3H5N3O9), and ni-trocellulose (NC; C6H7[NO2]3O5) (Berthelot et al. 2008; Ragnvaldsson et al. 2007).

Shooting ranges are world widely distributed as shown in Table 14.1. About 60,000 MT of Pb is being deposited every year from ammunition in the United States (Ma et al. 2002). In addition, several studies reported that heavy metals such as Pb, Sb, and Cu are highly concentrated in shooting range soils as shown in Table 14.2. According to the USGS report in 2002, shooting ranges are the second largest source of Pb contamination in the United Sates. Generally, factors such as the firing period and frequency, a type of used ammunition, soil properties, cli-mate, and management practices influence on a soil contamination level at shooting ranges. For example, at common shooting ranges, the concentrations of Pb reached serious levels ranging from 385 to 49,228 mg kg–1 in the United States, and from 8,684 to 29,200 mg kg–1 in East Asian countries. However, the importance of heavy metal contamination in the shooting range soils, particularly Pb, has been reported from only few countries such as the United States and Scandinavian Peninsula.

Table 14.1 Lead (Pb) deposition at shooting rangesCountry Pb deposition (ton y–1) Number of shooting

rangesReference

Canada 10–30 NA Scheuhammer and Norris (1996)

Denmark 800 NA Lin (1996)Finland 530 2,000–2,500 Hartikainen and

Kerko (2009)Korea 267 > 690 KMNDa (2002)Norway 103 NA Heier et al. (2009)Sweden 500–600 NA Lin (1996)Switzerland 400–500 > 2,000 Johnson et al. (2005)United States 60,000 > 10,000 Cao et al. (2008)NA Not availablea The Korea Ministry of National Defense

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14.1.2.2 Heavy Metal Mobility

High concentration of Pb from shooting range soils is commonly observed due to increased solubility and bioavailability of Pb pellets. In the past, metallic Pb in bullets and bullet fragments has been assumed as a material that is naturally stable in the soil and it has no detrimental impact on the environment (Ma et al. 2002). However, recent studies found that metallic Pb in the soils can be transformed into active Pb species, thereby increasing the mobility of Pb in the surrounding environ-ments (Astrup et al. 1999; Cao et al. 2003a, 2008; Ma et al. 2007).

Lead transformation mechanism has been well documented by Ma et al. (2007). Once, a bullet settles into soils, the weathering of Pb pellets is being processed with exposure to air and water. Oxidation of metallic Pb results in the formation of crust around bullet fragments consisting of secondary minerals such as massicot (PbO), cerussite (PbCO3), hydrocerussite (Pb3[CO3]2[OH]2), and anglesite (PbSO4). Disso-lution of these secondary minerals has also occurred by the mobilization of Pb (Cao et al. 2003a; Chrastný et al. 2010; Ma et al. 2007). Weathering and transformation of Pb pellets are affected by factors such as soil particle size, water flow rate, soil pH, redox-potential, available anion, cation exchange capacity (CEC), soil organic matter (SOM), and carbon dioxide (CO2) partial pressure in soil solution (Cao et al. 2003b; Dermatas et al. 2008; Heier et al. 2009; Manninen and Tanskanen 1993; Martin et al. 2008; Sorvari et al. 2006; Takamatsu et al. 2010). Generally, Pb in soils may be readily mobilized at the acidic condition compared to the neutral or alkali condition (Manninen and Tanskanen 1993; Ok et al. 2007b). Enriched soil with high SOM leads to increase the weathering rate of Pb pellets (Dermatas et al. 2006b; Heier et al. 2009). Mobility of Pb can also be significantly higher in the sandy textured-soil than the other textured-soils (Sorvari et al. 2006). Spuller et al. (2007) reported that iron hydroxides (Fe[OH]2 and Fe[OH]3) and secondary mineral

Table 14.2 Total contents of lead (Pb), antimony (Sb) and copper (Cu) at shooting rangesCountry Pb (ton y–1) Sb (ton y–1) Cu (ton y–1) ReferenceCanada 100–14,600 3.5–314 330–835 Ragnvaldsson et al. (2007)Finland 15,500–41,800 NA NA Hartikainen and Kerko (2009)Germany 16,760 437 817 Spuller et al. (2007)Korea 166 NA 161 Lee et al. (2002)

