inorganic and organic soil amendments used for the immobilization of cadmium in contaminated soils

7/25/2019 INORGANIC AND ORGANIC SOIL AMENDMENTS USED FOR THE IMMOBILIZATION OF CADMIUM IN CONTAMINATED SO

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In: Management of Hazardous Residues ... ISBN 978-1-61209-526-4Editor: M.J. Balart Murria, pp. 2011 Nova Science Publishers, Inc.

Chapter 3

INORGANIC AND ORGANIC SOIL

AMENDMENTS USED FORTHE IMMOBILIZATION OF

CADMIUM IN CONTAMINATED SOILS

Sil vana I rene Torr i*

School of Agronomy, University of Buenos AiresAv San Martn 4453, Buenos Aires, C1417 DSE, Argentina

ABSTRACT

Chemical stabilization is an in situ remediation method that usesinexpensive amendments to reduce contaminants availability in pollutedsoil. Amendments may adsorb, bind or co-precipitate the contaminatingelements. Cadmium (Cd) is known as more mobile and soluble thanmany other potentially trace element in soils. Furthermore, it has beenidentified as a major toxic element reaching the food chain, directlythrough crop uptake or indirectly through animal transfer. Recently therehas been increasing interest in the immobilization of Cd using a range ofinorganic compounds, such as lime and phosphate compounds, or organic

compounds, such as biosolids compost. In this chapter, the feasibility of

*E-mail:[email protected]
mailto:[email protected]:[email protected]


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Silvana Irene Torri2

using these amendments to immobilize Cd in Cd-contaminated soils is

discussed.

1.INTRODUCTION

Soil contamination with potentially toxic elements (PTE) is a worldwideproblem. Excessive accumulation of PTE in agricultural soils may not onlyresult in environmental contamination, but also lead to elevated PTE uptake bycrops, which may affect food quality and safety (McLaughlin and Singh 1999;Zhu et al, 2008). Among PTE, cadmium (Cd) and lead (Pb) have beenrecognized as priority pollutants by the United States Environmental

Protection Agency (USEPA) and other organizations. Cadmium may easilyreach the food chain through common agricultural practices such asfertilization, irrigation or pesticide application (Mees et al., 2002). Otheranthropogenic activities primarily associated with industrial processes,atmospheric fallouts, manufacturing and the disposal of domestic andindustrial waste materials may also result in a significant input of soil Cd.

The Pampas Region, Argentina, is one of the largest temperate fieldcropland areas of the Southern Hemisphere. At present, the concentrations anddispersion values of PTE in agricultural or grazed soils in this region aresimilar to other non-contaminated soils of the world (Lavado et al., 2004).However, these soils recently started to receive an increased amount of

phosphate fertilizers. Depending on its provenance, Cd in the phosphate rockcan be present in relatively large amounts, from 0 to 150 mg Cd kg1(LpezCamelo et al, 1997). Hence, there is an increasing local concern for protectingthe environmental quality of croplands of the Pampas Region.

In contrast to agricultural soils, some urban areas of Argentina and itssurroundings are starting to show signs of anthropogenic accumulation of Cdand other PTE (Wannaz et al, 2006; Lavado, 2006). Anthropogenic sources ofcadmium for urban and peri-urban areas include traffic emission (vehicleexhaust particles, tire wear particles, brake lining wear particles), industrialemission (power plants, coal combustion, metallurgical industry, chemical

plants, etc.), domestic emission, weathering of building and pavement surface,atmospheric deposition and so on (Sindern et al, 2007; Christoforidis, Stamatis

2009; Lu et al, 2009; Morton-Bermea et al, 2009; Wei, Yang 2010). Somealluvial soils of the Riachuelo River in Buenos Aires province were alsoreported to accumulate between 1-5 mg Cd kg-1due to anthropogenic activity(Ratto et al, 2004). High concentration of Cd in sediments may lead to Cd


