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Waste Management 28 (2008) 215–225 www.elsevier.com/locate/wasman

Review

Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments – A review
Jurate Kumpiene *, Anders Lagerkvist, Christian Maurice
˚ ˚ Division of Waste Science and Technology, Lulea University of Technology, SE-97187 Lulea, Sweden Accepted 6 December 2006 Available online 22 February 2007

Abstract The spread of contaminants in soil can be hindered by the soil stabilization technique. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces, formation of stable complexes with organic ligands, surface precipitation and ion exchange. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. The technique can be used in in situ and ex situ applications to reclaim and re-vegetate industrially devastated areas and mine-spoils, improve soil quality and reduce contaminant mobility by stabilizing agents and a beneficial use of industrial by-products. This study is an overview of data published during the last five years on the immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. The most extensively studied amendments for As immobilization are Fe containing materials. The immobilization of As occurs through adsorption on Fe oxides by replacing the surface hydroxyl groups with the As ions, as well as by the formation of amorphous Fe(III) arsenates and/or insoluble secondary oxidation minerals. Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to stable in natural environments Cr(III). The reduction is accelerated in soil by the presence of organic matter and divalent iron. Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and oxyhydroxides, ion exchange and formation of ternary cation–anion complexes on the surface of Fe and Al oxy-hydroxides. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments, which reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals. Zn can be successfully immobilized in soil by phosphorus amendments and clays. Ó 2007 Elsevier Ltd. All rights reserved.

1. Introduction The concentration of trace elements in the Earth’s crust is constant and their enrichment in one place causes depletion in others. In the soil remediation context, trace elements cannot be destroyed like organic contaminants but only be relocated from one place, e.g. contaminated site, to another, e.g. landfill. The high cost of traditional soil remediation techniques (excavation and landfilling) and limited resources allocated to remediate contaminated sites prompted the development of alternative techniques that are cost-effective and less
*

Corresponding author. Tel.: +46 920 493020; fax: +46 920 492818. E-mail address: juku@ltu.se (J. Kumpiene).

disruptive to the environment such as soil stabilization. For the comparison of soil stabilization with other commonly used soil remediation techniques, refer to Mulligan et al. (2001). In this review, the term stabilization refers to the chemical stabilization of trace elements induced by immobilizing soil additives (amendments). The paper is an overview of data published during 2000–2005 on immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. These elements are of environmental relevance as they are common soil contaminants. As, Cu, Cr, and Zn can be found all together in soil contaminated with a wood impregnation chemical, chromated copper arsenate (CCA), while Pb is a contaminant usually related to the mining industry.

0956-053X/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.wasman.2006.12.012

due to slight changes in environmental conditions. 2003). de Mora et al. 2003. 2002. The application of soil improvement or amelioration to reduce contaminant mobility through soil-plant path (phytoavailability) was initiated in a branch of soil remediation and this technique is named phytostabilization (for a review. barriers or vitrification. The S/S is conventionally used to describe the soil remediation method when soil is physico-chemically stabilized using cement based materials. the method is not a novelty. Panfili et al. 2003). can be released and leached to ground/surface water or taken up by soil organisms. Mixtures of appropriate industrial by-product and contaminated soil. 2006. organic matter. therefore. Immobilization of trace elements in soil The hazard of inorganic contaminants arises from their bioavailable concentrations and necessity for organisms. gypsumand lime-rich industrial by-products (Garrido et al. can reduce the leachable concentrations of contaminants. As described in the Remediation Technologies Screening Matrix and Reference Guide (FRTR. In such cases the term phytostabilization would not be accurate as the contaminant immobilization is initially caused by the soil amendments. coal or bio-fuel fly ashes (Clark et al... the treated soil can be disposed of at landfills designed for waste of lower hazard level... minespoils and tailings sites or mixing it into the spoils. redox potential. Mench et al.. 2005).. 