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Testing amendments for remediation of military range contaminated soil Grzegorz Siebielec a, * , Rufus L. Chaney b a Institute of Soil Science and Plant Cultivation e State Research Institute, Czartoryskich 8, 24-100 Pulawy, Poland b USDA e Agricultural Research Service, EMBUL, Beltsville, MD 20705, USA article info Article history: Received 20 May 2011 Received in revised form 12 April 2012 Accepted 20 April 2012 Available online xxx Keywords: Bioaccessibility Compost Lead Military range Phytotoxicity Zinc abstract Military range soils are often strongly contaminated with metals. Information on the effectiveness of remediation of these soils is scarce. We tested the effectiveness of compost and mineral treatments for remediation and revegetation of military range soil collected in Aberdeen, MD. The soil was barren due to zinc (Zn) phytotoxicity while lead (Pb) posed a substantial risk to soil biota, wildlife and humans through various pathways. Seven treatments were tested: untreated control, agricultural NPK fertilization, high phosphate fertilization plus agricultural rates of NK, CaCO 3 , Orgrobiosolid compost, Orgroþ CaCO 3 , Orgroþ CaCO 3 þ Mn sulfate. All compost treatments alleviated Zn phytotoxicity to tall fescue; however compost combined with liming reduced plant Zn content up to 158e162 mg kg 1 . Compost added with lime reduced Pb in-vitro bioaccessibility from 32.5 to 20.4% of total Pb and was the most effective among the tested treatments. The study revealed the effectiveness of biosolids compost and lime mixture in the rapid stabilization of metals and revegetation of military range contaminated soils. The persistence of the remediation needs to be, however, conrmed in the long-term eld study. Ó 2012 Elsevier Ltd. All rights reserved. 1. Introduction Military range soils may pose serious environmental risks related to their contamination with metals and various groups of organic compounds. The contaminants persist in soil being toxic to soil biota and wildlife or are leached out to the groundwater. The limited number of military site assessments available makes the existing data rather scarce in terms of level, complexity of contamination and effective methods to alleviate the risk. There are several articles available describing contamination of shooting ranges used for sport or hunting. Lead is a major component of bullets; therefore such sites are often heavily contaminated with Pb, depending on the intensity of shooting and operating timeframe (Chen et al., 2000; Dermatas et al., 2006; Murray et al., 1997). According to a Murray et al. survey (1997) in most of the investigated US shooting sites Pb content in soil exceeds 1000 mg kg 1 . The content of Pb in soils of the shooting site in Central Florida ranged from 330 to 17,850 mg kg 1 depending on the distance from shooting stands (Chen et al., 2000). Contamination of long-term military sites is more complex. The list of other potential contaminants is long since it may also include other metals and such compounds as 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive, RDX) or octahydro-1,3,5,7-tetranitro,1,3,5,7-tetrazocine (High Melting Explosive, HMX) (Ryu et al., 2007). According to Bannon et al. (2009), Pb is a major metal contaminant for small range arms in the U.S., as its total soil content ranged between 4500 and 24,480 mg kg 1 across the 8 sites investigated, whist copper ranged from 220 to 2900 mg Cu kg 1 . Lead originating from bullets is subjected to transformations in soil. Dermatas et al. (2006) found Pb in metallic, oxide and carbonate form (e.g. hydrocerrusite e Pb(CO 3 ) 2 (OH) 2 ) in a shooting site soil. Hydrocerrusite is present in weathering bullet residues and in soil under alkaline pH (Cao et al., 2003). Cao et al. (2003) also reported the presence of hydroxypyromorphite [Pb 10 (PO 4 ) 6 (OH 2 )], which is one of the most stable forms of Pb. Lewis et al. (2001) documented a risk of Pb toxicosis for wildlife foraging within shooting range zones, conrmed by elevated Pb concentrations in the kidneys and livers of birds and mammals. The elevated risk can be attributed to animals with small-size foraging ranges and eating earthworms such as the American robin and short-tailed shrew (Bennett et al., 2007). A study of Bannon et al. (2011) showed a clear relationship between the dose of Pb contaminated soil from a small arms-range and Pb concentration in the soft tissues of pigeons fed with the soil for 14 days. Knowledge on remediation attempts aimed at reducing metal bioavailability in contaminated soils of military sites is scarce. Dermatas et al. (2008) claimed limited effectiveness of monobasic calcium (Ca) phosphates in the reduction of Pb leaching and formation of insoluble Pb compounds whereas Wilson et al. (2006) * Corresponding author. Tel.: þ48 81 8863421x325; fax: þ48 81 8864547. E-mail address: [email protected] (G. Siebielec). Contents lists available at SciVerse ScienceDirect Journal of Environmental Management journal homepage: www.elsevier.com/locate/jenvman 0301-4797/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.jenvman.2012.04.028 Journal of Environmental Management 108 (2012) 8e13
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Testing amendments for remediation of military range contaminated soil