8,684 NA 285 Moon et al. (2010)Japan 29,200 NA NA Hashimoto et al. (2009)Sweden 71–24,500 NA NA Lin (1996)Switzerland 110–67,860 5–3,020 20–2,250 Vantelon et al. (2005)

1,450–515,800 35–1,750 100–445 Johnson et al. (2005)12,533 675 149 Knechtenhofer et al. (2003)

United States 2,520–35,868 NA NA Cao et al. (2008)3,165 NA NA Dermatas et al. (2006a)12,710–48,400 NA NA Cao et al. (2003a)1,025–49,228 NA NA Dermatas et al. (2006b)

385–12,400 NA NA Labare et al. (2004)NA Not available

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phases (Ca[Sb(OH)6]2 and Pb[Sb(OH)6]2) control the Sb mobility in shooting range soils. The high mobility of metal elements from the weathering of bullets and bullet fragments increases the bioavailability of metals (Ma et al. 2007).

14.1.2.3 Environmental Risks

Soluble phase of heavy metals induces fatal environmental risks due to its high mobility and bioavailability. Surface runoff and erosion may cause migration of a relatively less-soluble form of heavy metals in shooting range soils. The Pb is a toxic heavy metal that generates the most concern in shooting range soils. The bio-availability of Pb depends on its species in the soil. As mentioned above, metallic Pb which is contained in bullets and bullet fragments is being weathered and trans-formed into secondary minerals, especially PbCO3 which is a highly bioavailable form (USEPA 2003). The bioavailability of Pb can be measured by the juvenile swine test (as mimic childhood Pb exposure), stable Pb isotope technique (Pb inges-tion in adults), and physiological extraction test (PBET; in vitro test) (USEPA 2003). Investigation of metal leachability also determines an environmental risk (Cao et al. 2008). The United State Environmental Protection Agency (USEPA 1992, 1994) has developed several procedures to analyze the heavy metal leachability such as the toxicity characteristics leaching procedure (TCLP) and the synthetic precipitation leaching procedure (SPLP). The TCLP is often used to simulate specific conditions in a landfill, while the SPLP is used to reproduce the acid rain condition. An envi-ronmental risk at shooting ranges has been determined from contamination levels of groundwater and surface water (Heier et al. 2009; Sorvari et al. 2006), soil enzymat-ic activity (Lee et al. 2002), and accumulation of heavy metals into plant tissues (La-bare et al. 2004; Ma et al. 2002; Mozafar et al. 2002; Rooney et al. 1999), regarding to a human being or other animals (Braun et al. 1997; Gulson et al. 2002; Migliorini et al. 2004; Wixson and Davies 1994). Nowadays, concerns about heavy metal con-tamination at shooting range soils have been rapidly raised. In 1993, Pb residues in shooting range soils were defined as hazardous materials by the United States Court of Appeals (USCA), the Resource Conservation and Recovery Act (RCRA) (USEPA 2001). However, no strict regulation has been implemented in most of the countries.

14.1.3 Environmental Management Practices (EMPs)

A potential risk from contaminated shooting range soils needs to be managed by range owners cooperated with a trained specialist under controls of regulatory au-thorities and environmental management practices (EMPs). The EMPs mainly fo-cus on (i) recycling of used ammunition, (ii) prevention of groundwater and surface water contaminations by Pb, (iii) removal and recycling of Pb from a backstop, and (iv) remediation of shooting range soils which are contaminated with heavy metals (Cohen 2000; FDEP 2004). Investigation of shooting range soils should be periodi-


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cally implemented following Fig. 14.2 (FDEP 2004). In addition, the prevention of Pb migration into the soils by means of the immobilization or stabilization is the most essential part of remediation procedure (Ok et al. 2010a, 2011a). Physical removal of Pb from a backstop and exploration of its alternative such as steel (Fe compound), tungsten (W), and tin (Sn) have been suggested; however, these re-mediation managements require additional safety and preceded verification (FDEP 2004).

14.2 Remediation of Shooting Ranges Soil

Concentration of Pb in shooting range soils usually exceeds 1% due to the weather-ing of used Pb bullets (Levonmäki et al. 2006). Indeed, the analytical results com-monly showed > 20% Pb concentration in shooting range soils (Dermatas et al. 2006a; Lin 1996). The Pb may not be biologically degraded whereas it can readily be transformed into oxidation states or organic complexes (Garbisu and Alkorta 2001).