2003). Stabilization technique and its applications The stabilization of trace element contaminated soils is a remediation technique used to reduce element mobility in soils by adding immobilizing agents. Canada.. 2002.216 J. 2002). (2004) to describe natural biogeochemical processes regulating metal mobility in highly contaminated sites that are facilitated by soil amendments. focus is laid on the contaminant immobilization in soil due to amendments and effects of the treatment are then observed on vegetation and using bioassays (Gupta et al. 2005) was conducted on such plant properties in the soil remediation context. while As and Pb have not any known physiological function for plants or humans and even the smallest quantities can have adverse effects on organisms.. and a single mechanism rarely accounts for the immobilization of elements in soil. 2000. and Zn are essential micronutrients and are required in small quantities by living organisms... Stabilization can be considered a part of the solidification/stabilization (S/S) method. 2004. 2001).. as soil amelioration adding. Therefore. Hence the method seems to originate from the field of agriculture with crops being the focus. through solid covers. Sajwan et al. e.. chemical immobilization or reclamation using amendments are often used in the literature. Knox et al. Bleeker et al. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces. e. 1996). Ca and Mg) and reduce soil phytotoxicity to crops by decreasing mobility and bioavailability of toxic elements (Bolan et al. which needs to be disposed of at landfills for hazardous waste. Tripathi et al. / Waste Management 28 (2008) 215–225 The choice of amendments depends on the type of soil contaminants. Stabilization of contaminants in soil can be achieved by amendments able to adsorb. 2005). Establishment of the vegetation.g. 2002a.. reverse a depletion of nutrients (e. site colonization with ambient plant species and recovery of the ecosystem is considered an indication of remediation success. 2000. Industrial waste or bio-products.. 2001.. formation of stable complexes with organic ligands. little of the research (Caille et al. Tordoff et al.. Cr. Chiu et al.g. lime. Mench et al. 2004). The term ‘‘assisted natural remediation’’ was suggested by Adriano et al. 2005. ‘‘solidification/stabilization reduces the mobility of hazardous substances and contaminants in the environment through both physical and chemical means’’. 3. Arsenic. According to this definition. Guerrero et al. terms such as in situ stabilization. sewage and paper mill sludge (Merrington et al. The largest example of such an approach is Sudbury. cation exchange capacity. by-products from iron and aluminum industry (Lombi et al. Consequently. has been used for many years with the aim to improve plant growth. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. Instead. however. 2002)... . Seoane and Leiros. e. complex or (co)precipitate trace elements. Amendment application in field comprises spreading it over the areas devastated by near-by running industrial activities.g. Although phytostabilization is by definition. the main question to be answered by this review is: what amendments have been used lately to stabilize soil contaminated with one of the above named elements or their combinations? Particular attention is given to As due to its high toxicity to humans. Morgan et al. around mining and smelting areas. Therefore.. Rautaray et al. 2000. see Berti and Cunningham. etc. where more than 30 km2 of devastated land around a mining and smelting region was successfully re-vegetated after liming and fertilizing the soil (Winterhalder. Cu. the part of the S/S method which involves the reduction of contaminant mobility only by chemical means can be called chemical stabilization. 2000. 2. Kumpiene et al. 2003. vegetation is used to reduce contaminant spread and create an aesthetic environment (Gorman et al. 2001. In both cases. is classed together with elements that are essential in animal nutrition (Adriano et al. surface precipitation and ion exchange..g. ‘‘the phenomenon of the production of chemical compounds by plants to immobilize contaminants at the interface of roots and soil’’ (FRTR.. type of soil constituents. phosphates.b) can be used beneficially for the reduction of contaminant mobility. 2000). The method aims at element fractions that.. Different sorption/dissolution processes are influenced by many factors: pH. 2001.