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Page 1: Testing amendments for remediation of military range contaminated soil

at SciVerse ScienceDirect

Journal of Environmental Management 108 (2012) 8e13

Contents lists available

Journal of Environmental Management

journal homepage: www.elsevier .com/locate/ jenvman

Testing amendments for remediation of military range contaminated soil

Grzegorz Siebielec a,*, Rufus L. Chaney b

a Institute of Soil Science and Plant Cultivation e State Research Institute, Czartoryskich 8, 24-100 Pulawy, PolandbUSDA e Agricultural Research Service, EMBUL, Beltsville, MD 20705, USA

a r t i c l e i n f o

Article history:Received 20 May 2011Received in revised form12 April 2012Accepted 20 April 2012Available online xxx

Keywords:BioaccessibilityCompostLeadMilitary rangePhytotoxicityZinc

* Corresponding author. Tel.: þ48 81 8863421x325E-mail address: [email protected] (G. Siebielec).

0301-4797/$ e see front matter � 2012 Elsevier Ltd.doi:10.1016/j.jenvman.2012.04.028

a b s t r a c t

Military range soils are often strongly contaminated with metals. Information on the effectiveness ofremediation of these soils is scarce. We tested the effectiveness of compost and mineral treatments forremediation and revegetation of military range soil collected in Aberdeen, MD. The soil was barren due tozinc (Zn) phytotoxicity while lead (Pb) posed a substantial risk to soil biota, wildlife and humans throughvarious pathways. Seven treatments were tested: untreated control, agricultural NPK fertilization, highphosphate fertilization plus agricultural rates of NK, CaCO3, “Orgro” biosolid compost, “Orgro” þ CaCO3,“Orgro” þ CaCO3 þMn sulfate. All compost treatments alleviated Zn phytotoxicity to tall fescue; howevercompost combined with liming reduced plant Zn content up to 158e162 mg kg�1. Compost added withlime reduced Pb in-vitro bioaccessibility from 32.5 to 20.4% of total Pb and was the most effective amongthe tested treatments. The study revealed the effectiveness of biosolids compost and lime mixture in therapid stabilization of metals and revegetation of military range contaminated soils. The persistence of theremediation needs to be, however, confirmed in the long-term field study.

� 2012 Elsevier Ltd. All rights reserved.

1. Introduction

Military range soils may pose serious environmental risksrelated to their contamination with metals and various groups oforganic compounds. The contaminants persist in soil being toxic tosoil biota and wildlife or are leached out to the groundwater. Thelimited number of military site assessments available makes theexisting data rather scarce in terms of level, complexity ofcontamination and effective methods to alleviate the risk.

There are several articles available describing contamination ofshooting ranges used for sport or hunting. Lead is a majorcomponent of bullets; therefore such sites are often heavilycontaminated with Pb, depending on the intensity of shooting andoperating timeframe (Chen et al., 2000; Dermatas et al., 2006;Murray et al., 1997). According to a Murray et al. survey (1997) inmost of the investigated US shooting sites Pb content in soil exceeds1000 mg kg�1. The content of Pb in soils of the shooting site inCentral Florida ranged from 330 to 17,850 mg kg�1 depending onthe distance from shooting stands (Chen et al., 2000).

Contamination of long-term military sites is more complex. Thelist of other potential contaminants is long since it may also includeother metals and such compounds as 2,4,6-trinitrotoluene (TNT),hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive,

; fax: þ48 81 8864547.

All rights reserved.