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Inorganic and Organic Soil Amendments ... 3

release to water and pose risk to aqueous organisms and human health. Lavado

et al. (1998) reported that concentrations of Cd and other PTE in some urbanand peri-urban soils of Buenos Aires province, were much higher thanthresholds proposed by several international standards and by the ArgentineHazardous Wastes Law (law 24051). Like most other metals, Cd does notundergo microbial or chemical degradation and therefore persists in soils for along time after its introduction. Cadmium has been identified as a major toxictrace element reaching the food chain, directly through crop uptake orindirectly through animal transfer (Adriano 2001). Furthermore, Cd is the onlymetal that might pose human or animal health risks at plant tissueconcentrations that are not generally phytotoxic (Peijnenburg et al. 2000).Once ingested or absorbed by humans, it has a long biological half-life and

causes numerous health concerns (Goyer, 1997).Due to the growing size of the population of Buenos Aires City,horticulture in urban areas and its surroundings is a means of employment ofmigrants from agricultural areas or inmigrants from neighboring countries(Schnitzler et al., 1999). According to the United Nations (2001), nearly all ofthe expected growth in population in the next two decades (20102030) willtake place in urban areas, with almost no growth in the rural population. As aresult, peri urban environments are conducive to intensive production of

perishable foods (fruits, vegetables, meat and dairy products) to be consumedby urban inhabitants. Many studies have shown that Cd is readily taken up byroots crops and translocated to aerial organs where it accumulates to highlevels (Jiang et al, 2010; Perilli et al, 2010). In particular, vegetables are

capable of accumulating relatively high levels of Cd in the edible portion atconcentrations that may exceed food safety limits (McLaughlin et al., 2006,Peralta-Videa et al., 2009; Yang et al, 2009).

2.CADMIUM AVAILABILITY IN CONTAMINATED SOILS

Soils normally contain 0.11.0 mg Cd kg1 (Kabata-Pendias, 2004). TotalCd concentration over 10 mg kg1may be toxic for plants, inhibiting root andshoot growth (Palgyi et al., 2006), decreasing soil microbial activity and soilfertility (Belimov et al, 2005). Nevertheless, total soil concentration of PTE

gives some indication of the level of contamination, but provides no insightinto element bioavailability or mobility. Traditionally, bioavailability refers tothe biologically available fraction that may be taken up by organisms and mayreact with its metabolic machinery (Campbell, 1995), or it refers to the fraction


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that can interact with a biological target. The chemodynamics of Cd in the soil

environment is controlled by its interactions with both solid and aqueousphases. Processes such as adsorption/desorption, ion exchange,precipitation/dissolution, soil and solution phase composition regulate thetoxicity and mobility of Cd through soil profiles (Alloway, 1990; Helmke and

Naidu, 1996). Single extraction and/or sequential extraction procedures areused to estimate the distribution of PTE associated with particular phases insoils and sediments. A large number of sequential extraction schemes have

been proposed for soils, generally attempting to identify PTE held in any ofthe following fractions: soluble, exchangeable, sulfide/carbonate-bound,organically bound, oxides-bound, and residual or lattice mineral bound(Tessier et al, 1979; Sposito et al, 1982; Shuman 1985; Rauret et al, 1999).

Assessment of metal mobility and bioavailability in soils and sediments usingsequential extraction proceduress assumes that mobility and bioavailabilitydecrease in the order of extraction. Thus, metals in the exchangeable fractionsare most mobile and bioavailable, whereas metals in residual fraction aretightly bound and least mobile under natural environmental conditions.Technologies to minimize the chances of Cd reaching the food chain aim toreduce the concentration of bioavailable forms by increasing adsorption,

precipitation or entrapment of Cd in crystal lattices (Hamon et al, 2002).

3.REMEDIATION TECHNIQUES

Different remediation techniques have been developed in order to reducePTE and, in particular, Cd bioavailability in soils (Chen, Lee 1997; Gray et al.,2006). Several physicalchemical treatments based on excavation, landfilling,thermal treatment, acid leaching and electro-reclamation have been proposed.Unfortunately, these methods are not suitable for practical application, becauseof their high cost and low efficiency, limiting its use on vast contaminatedareas (Khan et al, 2005). Moreover, they are often environmentally invasiveand do not permit a natural reshaping of the environment (Lombi et al., 2002).In contrast, bioremediation is cost-effective and environmentally friendly. Two

bioremediation technologies, phytoremediation and stabilization, have beenwidely investigated for the remediation of Cd polluted sites (Dushenkov et al,

1997; Carrillo-Gonzlez et al, 2006).Phytoremediation of Cd-contaminated soils is a fast-expanding

technology, which uses specific plants species which have an innate ability totolerate and accumulate Cd (Blaylock and Huang, 2000; Ghosh, Singh 2005;


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2004). This technology is increasingly being considered as an alternative to the

conventional engineering-based remediation methods and has the advantage ofbeing cost effective, environmental friendly, and less disruptive to the soil andtherefore the associated site ecosystem (Marques et al, 2009). However, theability to accumulate Cd varies significantly between species and betweencultivars within a species (DalCorso et al, 2008). Further, this technique mayrequire extremely long times, e.g. centuries, to achieve the completeremediation of soil. The requisite time with no agricultural activity during theremediation process and the necessary biomass treatment after remediation arethe major drawbacks that limits its use (Marques et al, 2009).