3. 3. 2003.. Even if oxidation reactions of Fe(0) in soil are not as fast as those of salts. to a lesser extent. (2002) and Ritcey (2005). the most efficient ratio was 2 and higher. Co-mixing of lime is usually used to avoid soil acidification. (2003) and Warren and Alloway (2003).. such as metal oxides. scorodite (FeAsO4 Æ 2H2O) (Sastre et al.1. 2000. it might be beneficial in a long-term perspective. Precipitation of Fe oxides. Cu and Zn (Hartley et al. adsorption occurs by ligand exchange of As species for OH2 and OHÀ groups on Fe oxide hydroxide surface.. As–Fe precipitates of increasing stability at pH range 3–8 were formed when the Fe/As molar ratio exceeded 2 and increased up to 16. Application rates based on As/Fe molar ratio can be more informative seeing as different soils have different contamination levels requiring different amounts of reactive Fe. Sherman and Randall (2003) explained the exact mechanism of the adsorption of As(V) onto goethite. causes acid (H2SO4) release. depending on the soil type.. by ferrihydrite are summarized by Jain . 2004). Fe(II). 2005): Feð0Þ þ 2H2 O þ 1=2O2 ! FeðIIÞ þ H2 O þ 2OHÀ .. Iron compounds Iron salts are commonly used for As stabilization purposes. and goethite (Hartley et al. 3.. 2004). 2002)..1. According to their results. 2003. 2004) and phytoavailability (Warren et al. (2000) tested a range of Fe addition based on As/Fe molar ratio. Warren et al.. Al and Mn. which is easily adsorbed to further formed iron hydroxides. Warren and Alloway. 2002.. 2004) with Fe(III) sulfate being more efficient than Fe(II) sulfate (Kim et al. Generally. oxidation of Fe(0) is expected to have a minor influence on soil pH. 2001).. 3. Since the choice of a suitable amendment for soil treatment depends on the type of contaminant. surface area-normalized reaction rate constants are similar to micro-sized Fe(0) (Nurmi et al. Leupin and Hug (2005) observed that slow and continuous release of Fe(II) by iron corrosion provides ideal conditions for the oxidation of As(III) to As(V).1. Fe(0). while at pH around 5 and moderately oxidizing conditions. However. In contrast. Hacherl et al. However. The main advantage of using Fe(0) over Fe salts is that the former contains three times more iron by weight than the most common Fe salts. Therefore the most extensively studied amendments for As immobilization are oxides of Fe and. / Waste Management 28 (2008) 215–225 217 A practical way to choose the appropriate amendment for respective contaminant is to look at its affinity for element-bearing soil fractions.. As(III). sulfides. (2003) and Warren and Alloway (2003) observed increased plant uptake of other contaminants including Cu. 2002) and/or insoluble secondary oxidation minerals. FeðIIIÞ þ 3H2 O ! FeðOHÞ3 þ 3Hþ : À ð1Þ ð2Þ ð3Þ et al. concluded that Fe oxide rates >0. Nano-sized Fe(0) is a highly reactive material mainly due to its large specific surface area.1..1. based on pot and field experiments. Hartley et al. Hartley et al. Based on hydrometallurgical studies on As removal from process wastewaters. Fe(0) oxidizes in soil forming poorly crystalline Fe hydroxides (Leupin and Hug. 2004).g. e. lepidocrocite.g. The reported application rates of Fe compounds vary. According to the authors. Kim et al. ˜ 2004).. 3. 2005). reviewed by Carlson et al. Kumpiene et al.. 2000). Mn oxi- The mobility of As can be reduced by the formation of amorphous iron(III) arsenate (FeAsO4 Æ H2O) (Carlson et al. The authors explained that there was an insufficient amount of lime added and suggested a ratio of lime/Fe oxide necessary for maintaining soil pH should be higher than 1:1.2. 1980. efficiency of As retention increases with increasing amount of Fe oxides. and arsenate. Porter et al. Manganese oxides The applications of Mn oxides for As immobilization are less extensively studied compared to Fe oxides. adding high concentration of easily soluble Fe salts to soil can have a reverse effect on As retention as Fe(II) can adsorb to newly formed Fe hydroxides and inactivate them (Tamura et al. highly insoluble Fe3(AsO4)2 can possibly be formed (Porter et al... (1999). phosphates. 2003. Aluminum oxides Synthetic Al(OH)3 can be as highly efficient for As stabilization in soil as synthetic FeOOH (reaching nearly 100% efficiency) and give better results than natural Fe oxy-hydroxides and clay minerals (Garcia-Sanchez et al. FeðIIÞ þ H2 O þ 1=4O2 ! FeðIIIÞ þ 1=2H2 O þ OH .. Warren et al. 2003). As(V). the following review is divided into sections summarizing treatment possibilities for the individual elements. followed by the Fe sulfate application. At low pH and highly oxidizing conditions precipitation of scorodite has been observed (Magalhaes.J. In contrast. etc. Possible reactions of adsorption of arsenite. Application rates of Fe(0) greater than 5% by weight can lead to problems with soil structure such as aggregate cementation and changes in porosity. Ferrous. hematite and ferrihydrite to be the formation of inner-sphere surface complexes resulting from bidentate corner-sharing between AsO4 and FeO6 polyhedra. Iron (II)/(III) sulfates with simultaneous applications of lime were reported to be the most efficient in reducing labile As concentrations compared to zerovalent iron. 2004). Moore et al. Zn and Pb in soil amended with Fe(II) sulfate and lime.5% had no beneficial results on the reduction of As phytoavailability. while application rates greater than 1% can negatively effect vegetation (Mench et al. sulfate was demonstrated to effectively reduce As mobility (Moore et al. such treatment significantly increased the leaching of metals e. Arsenic The mobility of As in soil is mainly controlled by adsorption/desorption processes and co-precipitation with metal oxides.