RDX) or octahydro-1,3,5,7-tetranitro,1,3,5,7-tetrazocine (HighMelting Explosive, HMX) (Ryu et al., 2007). According to Bannon et al.(2009), Pb is a major metal contaminant for small range arms in theU.S., as its total soil content rangedbetween4500and24,480mgkg�1

across the 8 sites investigated, whist copper ranged from 220 to2900 mg Cu kg�1.

Lead originating from bullets is subjected to transformations insoil. Dermatas et al. (2006) found Pb in metallic, oxide andcarbonate form (e.g. hydrocerrusite e Pb(CO3)2(OH)2) in a shootingsite soil. Hydrocerrusite is present in weathering bullet residuesand in soil under alkaline pH (Cao et al., 2003). Cao et al. (2003) alsoreported the presence of hydroxypyromorphite [Pb10(PO4)6(OH2)],which is one of the most stable forms of Pb.

Lewis et al. (2001) documented a risk of Pb toxicosis for wildlifeforaging within shooting range zones, confirmed by elevated Pbconcentrations in the kidneys and livers of birds andmammals. Theelevated risk can be attributed to animals with small-size foragingranges and eating earthworms such as the American robin andshort-tailed shrew (Bennett et al., 2007).

AstudyofBannonetal. (2011)showedaclearrelationshipbetweenthe dose of Pb contaminated soil from a small arms-range and Pbconcentration in thesoft tissuesofpigeons fedwith thesoil for14days.

Knowledge on remediation attempts aimed at reducing metalbioavailability in contaminated soils of military sites is scarce.Dermatas et al. (2008) claimed limited effectiveness of monobasiccalcium (Ca) phosphates in the reduction of Pb leaching andformation of insoluble Pb compounds whereas Wilson et al. (2006)

Page 2: Testing amendments for remediation of military range contaminated soil

Table 2The treatments of the Aberdeen soil.

Treatment Amendments (dose pot�1) Equivalent per area unit(kg ha�1)a

Control e e

NPK 56.3 mg N 15056.3 mg P 15056.3 mg K 150

High P 56.3 mg N 150187.5 mg P 50056.3 mg K 1501.88 g CaCO3 5000

Orgro 84.4 g compost DM 225,00028.1 mg K 75

CaCO3 18.75 g CaCO3 50,00056.3 mg N 15056.3 mg P 15056.3 mg K 150

Orgro þ CaCO3 84.4 g compost DM 225,00018.75 g CaCO3 50,000

G. Siebielec, R.L. Chaney / Journal of Environmental Management 108 (2012) 8e13 9

demonstrated a reduction of Pb solubility and improvement ofmicrobial activity after amending shooting range soil with apatites.

An urgent task is to reduce the environmental risk related tomilitary contaminated sites e some of them are barren whichpromotes metal leaching and erosion driven transport. Suchmaterials as composts, biosolids, phosphate fertilizers or limestonehave been tested and documented as effective in the stabilization oftrace metals in contaminated soils (Vangronsveld et al., 1996;Chaney et al., 2000; Basta et al., 2005; Siebielec et al., 2007). Theeffectiveness of such methods for military range soils is uncertainsince they have not been tested for that type of contamination toany wider extent. Metals in such soils might be present in differentforms and mixtures and soils are often strongly infertile which mayinfluence remediation effects.

The aim of this workwas to test the effectiveness of compost andmineral treatments for remediation of military range contaminatedsoils measured by plant reaction and metals extractability.

28.1 mg K 75Orgro þ CaCO3 þ Mn 84.4 g compost DM 225,000

18.75 g CaCO3 50,00028.1 mg K 7537.5 mg Mn 100

a Assuming 2000 t of soil DM hectare�1.

2. Materials and methods

2.1. Experimental procedure

The soilwas collected from the 0e15 cm layer of amunitions burnpit pushout areaofAberdeenProvingGroundeAberdeenArea (APG-AA) located in Maryland, U.S. The ash from burned munitions wasspreadaroundcausing contaminationof soils adjacent to the pits. Thesite was deemed “hazardous” by US-EPA due to the high metalscontent andbarrencondition.TheUSArmyestablished theAPG-AAasthe Ordinance Proving Ground in 1917. The facility, which to a certainextent remains active today, has been used by the Army for research,development and field testing of munitions and weapons since 1918.An ecological risk assessment performed for the so-called J-Field siteby Hlohowskyj et al. (2000) involved a number of risk pathways. Thehighest environmental riskwas posed by tracemetals. Toxicity to soilbiota and vegetation was evident, especially at the push out area.