Considering the limitations described above, in situ immobilization isgaining considerable interest over the last decade (van der Lelie et al., 2001).

The aim of immobilization techniques is to use a soil amendment to alter thesoil chemistry and sequester or absorb PTE into the amendments matrix. Inthis way, the bioavailable fraction is reduced, and the detrimental effects ofPTE on environmental receptors, such as microorganisms, plants, animals,water bodies, and humans are minimized (Castaldi et al, 2005). A range ofinorganic compounds, such as lime and phosphate fertilizers (Bolan et al.2003a, b; Hong et al, 2010 a) or organic amendments (Mohamed et al, 2010;Basta et al., 2001) have been used to immobilize Cd in contaminated soils.Various mechanisms have been attributed to the effect of these amendments,including enhanced Cd adsorption (Adriano, 2001); precipitation of metals as

phosphates, hydroxides or carbonates (Basta et al., 2001); and formation ofinsoluble Cdorganic complexes in the presence of organic amendments

(Shuman 1999; Farrell, Jones 2010). This Chapter discusses the potentialvalues of phosphate compounds and biosolids compost, relative to their abilityto immobilize Cd in Cd-contaminated soils.

3.1. Phosphate Compounds

Although phosphate amendments have been initially applied to remediatePb-contaminated soil, they also proved to immobilize Cd and Zn incontaminated soils (Lambert et al., 1997; Hettiarachichi et al., 1998).Moreover, addition of phosphorus to soil is the basis of a patented process to

reduce bioavailability of PTE (Pierzynski and Hettiarachchi, 2002). Sources ofphosphate may include either water-insoluble minerals, such as natural orsynthetic apatites and hydroxyapatites, or water-soluble salts, such asdiammonium phosphate and phosphoric acid. Depending on the source, soil


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application of phosphate may cause the precipitation of Cd or phosphate-

induced Cd2+adsorption.

Water-i nsoluble Phosphate Compounds

Many apatite [Ap, Ca10(PO4)6(OH,F,Cl)2] based materials, such as naturalmineral phosphate and synthetic apatite, bind Cd and other PTE ions fromaqueous solutions and soils (Mandjiny et al., 1995; Chen et al., 2007a; Chen etal., 2007b; Peld et al, 2004; Knox et al, 2003). Calcium-hydroxyapatite (HAp,Ca10(PO4)6(OH)2) has also attracted considerable interests because of its highadsorption capacity, biological compatibility, low solubility in basic andneutral media, excellent buffer property, high stability and low cost. Bothsynthetic and natural HAp reduced bioavailability of soil Cd, limiting its

uptake by crops (Chlopecka, Adriano 1997; Keller et al, 2005). In general,HAp has demonstrated the best removal efficiency due to its moderatesolubilitybetween highly insoluble and highly soluble phosphate bearingmaterials such as phosphate rock and phosphate fertilizers, respectively(Hodson et al, 2000).

Several mechanisms were proposed to explain the sorption process of Cdon apatites, including superficial sorption, ion exchange, and precipitation.The sorption process was studied in detail by Jeanjean et al (1995) andFedoroff et al. (1999). A detailed description of the structure of calcium-hydroxyapatite was provided by Beevers and McIntyre (1945) and later byKay and Young (1964) and Hughes et al. (1989). Calcium-hydroxyapatitecrystallizes in the hexagonal system, where Ca2+ occupies two different

crystallographic sites, Ca(1) and Ca(2). Calcium(1) is found on ternary axes atx=1/3, y =2/3 whereas Ca(2) is found at sites with symmetry m at z=1/4,z=3/4; HO- ions are found in channels along the hexagonal screw-axes, atz=0,198. Sorbed Cd ions substitute for Ca, which is released into the soilsolution (Takeuchi, Arai 1990; Mandjiny et al, 1998). The ion exchangereaction mechanism can be expressed as (Equation 1):