where anaerobic conditions are expected to dominate. Moon et al. however.. 2002) or a highly insoluble mineral Mn3(AsO4)2 Æ 8H2O with lowest solubility around pH 6 and pE 6 (Porter et al. fly ashes. Generally it is believed that alkaline materials. Clay minerals The stronger As binding is the reason of the lower As toxicity in clayey soils compared to sandy soils.. (2002) studied As retention in two soils amended with bentonite (composed of 99% montmorillonite) and limonite. However.5) soil conditions. Beside the pH... Although the leaching of As is significantly reduced. reduction of As(V) to As(III) and consequent leaching was induced by the compost. hydroxyapatites. 2003.6.218 J. the As leaching and uptake was low due to its adsorption to OM. concluded that there is no evidence of OM contribution to the sorption of significant amounts of As in soils. 2004). 2003). admixture of sulfur-containing materials might be considered... 3. Fitz and Wenzel (2002). Dermatas et al. are undesirable in As contaminated soil as they increase As leaching (Seaman et al. Arsenic sulfides In cases of a disposal of non-solidified As contaminated soil at landfills. Cao and Ma (2004) used compost to remediate CCA-contaminated soils and observed As adsorption by organic matter and reduced accumulation by vegetables. the type of OM might play a role in its varying effect on As mobility. at strongly reducing conditions) or without iron (As2S3.6) achieved by limonite at 10% application rate.. HA and As sorption were not interfering and was suggested to be independent of each other. 2001). Mn can immobilize As ¨ through co-precipitation as MnHAsO4 Æ 8H2O (Tournassat et al. 2003. Dissolved organic matter can compete with As for sorption sites and displace both As(V) and As(III) from iron oxides (hematite) (Redman et al.5. Foster et al. orpiment. According to their results. 3. 2004)... while only CA was able to reduce As(V) adsorption on ferrihydrite.. The authors suggested this could be explained by the possible formation of As–Ca complexes. Leist et al..g. Garcia-Sanchez et al. even in calcareous soils. while Mench et al. The highest reported efficiency was 80% reduction in As leaching in one of the soils (pH 4. The sorption capacity of limonite was much smaller in the more acidic soil (pH 3. Alkaline materials The effect of alkaline materials on the As mobility is not less contradicting than that of OM. e. such a soil treatment is rather disruptive and considered only when the material is disposed of at a landfill. (2002) concluded that the effect of compost on As leaching and uptake by vegetables was pH dependent. 3.. At slightly acidic (pH 5. Application of liming materials was shown to increase As mobility in soil (Mench et al. However. that form complexes with Fe oxides (Seaman et al. phosphates and silicates.8) and accounted for less than 50% of the retained As. while the same amount of bentonite accounted for 50% of the retained As. Hartley et al. 2003). 2000) and applied alone or in combination with Fe oxides significantly reduce As mobility and toxicity in contaminated soils (Mench et al. cations might not necessary decrease As sorp- . Fe(III). insoluble sulfides can be formed either with iron (AsFeS. The sorption of As to clays depends on the clay type. 2003). Mn oxides can bind As as bidentate corner-sharing (bridging) complexes similar to As(V) sorption on ferric. 2004). 2003. 2004.1. Ca has insignificant effect on As binding. Grafe et al.g. hydroxides (Manning et al. The authors also observed that goethite had a higher affinity for dissolved organic carbon (DOC) with a higher surface coverage and stronger bonds than ferrihydrite. At lower redox. Organic matter Research of the influence of organic matter (OM) on As mobility presents controversial results. The immobilization of As in soil can be lessened at the presence of competing anions.. arsenopyrite. (2002) studied adsorption of As on synthetic ferrihydrite under the influence of three types of OM: peat humic acid (HA).1. Bentonite in that case was not effective at all. Suwannee River fulvic acid (FA) and citric acid (CA). 