The aqua-regiahotdigestionmethod (McGrath andCunliffe,1985)revealed extreme soil contamination with Pb e 10,300 mg kg�1. Thesoil was substantially contaminated with Zn which makes the sitesomewhat different from the firing range soils surveyed by Bannonet al. (2009) (Table 1). Despite neutral pH (pH 6.9, measured in the1:2 w/v, soil-water slurry) the soil was phytotoxic when untreated asbased on a short growth test with tall fescue, likely due to Zncontamination.

The soil was a sandy loam with a total C content of 2.1% asmeasured using a CNS combustion analyzer (Leco Corp.). Soilparticles size distribution was measured by hydrometer method(Gee and Bauder,1986). The test was conducted in 1 L plastic pots inthree replicated blocks in a greenhouse with a 16 h light period.Day/night temperatures were 27 �C/20 �C. The pots contained 750 gof air dry soil sieved through 2 mm mesh. The soil was treated in 7different ways: untreated control, agricultural NPK fertilization,high phosphate fertilization plus normal rates of NK, CaCO3,“Orgro” biosolid compost, “Orgro” þ CaCO3 and “Orgro” þ CaCO3with the addition of Mn sulfate (to avoid Mn deficiency).A summary of the soil amendments is presented in Table 2.

Table 1The selected properties of the Aberdeen soil.

pH 6.9C (g kg�1) 21.0Total Zn (mg kg�1) 7200Total Pb (mg kg�1) 10,300Total Cd (mg kg�1) 5.7Total Cu (mg kg�1) 910Total Mn (mg kg�1) 240

Mineral fertilizers were added to all pots except the controltreatment: phophorus (P) and potassium (K) as a solution ofK2HPO4, nitrogen (N) as a solution of Ca(NO3)2, and the rest of the Pdose as solid reagent grade (CaHPO4).

The high phosphate treatment pots that received a substantialamount of CaHPO4 (187.5 mg of P) as equivalent of 500 kg ha�1

were treated with 1.88 g CaCO3 in order to counteract the pH shift.The high phosphate treatment was used to test for an agricultural Prate sufficient enough to avoid P deficiency in plants grown on soilnot fertilized for decades and the potential contribution of this rateto reducing Pb bioavailability.

“Orgro” was a high organic (70% organic matter), iron (3.6% Fe)and phosphorus (1.85% P) compost manufactured at the BaltimoreCity Composting Facility using unlimed biosolids as feedstock. Thecompost was added at the rate of 84.4 g of dry matter per pot in allcompost combinations as equivalent of 225 Mg ha�1. This amountwas equal to the rate successfully applied by Li et al. (2000) toextremely contaminated soil in Palmerton, PA.

Ca-carbonate was a powder reagent and was added to all CaCO3treatments at the rate of 18.75 g per pot as an equivalent of50 tons ha�1 to make the soil calcareous. Such high rates of lime arerecommended to counteract future pH decrease and reduce risk forrelated metals re-mobilization. Compost treated soils did notreceive P and N mineral fertilizers due to the high content of thesenutrients in the compost while K fertilizationwas reduced to half ofthe dose applied to non-compost treatments.

Manganese (Mn)was addedonly to the “compostþCaCO3þMn”combination as a solution ofMn sulfate at the rate 37.5 g per pot, theequivalent of 100 kg Mn ha�1.

The amendments were mixed with the soil in plastic bags andtransferred to the pots. All pots were watered to approximately 70% ofthe field water capacity and soil incubated for 7 days to allow amend-ments to equilibrate with the soils prior to crop establishment. Soilswere then mixed thoroughly before seeding plants. “Houndog” tallfescuewas grown for 7weeks. Potswerewatered during plant growthwith deionizedwater as needed to keep themoisture at constant level.