Ca10(PO4)6(OH)2+ x Cd2+(Cdx,Ca10x)(PO4)6(OH)2+ x Ca

2+

(Equation 1)

For low sorbed quantities, Cd is located in Ca(2) sites, while for larger

quantities, it is located in both Ca(1) and Ca(2) sites (Fedoroff et al., 1999).Scanning electron microscope observations showed that there is nomodification of the crystallite morphology after Cd fixation. This process isonly partly reversible and takes place in a large pH range. In addition, Cd may


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diffuse into the bulk of apatite crystals. Nuclear microprobe measurements

showed that Cd penetrated into the whole thickness of the crystals (Toulhoat etal., 1996). Fedoroff et al. (1999) concluded that Ca(2) sites, which are adjacentto the channels centred on the hexagonal screw-axes, are first substituted bysorbed Cd, suggesting that these channels are the main pathways for diffusioninto the solid. Nonetheless, diffusion seems to slow down as the concentrationof Cd increases in apatite crystals.

Chen et al (1997b) reported that the sorption of aqueous Cd onto apatiteincreased abruptly when pH increased above 6,2. X-ray diffraction (XRD)

patterns of the reaction products also indicated the formation of otavite (Chenet al, 1997a; Chen et al, 1997 b) and cadmium hydroxide, as expressed byEquations 2 and 3 respectively (Chen et al, 1997 b).No crystalline cadmium

phosphates were detected.

Cd2++ HCO3- CdCO3(c) + H

+ (Equation 2)

Cd2++ 2H2O Cd(OH)2(c) + 2H+ (Equation 3)

Therefore, the main mechanisms of Cd retention by apatite seem to bediffusion and ion exchange, leading to the formation of a (Cd-Ca) solidsolution; while Cd surface complexation or precipitation are minorcontributing processes. The fact that Cd is incorporated into the bulk of theapatite with only partial reversibility is important in the context of the safestorage of used sorbent material.

Water-soluble Phosphate Compounds

Soluble phosphate compounds include fertilizers such as singlesuperphosphate, triple superphosphate, monoammonium phosphate anddiammonium phosphate. Several studies reported that application of highlevels of water-soluble P compounds decreased the bioavailability andmobility of Cd in contaminated soils, which has been attributed to a decreasein Cd solubility (Pearson et al., 2000; McGowen et al., 2001; Chen et al. 2007a; Thawornchaisit, Polprasert 2009).

Two reasons have been attributed to phosphate-induced immobilization ofCd in soils: phosphate-induced Cd2+ adsorption; or Cd precipitation as

Cd(OH)2and/or Cd3(PO4)2.Phosphate-induced Cd2+adsorption may be the result of an increase in pH(Levi-Minzi, Petruzzelli 1984), increase in surface charge (Naidu et al., 1997)or the formation of surface complexes of Cd on the phosphate compound


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(Helyar et al. 1976). Different phosphate sources may impact the effectiveness

of Cd stabilization. Thawornchaisit and Polprasert (2009) evaluated theefficiency of three commercial phosphate fertilizers: triple superphosphate,diammonium phosphate, and phosphate rock as stabilizing agents in Cd-highlycontaminated soils. Addition of all tested phosphate fertilizers induced a shiftof Cd mobile forms towards more stable fractions; however, the shiftingdegree occurred at different rates depending on the phosphate fertilizer used,and followed the sequence: triple superphosphate > diammonium phosphate >

phosphate rock. Consequently, stabilization efficiency appeared to becorrelated with dissolution of phosphate sources.

Other studies have shown that many PTE-phosphates arethermodynamically stable and relatively insoluble in natural environments

(Santillan-Medrano, Jurinak, 1975; Nriagu, 1984; Vieillard and Tardy, 1984;Ruby et al., 1994). The possibility of forming cadmium phosphate [Cd3(PO4)2]upon the addition of soluble phosphate compounds in Cd contaminated soilshas been proposed, without direct evidence (Ma et al., 1993; Cotter-Howells,Caporn, 1996). In effect, Bolan et al. (2003 a) found no evidence of Cd3(PO4)2formation in soil samples even at the highest level of KH2PO4and Cd addition.Moreover, the solubility of Cd3(PO4)2has been shown to be too high to controlthe concentration of Cd in soil suspensions involving iron and aluminiumhydrous oxides (Kuo, 1986; Soon, 1981). Thus, although the precipitation asPb or Zn phosphates has been proved to be one of the main mechanisms forthe immobilization of Pb and Zn in contaminated soils (Hettiarachchi et al.2000; McGowen et al., 2001) no conclusive evidence was provided up to this

time on the existence of new solid phases of Cd-phosphate compounds uponaddition of phosphates on Cd-contaminated soils.