2002) and contribute to the toxicity reduction. In contrast. Kumpiene et al.. 2002). e. 3. Mn oxides can effectively oxidize As(III) to As(V) (Tournassat et al.1. (2004) observed that lime actually reduced As leaching in soil by 8%. lime.5–8. 2000). In contrast.4. While at neutral soil pH. the total As concentrations in aqueous solutions in equilibrium with calcium arsenates at the pH range 4.. The authors concluded that compost amendment can significantly reduce risk of human exposure to toxic As concentrations. Also.. / Waste Management 28 (2008) 215–225 des can adsorb high amounts of As (Chiu and Hering. Solidified monoliths are created. 2002). Shiralipour et al. In the presence of Ca under highly oxidizing and moderate pH conditions. 2001). at moderately reducing conditions) (Porter et al. Studies on nine artificially CCA-contaminated soils revealed that in mineral soils on average 92% of total As was As(V). Hartley et al. Mn oxides can be reduced at higher Eh values compared to Fe oxides and therefore can release adsorbed As before Fe oxides get dissolved (Stuben et al.. According to ˜ Wenzel et al. while in highly organic soils the proportion of As(III) significantly increased to one third of the total soil As (Balasoiu et al. where the mobility of As is a diffusion controlled process..5 are too high to consider this as a feasible remediation measure (Magalhaes. FA and CA adsorption to ferrihydrite outcompeted As(III) adsorption at low pH. 2002.. calcium hydrogen arsenate (CaHAsO4) and calcium arsenate (Ca3(AsO4)2) can precipitate (Porter et al. Alkaline materials usually are used to stabilize/solidify As contaminated soils (Jing et al. (2001). (2003) observed a drastic increase in As leaching from a compost amended soil.1.7. 2004) due to the higher mobility of As at higher pH range. 2004). Organic matter can change As speciation by reducing As(V) to more toxic and mobile As(III).

2003) and... 2000). 2001. 2005). such as synthetic and natural apatites and hydroxyapatites (Shi and Erickson. The reduction of Cr in soils is accelerated by the presence of organic matter and divalent iron. Cu mobility increases as Cu–HA and Cu–FA complexes are formed (Hsu and Lo. 2001). 2003. Cr was not a contaminant in focus and the effects of soil amendments on the Cr stabilization were observed in a context of the other contaminants.. although composting of sewage sludge prior to the application was recommended (Sanchez-Monedero et al. Brown et al. Recent studies show that the mobility and availability of Cu can be reduced by OM applications. 2001. Cl. An increased amount of clay minerals (palygorskite) in soil by 4% decreased Cu mobility by 77% (Alvarez-Ayuso and Garcia-Sanchez. CaCO3 that increase soil pH above neutral favor the oxidation of Cr(III) to Cr(VI) (Pantsar-Kallio et al.. Carbonates. The suggested mecha- nisms of Cu retention were precipitation of Cu carbonates and oxy-hydroxides. 2001.3. The mobility of Cu is usually the lowest at slightly alkaline pH but can increase in highly alkaline conditions (>10) due to the formation of OHÀ complexes (van der Sloot et al... 2001. Application of fly ash-stabilized sewage sludge also reduced Cu leaching and availability to corn (Su and Wong. 2005). 2005. Higher Cu mobility and availability to earthworms was reported in soil amended with sewage sludge (Kizilkaya. Chen et al. Application of coal fly ash to soil. 3. 1999). phosphate-based salts (Cao et al.. 2004). iron grit (Fe(0)).. This can cause a higher Cr mobility and uptake by vegetation (Rai et al.. Seaman et al. Kim and Dixon. X = F. 2002. hydroxyapatite. 