2.2. Soil and plant analysis

After harvest plant tissues were washed in DI water, dried in anoven (65 �C), weighed to record yield and ground. Plant material

Page 3: Testing amendments for remediation of military range contaminated soil

Fig. 2. The effect of different treatments on yield of tall fescue grown on Aberdeen soil.Different letters above the bars indicate significant differences between the treatmentsaccording to the Tukey’s test with P < 0.05. The whiskers represent standard deviationfor 3 replications.

G. Siebielec, R.L. Chaney / Journal of Environmental Management 108 (2012) 8e1310

was then ashed in a muffle oven at 480 �C for 16 h, and digested inconcentrated HNO3 followed by refluxing with 3 M HCl andfiltering. National Institute of Standards and Technology (NIST)standard reference material 1573a tomato leaves was used tocontrol the quality of the procedure. Standards were run every 20plant samples and blanks every 10 samples. Filtrates were analyzedby ICP-AES (inductively coupled plasma atomic emission spec-trometer) with yttrium as an internal standard for P, K, Ca, Mg, Mn,Cu, Fe, Zn, Pb and Cd.

After the removal of roots, the soil from the potswasmixed beforecollecting samples for analysis; samples were then air dried, crushedand homogenized for analysis. Extractable metals were analyzed bystrontium nitrate extraction procedure e 20 mL of 0.01 M Sr(NO3)2solution per 10 g of dry soil shaken for 2 h (Madden, 1988). Final pHwas measured in the 1:2 soil-water slurry after 1 h incubation.

An in vitro bioaccessibility test was designed to measure thefraction of soil Pb extractable under simulated gastric conditions asan alternative to expensive and time-consuming animal feedingstudies (Ruby et al., 1993). Different extraction procedures havebeen proposed in literature consisting with one gastric phase ortwo phases (gastric and intestinal) (Ruby et al., 1993; Oomen et al.,2003; Juhasz et al., 2009). We measured bioaccessible Pb in 2 mmsieved samples using a simplified method e gastric solutionconstituted with 0.4 M glycine adjusted to pH 2.2 with HCl. The 1 gsoil samples were shaken (30 rpm) in a HDPE bottles with 100 mLof the solution for 1 h at 37 �C. After shaking the extract was filteredthrough membrane filters with a 10 mL syringe and analyzed withAAS for Pb concentration.

2.3. Statistical analysis

Statistical testing involved the General Linear Models procedureused for analyses of variance and Tukey test to separate significantlydifferent means. The data was analyzed using Statistica software.

3. Results and discussion

3.1. Plant Performance

Performance and growth of tall fescue were strongly affected bythe tested treatments. In the control soil the plants showed severelyreduced growth and intensive chlorosis (Fig. 1). Regular NPKfertilization and the phosphate treatment slightly increased theyield but did not allow healthy growth of plants. Liming reducedvisible toxicity symptoms (chlorosis) but did not ensure higheryield (Fig. 2), which might be indicative of a disturbed metabolism

Fig. 1. Tall fescue growth on Aberdeen soil depending on the treatment used e fromthe left: untreated control, agricultural NPK fertilization, high phosphate fertilizationplus normal rates of NK, CaCO3 powdered reagent, “Orgro” biosolid compost,“Orgro” þ CaCO3, “Orgro” þ CaCO3 þ Mn.

of P (Boawn and Rasmussen, 1971). Plants looked healthy in allcompost treatments, without significant differences in yieldbetween “Orgro”, “Orgro þ CaCO3” and “Orgro þ CaCO3 þ Mn”combinations (Figs. 1 and 2). Examples of compost or biosolidseffectiveness in plant establishment on barren metal contaminatedsoils are provided by the works of Li et al. (2000); Brown et al.(2003b) or Stuczynski et al. (2007). Such hindrances as metaltoxicity, soil infertility andweakwater retentionmight be erased bythe organic treatments when properly applied. High rates oforganic materials (composts, biosolids) substantially improvecation exchange capacity and water holding capacity of the soil andprovide nutrients and microbial inoculum.