Problems Associated with the Use of Phosphate as an Immobili zing

Agent

Numerous studies have demonstrated that phosphates should be applied atvery high rates to decrease Cd availability in field contaminated soils(McGowen et al., 2001; Hong et al, 2009; Hong et al. 2008), resulting in newenvironmental problems. Surface runoff from croplands with high levels ofsoil phosphorus may originate phosphorus enrichment of streams, lakes andestuaries (Sharpley et al., 1996). Accumulation of phosphorus in water bodies

can result in rapid algae growth, oxygen depletion when algae decompose, andaccelerated eutrophication in saline and fresh waters (Sims et al., 1998; Lin etal., 2009).


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Although phosphate fertilizers provide effective immobilization of Cd in

highly contaminated soil (Wang et al, 2008), their application may also resultin soil acidification (Chen et al., 2007c; Thawornchaisit, Polprasert 2009). Theeffect of phosphate addition on soil pH depends on the buffering capacity ofthe soil, the nature of phosphate compounds and the extent of phosphateadsorption (Havlin et al., 1999). Dissolution of phosphate fertilizers,

particularly triple superphosphate and diammonium phosphate, yield therelease of phosphoric acid (Chrysochoou et al, 2007; Spuller et al, 2007),decreasing soil pH. Thus, phosphate-induced variation in soil pH mayinfluence the solubility of Cd in soils, as reported by Levi-Minzi andPetruzzelli (1984). It has often been observed that the phytoavailability of Cdincreased with decreasing pH (Naidu et al., 1994). Hence, if immobilization of

Cd is followed by soil acidification, the contaminated soil will continue topose a potential ecological risk and the remediation treatment may not besustainable without continued management inputs. Consequently, co-application of liming materials with phosphate fertilizer would be necessary tooffset soil acidification, especially in non-alkaline soils.

3.2 Organic (Biosolids) Amendments

Organic matter has been of particular interest in studies of PTE retentionby soils, because of its significant impact on cation exchange capacity (CEC),and more importantly, the tendency of transition metal cations to form stable

complexes with organic ligands (Elliott et al., 1986; Chen, 1996). Organicmaterials provide a large number of non-specific and specific sorption sites formetals from which they may be difficult to displace (Shuman, 1999). Thus, insituapplication of organic amendments is becoming increasingly widespreadfor its low cost and beneficial effect on soil fertility (Tapia et al, 2010).

Organic matter has quite a different effect on Cd availability dependingupon whether it is in soluble or insoluble forms. Soil addition of insoluble(humified) organic amendments encourage the formation of stable organo-cadmium complexes, which diminishes Cd solubility (Udom et al. 2004;Mohamed et al, 2010). The ability of humic substances to bind Cd wasattributed to their high content of oxygen-containing functional groups,

including carboxyl, phenol, hydroxyl, enol, and carbonyl structures of varioustypes (Rocha et al. 2009). Some studies reported different interactions betweenhumic acids and Cd, depending on the nature and properties of functional


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groups, especially regarding their content of phenolic groups (Datta et al.,

2001).Dissolved or soluble organic carbon consists of several types of low

molecular weight organic compounds, such as polyphenols, simple aliphaticacids, amino acids and sugar acids (Fox, Comerfield 1990). Soluble organiccarbon can facilitate the transport of Cd through the formation of solublecomplexes (Antoniadis and Alloway, 2002; Kaschl et al, 2002; Pan, Zhou2007). Although these compounds may reduce Cd adsorption onto soilsurfaces (Guisquiani et al., 1998), they have been shown to be less readilyavailable for plant uptake (Hamon et al., 1995; Han et al., 2001).