14.2.1 Soil Characteristics and Remediation Technologies

At a shooting range, soil physiochemical properties should be considered for the selection of a proper remediation technique. Soil pH is an important soil charac-teristic that can be mostly affecting the bioavailability of heavy metals (Jin et al. 2005; Ok et al. 2007a, c). Range of optimum soil pHs in shooting range soils is from 6.5 to 8.5 because Pb may be readily reacted and became a highly mobile material under the acidic pHs < 6.5 (Cao et al. 2003a) or alkaline pHs > 8 thereby inducing the rapid weathering of Pb in contaminated shooting range soils (USEPA 2001).

Fig. 14.2 Environmental management practices (EMPs) at outdoor shooting ranges (FDEP 2004)

EMPs at Shooting Range

Site Characterization

Physical Characteristics

• Range Size• Soil Characteristics• Annual precipitation / soil erosion• Topography• Groundwater / surface water• Vegetation

Management Techniques

Bullet and ShotContainment

• Earthen Berms• Sand Traps• Steel Traps• Rubber Granule Traps

Prevention of PbMigration

• Immobilization of Pb• Monitoring and adjusting soil pH• Controlling runoff

Pb Removal andRecycling

• Hand Raking• Sifting & Screening• Soil Washing• Soil Flushing• Wet Screening• Gravity Separation• Pneumatic Separation• Phytoremediation• Vacuuming

Pb ShotAlternatives

• Tin• Steel• Iron• Tungston• Bismuth

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Some anionic ligands, especially phosphate (PO3−4 ) and carbonate (CO2−

3 ), are very effective in controlling Pb solubility because of the formation of less soluble forms which are stimulating Pb stabilization. Soil texture and SOM content are also criti-cal factors for heavy metal remediation. Soils which have high clay and silt contents may have difficulty to extract heavy metals because these can be easily absorbed by iron-manganese oxide (Fe-Mn oxide) at soil particle surface. Moreover, specific site conditions such as bedrock appearance, large boulder clay, soil moisture con-tent, and oily patch should be considered for the selection of proper remediation practices (Evanko and Dzombak 1997).

Excavation is a physical removal of surface soil contaminated with heavy metals and reburial in special landfills (Conder et al. 2001; Jing et al. 2007; Lanphear et al. 2003). This ex-situ technique is often used for closed or inactive shooting ranges. Sorvari et al. (2006) reported that > 90% of shooting range soils in Finland has been remediated by the excavation management practice. Contaminants from shooting range soils can be permanently removed; however, the excavation practice is too costly and produces the secondary environmental problems such as loss of biota or habitat, and dust pollution.

Soil washing is an ex-situ technique to remediate the soils contaminated with heavy metals (Khan et al. 2004; Peters 1999). Basically, the soil washing technique isolates contaminants from soils using water. A mixture of water and synthesized complex agents such as ethylendiaminetetraaceticacid (EDTA) and nitrilotriacetate (NTA) is occasionally used to enhance the removal ability of heavy metals from soils (Arwidsson et al. 2010; USEPA 1991). As a remediation technique at shooting ranges, advantages of soil washing technique have been reported by Fristad (2006) and Lin et al. (2001). Lin et al. (2001) found that > 0.15 mm metallic Pb particles are effectively removed by gravity separation and the solution of sodium chloride (NaCl) with sodium hypochlorite (NaOCl) as an oxidant is an effective way to re-move < 0.15 mm metallic Pb particles from the soils. However, this technique may generate the secondary environmental pollution and is not effective on soils having high clay and SOM contents.

Electrokinetic remediation is an in-situ technique using a direct current with low voltage into the soil. Once applying electricity into contaminated soils, heavy met-als migrate to electrode chamber by the electromigration reaction (Cang et al. 2009). Solution or water can be used to enhance the electromigration reaction (Smith et al. 1995). Braida et al. (2007) conducted a remediation experiment using a 30 V abso-lute voltage at contaminated shooting range soils. They found that heavy metals of W, Cu, and Pb in shooting range soils are effectively removed or stabilized; how-ever, the effectiveness of electrokinetic remediation depends on soil bulk density, soil particle size, and heavy metal mobility in soils.