2003a). ¨ 3. Copper Stability of Cu in soil is strongly pH dependent – the mobility increases with decreasing pH. non soluble high molecular weight organic acids can retain significant concentrations of Cu in soil upon soil acidification (Chirenje and Ma. phosphoric acid (Melamed et al. 2000). Cr(VI). The well-known high affinity of Cu for organic matter has two-sided consequences.. (2003).. as demonstrated by Arnich et al. By-products like sugar foam. (2004) tested several iron amendments: goethite. 2004. Cao et al. iron(II)/(III) sulfates plus lime. Pantsar-Kallio et al. alkaline materials like fly ash. 2003. Less research done on the Cr stabilization is likely due to a low reactivity of its usual species found in soil – hydrous chromium oxide.. but none of the treatments were efficient for the Cu stabilization. Ownby et al. 1995).. Scheckel et al.J. Lead Most of the studies on the Pb stabilization were performed using various phosphorus-containing amendments. 1997). dolomitic residue and to a lesser extent gypsum and phosphogypsum. phosphate rock (Geebelen et al. Therefore. However.. 2006). The OM-bound Cu fraction was reported to account for 96% of the total Cu in CCA-contaminated soil (Balasoiu et al. Even if Cr added to soil is in its mobile form. diammonium phosphate (McGowen et al. Hizal and Apak. 2005). is an efficient measure controlling Cu mobility (Jackson and Miller. their application to soil may not always lead to a success. The phosphate amendments added to contaminated soils reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals [Pb5(PO4)3X. 2005. If Cr in soil is converted to trivalent oxide or co-precipitated with Fe hydrous oxide that have low mobility and bioavailability in soils (Fendorf.. In the recent studies. phosphates and clays can keep Cu mobility in soil low by chemisorption (Kabata-Pendias and Pendias. 3. However. can also reduce the mobility and availability of Cu in soil (Garrido et al. Manganese oxides can negatively affect a Cr valence by oxidizing Cr(III) to Cr(VI) in soil (Guha et al. 2005. while a combination of these amendments even increased Cu leaching by 170% over the untreated soil (Ciccu et al. 2002. are not bioavailable. it is likely to remain stable for a long time. PO3À Þ complexes on the surface 4 4 of Fe and Al oxy-hydroxides. Mn oxides are generally good sinks for Cu (Kabata-Pendias and Pendias. Chromium The mobility of Cr in soil depends on its oxidation state.. Brown et al. B or OH]. 2004). Al. Peat and highly organic soils can bind significant amounts of Cu. In the presence of dissolved OM. ion exchange and formation of ternary cation–anion ðSO2À .. respectively. Also. Kumpiene et al. Hartley et al. Impellitteri.. Mixing organic matter and fly ash can be beneficial for offsetting a decrease in soil pH due to the decomposition of OM (Jackson and Miller. 2003). 2003.. 2002).. 2000). 2005) and their combinations.4. 2004). that usually increases soil pH and an amount of carbonates. The newly formed minerals have a very low solubility and bioaccessibility (Hettiarachchi et al. / Waste Management 28 (2008) 215–225 219 tion. Raicevic et al. It was observed that the presence of Zn increased As sorption on goethite by fivefold at pH 7 through surface precipitation of Zn–AsO4 complexes (Grafe et al. Acid extractable Cu fraction decreased in soils amended with four different mixtures of sewage sludge and cotton waste. Ownby .. 2001). the use of certain amendments should be avoided in Cr contaminated sites. Scheckel and Ryan. 2004). On the other hand. 2000) and enhancing Cu sorption on clay mineral surfaces through ternary Cu-mineralhumic acids complexes (Arias et al.2. 1997). Although Fe.... Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to a rather stable in natural environments Cr(III). 2001). 2001. 2000).. it tends to be converted to the trivalent oxide when in contact with the natural environment (Barnhart. Ownby et al. increasing of soil pH to above 8 by the application of coal fly ash (15% by weight) and red mud–gypsum (15% by weight) showed less than 50% and 10% efficiency. 2005). 2004).