Throughout the world, there have been increasing interests in theutilization of waste materials such as biosolids or biosolids compost as low-

cost adsorbents rather than disposal in a landfill. Traditionally, biosolids havebeen viewed as one of the major sources of PTE accumulation in soils, and alarge volume of work has been carried out to examine the mobilization and

bioavailability of biosolid-borne metals in soil (Merrington, Madden 2000; Liet al, 2001; Li et al, 2006; Torri, Lavado 2008 a, Torri, Lavado 2008 b).Biosolids contain a high proportion of humified organic matter. Torri et al(2003) reported that between 29-45% of biosolids-borne carbon wasrecalcitrant in three representative soils of the Pampas Region, Argentina.During composting, organic compounds are transformed through successiveactivities of different microbes into stabilized humic substances (Garca et al.,1993; Par et al., 1998).

Although biosolids and biosolids compost may contain Cd themselves,

further studies have shown that biosolid addition to soil enhanced the ability ofsoil in adsorbing heavy metals, thereby limiting its bioavailability (Merringtonand Smernik, 2004, Tapia et al, 2010). Actually, soil application of thisorganic waste has improved Cd immobilization in extremely contaminatedsoils (Li et al., 2001; Bolan et al., 2003 c;Brown et al., 2003; Hettiarachchi etal, 2003; Tapia et al, 2010, among others), aiding the re-establishment ofvegetation (Castaldi et al., 2005; Gadepalle et al, 2009). The presence of

phosphates, aluminum compounds and other inorganic minerals in biosolids isalso responsible for the retention of Cd, preventing the increased metalavailability suggested in the time bomb hypothesis (Li et al, 2001;Hettiarachchi et al., 2003; Torri, Lavado 2009). Such observations imply that

the sequestration capacity of biosolids of sludge origin might be indefinite dueto the residual effects of the mentioned constituents. This observationcomplements those of Mahler et al (1987) and Brown et al. (1998) whichindicated that either inorganic phases in biosolids or recalcitrant organic


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carbon are responsible for maintaining low plant availability in biosolids-

amended soils. Currently, there is intense debate whether the organic or theinorganic fraction is responsible for Cd and other PTE immobilization (Li etal., 2001; Stacey et al., 2001, Bolan et al., 2003 c, Hettiarachchi et al., 2003,Merrington et al., 2003; Kumpiene et al., 2008).

Liming of contaminated soils is the most widely used remediationtreatment to reduce the bioavailability of Cd (Bolan et al. 2003 b; Tlusto etal., 2006; Hong et al, 2009). Alkaline amendments increase soil pH (McBrideet al., 1997 and Filius et al., 1998) and facilitate the formation of oxides,metal-carbonate precipitates and complexes that decrease metal solubility(Mench et al., 1994). Biosolids compost can therefore be combined withalkaline materials to complement Cd sequestering ability on compost

components (Mench et al., 1994 and Chlopecka and Adriano, 1996). Recentstudies have shown that alkaline-stabilized biosolid compost that are low intotal and/or bioavailable metal content can be used as an effective sink forreducing the bioavailability of Cd in contaminated soils (Brown et al., 2000; Liet al., 2000; Basta et al., 2001; Clemente et al., 2005). Numerousinvestigations have been carried out for biosolids compost as potentialcontamination sources of heavy metals. Conversely, limited work has beendone regarding the capacity of biosolids compost obtained at different stagesof the composting process, lime and a mixture of mature compost and lime toimmobilize Cd on an artificially Cd contaminated soil of the Pampas Region,Argentina. These aspects are further discussed.

3.2.1. Immobil ization Studies on a Typical Soil of the Pampas Region,

Argentina Soil

The study selected a typic Argiudoll (U.S. Soil Taxonomy) of the PampasRegion, Argentina. Pristine topsoil samples (


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Table 1. Selected properties of the soil and the organic amendments used

in the study

pH EC % C SolubleC

Texture (%) CEC TotalCd

(dSm-1)

%C Clay(%)

Silt(%)

Sand(%)

(cmolkg-1)

(mg kgMS-1)

Conta-minated soil

5.72 0.7 2.02 - 30.3 53.6 16.1 24.5 10.94

Compost 1 7.5 2.10 13.42 0.24 24


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EXCH-Cd); 0.5 M NaOH for 16 h (organic matter bound fraction, OM-Cd );

0.05 M Na2EDTA for 1 h (inorganic precipitate fraction, INOR-Cd) at a soil:solution ratio of 1:10. The concentration of Cd in each fraction wasdetermined by Flame Atomic Absorption Spectroscopy (FAAS).