Zinc was definitely toxic to plants in control, NPK and high-Ptreatments. Liming and compost applications reduced Zn uptakebelow toxicity level with “Orgro þ lime” treatment being the mosteffective (Table 3). Zinc is generally toxic for most crop plants andPoaceae species when its plant content reaches 400e500 mg kg�1

(Boawn and Rasmussen, 1971; Chaney, 1993). It is worth notingthat a significantdifference inbiomassyieldbetween limeandOrgrotreatmentswasobserveddespite similar Zn contents inplant shoots.This might likely be attributed to a sufficiency of such nutrients as P,Mn or K in plants on soil fertilized with the compost. Liming asa single treatment inducedmilddeficienciesof these elements as theeffect of pH shift from 6.9 (control) to 8.2 (Tables 3 and 4).

Despite the fact that Orgro compost alleviated Zn toxicity andenabled plant growth, it is recommended to apply composts to suchcontaminated soils alongwith limestone. Organic fertilizers appliedat high rates will generate acidification processes related to organicmatter decomposition over time. In our study the Ca-carbonateapplication with compost reduced plant Zn to 158 and162mgkg�1 compared to357mgkg�1 inOrgro treated soil (Table 3).

Zinc phytotoxicity symptoms are often attributed to Zn-induceddeficiencies of P. They might result from inhibition of root length orprecipitation of Zn-phosphate in root cells (Boawn and Rasmussen,1971; Chaney, 1993). P content in plant tissue was low for all amend-ments, excepthighphosphateandcompost-alone treatments (Table2).The soil had not been fertilized with P for many years before the soilmaterialwascollected for thispot study.PrecipitationofweaklysolubleCa-phosphates under alkaline soil pH may have contributed to low Puptake in all limed soils. Using a compost-lime combination forremediation of such soil inpracticemight require P fertilizationdespitethe fact that Orgro introduces a substantial amount of P.

Page 4: Testing amendments for remediation of military range contaminated soil

Table 3Composition of tall fescue shoots (mg kg�1) grown on Aberdeen soil amended with different materials.

Treatment P K Ca Mg Mn Fe Cu Zn Pb Cd

Control 1878aa 13,370d 7024ab 8552b 34.2b 211a 23.2ab 805a 159a 1.54aNPK 1626a 16,277cd 7246a 8762b 20.4bc 161ab 26.6a 708a 135ab 1.23aP 1958a 16,666cd 6956ab 9378b 17.4c 130ab 25.8a 562b 111ab 0.99abCaCO3 1605a 17,376cd 3175c 11995a 20.1bc 140ab 26.7a 318c 84.7bc 0.30bOrgro 2128a 26,209a 5972b 5843c 62.9a 62.6b 15.8bc 357c 49.1cd 1.11abOrgro þ CaCO3 1625a 22,910ab 3755c 8725b 18.5bc 52.5b 10.9c 158d 23.9d 0.32bOrgro þ CaCO3 þ Mn 1786a 20,568bc 3751c 8616b 28.4bc 55.8b 10.4c 162d 22.7d 0.28b

a Means followed by different letters are significantly different between the treatments according to the Tukey’s test with P < 0.05.

G. Siebielec, R.L. Chaney / Journal of Environmental Management 108 (2012) 8e13 11

Iron deficiency symptoms are common in plants grown on Zncontaminated soils (Chaney,1993). Themeasured Fe shoot contentswere not deficient for either treatment and the lowest contentswere detected in “Orgro” treatments (Table 2). However, even if Fecontent in shoots is not at a deficient level, Zn might interfere withFe in leaves, hampering chlorophyll biosynthesis (White et al.,1979; Chaney, 1993).

Potassium content was likely deficient in plants on control soiland low in other mineral treatments which can be attributed toroot conditions and/or deficient K content in soil. The K content inshoot DM increased above 2% after compost treatment. Ca in plantswas the lowest in limed soils as a result of pH increase. Magnesium(Mg) was not deficient regardless of the treatment (Table 2).

Manganese deficiencies in plants grown on soils fertilized withhigh rates of compost or biosolids combined with limestone havebeen observed (Brown and Chaney, 1998). In our study compostapplied as single amendment resulted in the highest Mn content ingrasses among all treatments. Mn content in tall fescue shootsgrown in “Orgro þ lime” combination did not drop below15 mg kg�1 DM, which is the indicative level for Mn deficiency inmost plant species (Römheld and Marschner, 1991). However, Mnwas low in all pots that received CaCO3 which suggests a risk of Mndeficiency in this soil when high rates of limestone are appliedunder field conditions (Table 3). Soil pH shift from 6.9 to above 7.8after liming results in reduction in soil Mn phytoavailability. Soilfertilization with Mn sulfate had no influence on plant Mn.