Phytoremediation is an in-situ technique using specific plant species to extract heavy metals from contaminated soils, which is also known as phytoextraction (Bennett et al. 2003; Ok and Kim 2007), or to physically stabilize contaminated soils adjacent to the aboveground root system, as also known as phytostabilization (Jing et al. 2007). Wilde et al. (2005) showed that the use of Vetiver grass combined


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with chelating agents (EDTA) is a well suited remediation technique for shooting ranges soils. Hashimoto et al. (2008) found that the use of proper plant species with poultry waste as an immobilizing agent reduces Pb leaching and enhances the stabi-lization of Pb in shooting range soils.

Stabilization/Solidification (S/S) technique chemically stabilizes and physical-ly encapsulates heavy metal contaminants in the soils (Cao et al. 2008; Ok et al. 2010b). The heavy metals can be transformed into less soluble forms using the S/S technique, thereby reducing a potential health risk. The S/S technique induces physical heavy metal encapsulation in a solid matrix using a pozzolanic solidifica-tion system or using chemical additives (Cao et al. 2008). Applications of P, zeolite, lime, and Fe-Mn oxides have been considered to stabilize Pb in shooting range soils (Alpaslan and Yukselen 2002; Ma et al. 1995). Solidification of Pb using lime-based materials and the formation of crystalline phases (less soluble forms) which are involved in the stabilization of Pb can be effective ways as one of the S/S re-mediation techniques (Cao et al. 2008; Moon et al. 2010). For the formation of crystalline phases, the reaction of calcium hydroxide (CH; Ca[OH]2) and silicic acid (SH; [SiOx(OH)4−2x]n) is required to produce calcium silicate hydrate (CSH; CaH2SiO2.2H2O) and calcium aluminate hydrate (CAH; CaOAl2O3.10H2O) as so-lidification process. The Pb can also be precipitated as a metal hydroxide (OH−) un-der the alkaline pH condition associated with cementitious lime materials, thereby reducing the Pb bioavailability (Moon and Dermatas 2006; Palomo and Palacios 2003). To ensure the effectiveness of S/S technique, sequential or ascertaining ex-traction tests are commonly used (Ruby et al. 1996; Ryan et al. 2001).

14.3 Remediation of Shooting Range Soils Using Lime-Based Waste Materials

Soils contaminated with heavy metals pose a potential threat to the environment. In recent, exploration of cost-effective remediation techniques has received increased attention. The S/S techniques were recommended as the Best Demonstrated Avail-able Technology (BDAT) by the USEPA and are being widely used at contami-nated soils with heavy metals (Singh and Pant 2006). To accomplish stabilization or immobilization, several soil amendments were commonly used to contaminated soils for its remediation, revitalization, or recycle. Soil amendments are achieved from various sources of natural materials, industrial or agricultural by-products, and artificial or synthetic materials. Recently, the use of a natural or waste material is highlighted as a cost-effective and friendly-environmental remediation method (Guo et al. 2006).

The biologically available fraction of metal can be taken up by organisms de-pending on metabolic activities and metal bioavailability (Geebelen et al. 2003). Soil amendment may reduce the bioavailability of metals in the soils by immo-bilization. Factors such as cation exchange, adsorption, precipitation, and surface complexation mainly influence on the metal immobilization in the soils (Chen et al.

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2009; Guo et al. 2006; Kumpiene et al. 2008). However, different mobilities of metals and distinct organism speciation in the soils indicate difficulty to determine an appropriate soil amendment for simultaneously immobilizing various metals. Therefore, the exploration and selection of cost-effective and suitable soil amend-ments are critical to success.