The statistical analysis was done with the Statistics 7.0 (2000) package,processing the data for Analysis of Variance (ANOVA) for a completelyrandomized design. One-way ANOVA was carried out to compare the meansof different treatments; where significant F values were obtained, differencesbetween individual means were tested using Tukeys test. Statisticalsignificance was defined as p < 0.05.

Treatment Effect on Cd Soil Fractions

The percent of total Cd associated with different fractions in the controlsample was in the following order: exchangeable fraction (55%) > organicmatter bound fraction (31%) > inorganic precipitate fraction (13%). Theseresults indicate that a substantial quantity of Cd in the contaminated soil may

be available for plant uptake (Basta and McGowen, 2004), in good agreementwith results reported by Chen et al, (2007). The concentrations of Cd in thedifferent soil fractions following treatments in each sampling date are shownin Figures 1, 2 and 3.

Figure 1. Water-soluble and exchangeable fraction of Cd (EXCH-Cd) in the

contaminated soils as a result of the addition of amendments: SC: control, Ci: soilamended with compost i; L: soil amended with lime. For each date, different lettersindicate significant differences according to Tuckey's test at 5% probability level (n =3).

aa a

bb b

0

1

2

3

4

5

6

7

0 14 28 42

EXCH-Cd(mgkg-1)

days

CS

C1

C2

C3

C3+L

L


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Changes in Cd Water-Soluble and Exchangeable Fraction (EXCH-Cd)

The addition of C1, C2 or C3 did not significantly modify EXCH-Cd overthe incubation period compared to control (Figure 1), which ranged from 47 to55% of Cd total content. These results are at variance with some other

published papers where the application of compost significantly reduced theconcentration of EXCH-Cd in contaminated soils (Castaldi et al, 2005; Lin,Zhou 2009; Tapia et al, 2010). Conversely, the application of L or C3+Lsignificantly reduced the concentrations of EXCH-Cd compared to control,revealing that there was a net movement of Cd towards other soil fractionsfollowing the addition of this amendment. These results are similar toobservations made by others for EXCH-Cd in the presence of lime (Brallier etal. 1996; Fernandes et al. 1999; Hong et al. 2007, 2009).

Among soil factors controlling the adsorption of Cd, pH is probably themost important (Christensenn, 1984). It has often been observed that theadsorption of Cd2+ increased with increasing pH, resulting in low Cd

phytoavailability (Naidu et al., 1994; Bolan et al., 1999; Hong et al. 2007).The effect of pH is related to its great influence on the charge and structure ofthe adsorbing surfaces and on the ionic composition of the soil solution(Garcia-Miragaya and Page, 1978; Abd-Elfattah and Wada, 1981). An increasein pH increases soil net negative charge, which is attributed to the dissociationof H+from weakly acidic functional groups of organic matter or from someclay minerals (Curtin et al. 1996).

Table 2. pH in the contaminated soils as a result of the addition of

amendments: SC: control, Ci: soil amended with compost i; L: soil

amended with lime. For each date, different letters indicate significant

differences according to Tuckey's test at 5% probability level (n = 3)

day 14 day 28 day 42

treatment pH

CS 5,72 0,05 a 5,54 0,01 a 5,54 0,13 a

C1 5,66 0,07 a 5,55 0,10 a 5,47 0,14 a

C2 5,83 0,05 a 5,66 0,06 a 5,48 0,10 a

C3 6,00 0,04 a 5,62 0,13 a 5,54 0,01 a

C3+L 7,75 0,03 b 7,72 0,13 b 7,74 0,12 b

L 7,93 0,01 b 7,98 0,09 b 7,95 0,31 b


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Application of liming materials significantly increased soil pH compared

to the other treatments (Table 2). The increase in pH by lime can be explainedby the release of hydroxyl ion after hydrolysis of calcium carbonate. Thisincrease in pH resulted in enhanced Cd adsorption, as reported by otherauthors (Szkov et al, 2007; Ghafoor et al., 2008; Hong et al, 2010b).Conversely, no significant differences in soil pH values were observed

between control and soils treated with C1, C2 and C3 in each sampling date.Interestingly, in most of the studies reported in the literature, biosolidscompost addition increased soil pH across all treatments in comparison tocontrol samples (Castaldi et al, 2005; Gadepalle et al, 2009; Tapia et al, 2010).The lack of significant differences in soil pH values between control, C1, C2and C3 in this study suggests that pH may be regarded as the key factor

controlling the concentration of exchangeable Cd in Cd contaminated soils. Anegative and significant correlation could be established between EXCH-Cdand soil pH [EXCH-Cd (mg kg-1) = -1,4818 pH + 13,66, R2= 0.98, p


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slight increases in humic substances originated in the compost process,

explaining the lack of significant differences in OM-Cd between C1, C2 or C3.Moreover, there was no difference in the concentration of OM-Cd betweencontrol and C1, C2 and C3, which may be attributed to the high level oforganic matter in the control, together with the fact that Cd is one of the moreweakly bonded ions by soil organic matter (Harter, Naidu 2001).