. 2005). 2004). 2004).. According to Porter et al. however. Kumpiene et al. Lombi et al. limestone. which is mainly caused by an increase in soil pH. The leaching of Pb in field can be reduced to >99% (Wang et al. The precipitation of fluoropyromorphite was the main mechanism responsible for Pb retention (78%) that dominated over surface sorption/complexation reactions. P added to soil can easily form other minerals e.. The amount of amendment used is one of the key factors controlling remediation efficiency. However.. Brown et al. besides the very high concentrations of needed P.0 even for the soil contaminated with Pb concentration as high as 11... Competition of Zn for phosphorus amendments was suggested to be responsible for remaining Pb bioavailability in treated soils (Ownby et al. Garcia et al. Ca compounds are generally efficient for the Pb immobilization. 2003). 2003. Brown et al... Garcia et al. such as rock phosphate.. (2004) cautions that the high rates of P needed to immobilize Pb remain questionable seeing as an excess of soil P is a potential source of the eutrophication of surface waters. 2005. (2005) performed a comparative study on a row of soil amendments. Despite the reported high treatment efficiencies. (2002) observed a significant reduction of acid extractable Pb fraction (using CH3COOH as extractant) after phosphate rock (1%) application to eight contaminated soils from four countries.b. 2004.. or as a molar ratio of P/Pb. Geebelen et al.  Zeolites (Chen et al.. 2004). By contrast. Sauve et al. are also suggested (McGowen et al.. / Waste Management 28 (2008) 215–225 et al. 2002a.g. Brown et al. The increased soil acidity. Castaldi et al. triple super phosphate. soil acidification may be needed. 2003.g. 2002a. Garcia et al. 2005). e. 2005). Alkaline compounds are more useful if used as supplements to neutralize soil acidity caused by other amendments.. Melamed et al. 2002). (2004) found that insoluble fluoropyromorphite [Pb10(PO4)6F2] was formed in soil amended with phosphate rock containing F.. such as liming. 2005). Castaldi et al. phosphoric acid. Brown et al. limestone (CaCO3). 2004. such high pH values are unusual for soils.1 and below (Geebelen et al.. However.. compost (Chen et al. 1997. (2003) suggested the sufficient molar ratio of P/Pb to be 4.b. an admixture of more soluble P amendments followed by the application of phosphate rock and calcium phosphates were recommended (Melamed et al. (2005) reported reduced Pb bioavailability to earthworms as a result of phosphate rock addition to a Pb contaminated soil... Brown et al. Traditional means. may affect the leaching of other trace elements and increase soil toxicity (Ownby et al. As such..  Iron and manganese oxides (Chen et al. 2002a. Application of 1% lime to ten contaminated soils showed no significant effect on the acid extractable Pb fraction or even increased the Pb leaching at soil pH 8. Presence of competing ions usually reduces the treatment efficiency. cyclonic ashes. 2000. 2005).b. Based on their thermodynamic calculations. 2004. 2000. makes direct efficiency comparisons between various studies difficult. 2002. Brown et al. H3PO4. To avoid the negative effects of soil acidification. coal fly ash (Ciccu et al. A number of other soil amendments have been tested for their ability to immobilize Pb in soils showing a varying degree of their efficiency:  Alkaline compounds: calcium hydroxide (Ca(OH)2).. 2000. 2005).220 J. 2005). 2003). apatite and manganese hydrogen phosphate (MnHPO4) rather than pyromorphites. and concluded that application of P as triple super phosphate and . e. (2004).. This mineral was shown to be highly stable under a wide range of pH (3–9). lime (CaO) (Chen et al.6 g kgÀ1. To dissolve other P amendments. the use of differing amendment rates and differing ways of presenting them. Melamed et al. In general. 2005).. Brown et al. steel shots and red muds.. application of Ca compounds alone might not be sufficient for a long-term Pb immobilization.  Red gypsum and phosphogypsum (Garrido et al. Geebelen et al. Highly alkaline conditions can have a reverse effect on Pb stability due to the amphoteric nature of Pb and at pH > 11–12 formed soluble hydroxide complexes can increase Pb mobility (van der Sloot et al.. 2001). 2004). The formation of pyromorphite in soil requires dissolution of Pb and P amendments. calcium carbonate.. The amount of added material is usually expressed as a percent of amendment added to soil (weight ratio). phosphate rock. 2005). Pb removal by phosphate rock was least affected by the presence of competing metals compared to Cu and Zn (Cao et al... Since soil pH might not be stable and acidification would lead to Pb release.. 2003). the treatment efficiency of soil contaminated with Pb by phosphorus compounds is very high. a range of biosolids. According to Porter et al. the amount of P in soil needs to be increased to the levels that are 20 times the normal P concentration in soil... Ciccu et al.  Biosolids. Castaldi et al.g. 2004. steel shots (Brown et al. 2000. 2000... Easily soluble phosphoric amendments lower soil pH and increase the concentration of Pb in solution (available for reactions) leading to an instantaneous formation of pyromorphitetype minerals (Chen et al. The rate and effectiveness of the Pb immobilization depend on the solubility of Pb and P compounds. Basta and McGowen.. 2005). cyclonic ashes (Lombi et al.. as a concentration of P per kg soil or t per ha. Cao et al. The authors suggested that the only way to avoid this is to increase the amount of added phosphorus.. precipitated high amounts of apatite-like minerals can adversely change the soil structure.. 2001). stable pyromorphites in soil can be formed only after all soluble Ca and Mn are excluded. red mud (Lombi et al. some doubts about stabilization of Pb contaminated soil by P are expressed (Porter et al. Phosphate-based salts and phosphoric acid are more soluble compared to phosphate rock and therefore more efficient (Brown et al. (2004).