Cadmium (Cd) uptake was not high even in control soil (shootscontent 1.5 mg kg�1) which is attributed to its relatively low totalcontent and neutral pH of soil. Thus this element does not posea risk for wildlife in this area.

Lead content was high in plant tissues on untreated soil(Table 3). We assume that the type of Pb contamination and, inconsequence, Pb speciation might be responsible for the greaterphytoavailability of the element. The high accumulation of Pb inplants grown on military land soils have been observed by otherresearchers (Cao et al., 2003; Bennett et al., 2007). Liming andOrgro treatments significantly reduced shoot Pb concentration;however, compost combined with Ca-carbonate lowered plant Pbfrom 159 up to 24 mg kg�1 (Table 3).

Table 4Aberdeen soil properties as a result of the tested treatments after the harvest (meansand standard deviations are provided).

Treatment pH Sr-nitrate extractable metals (mg kg�1)

Zn Cd Pb

Control 6.90 � 0.17ca 21.8 � 2.18a 0.058 � 0.017a 0.93 � 0.12aNPK 6.93 � 0.13c 15.2 � 2.30b 0.043 � 0.010a 0.47 � 0.10bP 7.40 � 0.09bc 2.03 � 0.43c 0.011 � 0.002b 0.02 � 0.00cCaCO3 8.22 � 0.07a 0.31 � 0.06c 0.002 � 0.000b 0.02 � 0.00cOrgro 7.22 � 0.07c 5.65 � 1.39c 0.011 � 0.004b 0.27 � 0.07bcOrgro þ CaCO3 7.87 � 0.04ab 0.55 � 0.14c 0.004 � 0.002b 0.02 � 0.00cOrgro þ CaCO3 þ

Mn7.87 � 0.01ab 0.39 � 0.11c 0.003 � 0.001b 0.02 � 0.00c

a Means followed by different letters are significantly different between thetreatments according to the Tukey’s test with P < 0.05.

3.2. Metals solubility

All remediation treatments significantly lowered Zn, Pb and Cdsolubility as measured by Sr-nitrate extraction (Table 4). Thischange was a result of a pH shift and/or sorption capacity increase.Zn extractability was a function of soil pH (Fig. 3) after the soilamendment with different materials. The lowest metals extract-ability was recorded for CaCO3 treatment; however, this observa-tion was not fully consistent with metals content in plants and thegrass yield (Table 3, Figs. 2, 3). Sr-nitrate extractable Pb was slightlyreduced even by NPK treatment while in all limed soils theextractable Pb was hardly detectable (Table 4).

In our study Sr-nitrate extraction underestimated Zn availabilityto plants for CaCO3- and phosphate-treated soils (Fig. 3). Suchextractions with mild solutions of neutral salts usually sufficientlypredict metals content in plants growing on different soils or thesame soil with different pH levels (Siebielec et al., 2007). Whentesting diverse treatments of the same soil, there might be somediscrepancies between extractable soil Zn and its content in plantshoots for certain soil treatments.

There are examples of successful limestone application forremediation of metals toxicity (Siebielec et al., 2007) but oftenliming as a single treatment is not effective for establishment ofplant cover on heavily Zn contaminated soils (Li et al., 2000). Theliming effectiveness may strongly depend on soil properties,contamination type and metal content. In soils with weaker sorp-tion capacity liming may fail to alleviate Zn toxicity. Furthermore,liming may induce deficiencies of macro- and microelements pre-venting full remediation of the soil.

Compost applied as single treatment secured high biomass;however, Zn solubility was significantly greater than for limed soilor compost-lime mixture. This was the result of soil pH lower by0.65 and 1.0 units than in compost-lime and lime treatments,respectively.

One of the primary pathways responsible for elevated Pb inhuman blood is direct ingestion of soil contaminated with Pb(Brown et al., 2003a). In vitro bioaccessibility measurements areaimed at predicting potential absorption of Pb when the contami-nated soil is ingested.