Nonetheless, an increase in OM-Cd was observed in control andcomposts, lime or lime + compost amended soils during the incubation period,and accounted between 30-50% of the total soil Cd.

Changes in Cd Precipitated Fraction (INOR-Cd)

The amounts of INOR-Cd in control and amended soils are shown in

Figure 3. No significant differences in INOR-Cd were observed with theaddition of C1, C2 or C3 compared to control in all sampling dates. On thecontrary, lime application resulted in a significant increase of INOR-Cdcompared to control. These results are in agreement with some other published

papers which indicate that application of lime can significantly increase theprecipitated fraction of Cd in contaminated soil (Knox et al. 2001; Hong et al,2010 b), possibly as Cd-carbonate (Knox et al. 2001; Basta et al., 2001) at theexpense of the EXCH-Cd fraction. A positive and significant correlation could

be established between INOR-Cd and soil pH [INOR-Cd (mg kg-1) = 0,6443pH - 2,267 (R2 = 0,96, p


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low phytoavailability, and could become no phytoavailable as surfaces become

occluded.

Figure 2. Organic fraction of Cd (OM-Cd) in the contaminated soils as a result of theaddition of amendments: SC: control, Ci: soil amended with compost i; L: soilamended with lime. For each date, different letters indicate significant differencesaccording to Tuckey's test at 5% probability level (n = 3).

Figure 3. Inorganic precipitates of Cd (INOR-Cd) in the contaminated soils as a resultof the addition of amendments: SC: control, Ci: soil amended with compost i; L: soilamended with lime. For each date, different letters indicate significant differencesaccording to Tuckey's test at 5% probability level (n = 3).

b

b b

ab

ababa

aa

0

1

2

3

4

5

6

7

0 14 28 42

OM-Cd(mgkg-1)

days

CS

C1

C2

C3

C3+L

L

b b b

aa a

0

1

2

3

4

5

6

7

0 14 28 42

INOR-Cd(mgkg-1)

days

CS

C1

C2

C3

C3+L

L


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Considerations on Compost Application

Biosolids and biosolid composts are likely to increase in many countries,so there is an urgent need for sustainable ways for their disposal. In this short-term study, EXCH-Cd and INOR-Cd were closely related to soil pH.Application of biosolids compost alone did not substantially modify theavailability of Cd in Cd contaminated soils, possibly because soil pH was notmodified. The application of mature compost plus lime significantly reducedCd soluble/exchangeable fractions, with a proportional increase in the organicand, to a lesser extent, inorganic-bound fractions. However, some uncertaintymay raise about Cd becoming more bioavailable with time throughmineralization or soil acidification. The long-term efficacy of this amendmentrequires careful examination.

4.CONCLUSION

Remediation of Cd-contaminates soils can be achieved by addingphosphate compounds or biosolids compost. Both amendments can enhanceCd immobilization by redistribution of Cd to less available fractions.Phosphateaddition was found to decrease Cd availability, although the mechanisms ofCd fixation is not fully known. Alternatively, the addition of alkaline biosolidcompost decreased the concentration of the soluble and exchangeable Cdfraction, and increased the concentration of organic and, to a lesser extent,inorganic-bound Cd fractions.

The environmental factor more likely to have the largest effect on Cdavailability is soil acidification. Consequently, if in situ remediation materialsexert their effect through changes in soil pH, then reacidification of soil wouldreturn Cd to the original toxic level. Therefore, there may be a need to managesoil pH in perpetuity if toxicity is to be avoided. Nevertheless, one of themajor inherent problems associated with these immobilization techniques isthat, although Cd becomes less bioavailable, total Cd concentration in soilsremains unchanged. In the long-term the immobilized element may becomemore mobile and bioavailable through natural weathering processes.


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