14.3.1 Lead Immobilization Using Waste Materials

Most shooting range soils are contaminated by Pb which is contained in used bullets through its weathering and transformation. Toxicity of Pb has been well known as one of the adverse heavy metals on human health and environment. With this reason, several approaches using waste materials have been suggested to stimulate the Pb immobilization in contaminated soils. Different waste materials have been applied

Table 14.3 Different waste materials to immobilize lead (Pb) in contaminated soilsWaste material Source Reference

Red mud Waste alumina industry Lee et al. (2009)Garau et al. (2007)Brown et al. (2005)Lombi et al. (2002)

Beringite Burning of coal refuse Lombi et al. (2002)Cyclonic ash Burning of coal refuse Brown et al. (2005)

Geebelen et al. (2003)Fly ash Coal fired power stations

Flue gas desulfurizing productCiccu et al. (2003)Clark et al. (2001)

Furnace slag Steel industry waste Lee et al. (2009)Poultry waste Poultry farming industry Hashimoto et al. (2008)Dolomitic residue Steel industry waste Rodríguez-Jordá et al. (2010)

Garrido et al. (2005)Sugar foam Sugar manufacturing industry Rodríguez-Jordá et al. (2010)

Garrido et al. (2005)Waste oyster shells Oyster farming industry Ok et al. (2010a, b)

Moon et al. (2010)Lim et al. (2009)

Waste eggshell Food waste Lim et al. (2009)Steel shot Steel-iron industry waste Geebelen et al. (2003)Water and wastewater Treatment Residue Water and

wastewater treatment plantsSpuller et al. (2007)Brown et al. (2005)

Red gypsum TiO2 industry waste Rodríguez-Jordá et al. (2010)Garrido et al. (2005)

Phosphogypsum Production of phosphoric acid from rock phosphate

Rodríguez-Jordá et al. (2010)Garrido et al. (2005)


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to soils for the Pb immobilization as shown in Table 14.3. Natural alkaline materials such as red mud, beringite, cyclonic ash, fly ash, furnace slag, poultry waste, dolo-mitic residue, sugar foam, waste oyster shell, and eggshell generally increase soil pH; therefore, these materials reduce Pb solubility in the soils. Lindsay (1979) found that Pb can be precipitated as OH− at pH 8 and became a less bioavailable form. Sorption of Pb to soil particles is also increasing at high soil pH because of an increase in a net negative charge of colloidal particles such as clay, SOM, and Fe-Al oxides (Lee et al. 2009). This review focuses on the use of waste materials or industrial by-products for stabilizing Pb in shooting range soils and evaluates their effectiveness.

14.3.2 Use of Lime-Based Waste Materials

The S/S technique using P has been considered as an effective way to remediate Pb in shooting range soils. However, the overuse of P may induce the secondary environmental pollution like eutrophication resulting from leaching of excess P and extremely slow reaction between Pb and P (Dermatas et al. 2008). Use of lime-based waste materials is an emerging remarkable way to remediate heavy-metal-contaminated soils with advantages of cost and time. Ok et al. (2010a) found that the use of oyster shell waste effectively remediates Cd and Pb in the soils, and used oyster shells as a source of CaCO3 for immobilizing heavy metals as shown below:

Ok et al. (2010b) also suggested that a form of calcium oxide (CaO) or quick lime which is obtained from the calcination of CaCO3 at a high temperature (900ºC) may increase the efficiency of waste oyster shell on heavy metal remediation in the soils:

The CaO can effectively immobilize Pb and Cd in the soils because of pozzolanic reactions compared to CaCO3. Formation of CAH or CSH by CaO in the soils re-sults in hardening of soil particles, thereby reducing the bioavailability of metals (Kostarelos et al. 2006). Moon et al. (2010) applied both calcined and uncalcinated oyster shell to highly contaminated shooting range soils indicating 29,000 mg kg–1 Pb and found that the calcined oyster shell material has a higher Pb immobilization rate because of the formation of CAH or CSH at high soil pHs.

14.4 Conclusion

Lime-based waste materials such as eggshell, oyster shell and mussel shell are eas-ily accessible in our surrounding. More than 100,000 tons of oyster shell and 50,000 tons of eggshell are being annually generated in Korea (Lee et al. 2005; Ok et al.

CaCO3 + H2O → Ca2+ + HCO3− + OH−

M + OH− → M − OH

CaCo3 + heat → Cao + Co2

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2011b; Palka 2002). Recycling or reuse of such waste materials promises to not only reduce environment pollution but also be a cost-effective way to remediate the shooting range soils which are highly contaminated with heavy metals. Fur-thermore, the exploration or evaluation of lime-based waste materials would be a valuable study to select an appropriate remediation material depending on heavy metal contaminants. Longevity of lime-based waste materials or their additional advantages of plant growth also needs to be addressed in the future.

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