The level of bioaccessible Pb determined for unamended Aberdeensoil was 3198 mg kg�1, which represented 32.5% of the total Pb. Pbbioaccessibility in treated soils was not a linear function of soil pH.Liming alone and all compost treatments reduced bioavailability of Pbto a certain extent, comparing to the unamended soil, but compostappliedalongwith limegave thebest result (Fig. 4). Reductionof soil Pbbioavailability is usually associated with the presence of insoluble Pbminerals pyromorphites [Pb5(PO4)3]X (hydroxyl-, chloro-, or fluoro-pyromorphites) that are formed in the presence of phosphates (Maet al., 1993; Cotter-Howels, 1996). Thus, various forms of phosphoruswere tested as amendments aimed at immobilization of soil Pb (Maet al., 1993; Hettiarachchi et al., 2000; Basta et al., 2001; Chen et al.,2003). In our study Ca phosphate did not significantly reduce the Pbbioaccessibility, which might be attributed to the lower rate of phos-phates than those tested by other researchers. Our experiment

Page 5: Testing amendments for remediation of military range contaminated soil

Fig. 3. The relationship between soil pH and soil extractable and/or plant Zn contentfor different treatments.

G. Siebielec, R.L. Chaney / Journal of Environmental Management 108 (2012) 8e1312

confirmed the effectiveness of high-Fe and P-rich biosolids compost inreducing Pb bioavailability observed for high-Pb urban soils (Brownet al., 2003a). The mechanism for reducing Pb bioaccessibility incompost-lime treated soils is apparently a combination of Pb immo-bilization by organic matter, phosphates and Fe-oxides introduced tosoil alongwithcompost (StrawnandSparks,2000;Brownetal., 2003a).

Combiningorganic and lime amendments is a commonapproachfor remediation of industrially contaminated sitesepH increase dueto lime application increases metals adsorption on compostcomponents such as organic matter and Fe oxides (Hettiarachchiet al., 2003; Basta et al., 2005; Stuczynski et al., 2007) while phos-phates present in composts conduce precipitation of insoluble Pbcompounds. Furthermore, organic materials favor plant growth byimprovement of soil fertility, microbial activity and physical prop-erties of often abandoned and barren soils. Our study has proven theshort-term effectiveness of compost and lime combination forremediation of soils contaminated by military activities. The higherrates of compost would not be recommended due to a risk ofexcessive N release to groundwater whereas the tested limestonerate was sufficient to make the soil calcareous. Further reduction ofmetals solubility and uptakemight be achieved through progressiveadsorption/occlusion of metals by the soil. However the potentialtime driven changes need further testing in a dynamic manner. Theeffectiveness of the proposed combination of soil treatments needsalso to be tested under field conditions in the long termperspective.

Fig. 4. The effect of different treatments on Pb bioaccessibility in Aberdeen soil.Different letters above the bars indicate significant differences between the treatmentsaccording to the Tukey’s test with P < 0.05. The whiskers represent standard deviationfor 3 replications.

4. Conclusions

Summarizing, the treatment of highly Pb/Zn contaminated soilwith biosolids compost combined with liming was the mosteffective remediation method among all those tested. Its effec-tiveness was demonstrated by a strong reduction of metals contentin plant shoots, Zn phytotoxicity symptoms and Pb bioaccessibility.The approach based on the application of so-called tailor-madecomposts combining biosolids with other materials into one highorganic, high Fe and high P amendment (Chaney et al., 2000)proved its usefulness for military range contaminated soils. Theefficiency of this treatment was complex in nature e it reduced Zntoxicity through improved sorption, transformed Pb into morestable forms and prevented deficiencies of macro- and microele-ments enabling growth of grasses. The remediation effect was nota simple pH effect, thus liming as a single treatment was notsuccessful. Establishment of plant cover and reduction of metalsbioavailability will substantially lower the risk for humans andwildlife and the transfer of contaminants to ground- and surfacewater. However, the persistence of the tested approach needs to beconfirmed in the long-term study under field conditions.

Acknowledgments

We gratefully acknowledge Harry Compton, US-EPA, Edison, NJ,USA, for obtaining access to the site and requesting our study ofremediation treatments. Dr. C.E. Green kept analytical equipment inworking order and assisted with analysis.

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