(2005) reduced the extractable Zn in amended soils. 2003b) were shown to be very efficient for Zn retention. a range of biosolids.. the presence of As anions were observed to increase Zn sorption to goethite by an order of magnitude (Grafe et al. molybdates and several other anions as well as form complexes with organic ligands (Kiekens. several contaminants of an opposite charge can have a synergistic effect on each other and significantly increase the retention capacity by. Cation exchange and complexation by organic ligands were suggested to be the main Zn mobility controlling mechanisms in acidic soils. 2003). 2004). Pb.7% and 99. no improvement in plant uptake and bioavailability over the non amended soil was observed.. 2000). Magnesium aluminum silicate clays. Mn and Fe oxides. Although a number of soil additives (limestone. 2004). Zn can precipitate with hydroxides. Hartley et al. and organic matter. Alkaline industrial by-products like fly ashes can neutralize soil acidity arising from acid mine drainage generation in sulfide-rich waste and prevent contaminant spread (Iyer and Scott. including Zn-phosphate and Zn sorbed to ferrihydrite... Both transformed species are much more mobile and toxic. The remediation of soils contaminated with several elements at different concentrations requires solutions effective for all target elements. Mg.g. The application of different organic mixtures to soil also considerably increased the fraction of available Zn (SanchezMonedero et al. 2004). The treatment efficiency using a 4% clay dose reduced the readily extractable (water soluble + exchangeable) Zn fraction by 76% (palygorskite) and 99% (sepiolite) from highly polluted mining soils. Undesirable reduction of available quantities of nutrients in the Fe amended soil requires additional soil amelioration. Fly ashes have a more sustained neutralizing effect than lime (Seoane and Leiros. Cd and Cu concentrations were decreased five to tenfold. (2004) reported a fivefold increase in Zn mobility when treated with iron sulfate and lime. respectively (Ciccu et al. Impellitteri (2005) observed only a slightly reduced Zn solution concentration after an application of phosphoric acid. Al. ¨ Lime can effectively reduce the mobility of Cu and Pb in contaminated soils by raising the soil pH. Treatment with zerovalent iron significantly reduces concentrations of contaminants accompanied by the immobilization of macro elements. Phosphorus addition significantly reduced soil solution. Stabilization of multi-element contaminated soil Most contaminated sites have elevated concentrations of more than one element making the solution to the problem more complex. 2001. forming complex As– Zn precipitates on Fe oxy-hydroxides (Grafe et al.. 2003). sulfides. Based on extended X-ray absorption fine structure (EXAFS) spectroscopic analysis of inorganic fractions of a clayey soil. 2001. Cu) for adsorption sites (Cao et al. 2004) may seem to facilitate the choice of stabilizing amendments. The presence of one contaminant (e. 2002). Cu or Pb) can decrease the stabilization efficiency of the other (e. The different properties of the contaminants restrict the choice of possible amendments in order to avoid. did not grow on As contaminated spoils amended with 1% steel shot (Fe(0)) without fertilization (Bleeker et al. Zn was predominantly associated with phyllosilicates (layer silicates) and all other fractions. But when sewage sludge was mixed with fly ash. Grasses like Holcus lanatus and Agrostis castellana. while Al. 2003). Amorphous Fe(III) hydroxide (ferrihydrite) can be an effective sorbent for both anions and cations. 2002).g. Xenidis et al. 3. McGowen et al. phosphates. Contrary to that. bioavailable and NH4NO3 extractable Pb and its concentration in plant tissue.. Alkaline materials like coal fly ash and red mud also decreased Zn leaching by 99. It is possible to improve the treatment efficiency of multi-element contaminated sites by applying a combina- . at the same time as Pb. 2004). The mobility of Zn is modified by the presence of P... 1995)... / Waste Management 28 (2008) 215–225 221 H3PO4 were the most effective over all the amendments tested. 2003a) and sepiolite (Mg4Si6O15(OH)2 Æ 6H2O) (Alvarez-Ayuso and Garcia-Sanchez. 2001.g. The surface of Fe hydroxide particles can be positively or negatively charged depending on pH making the Fe hydroxides amphoteric (Cornell and Schwertmann. 2005). Mn and Fe oxides were of less importance (Kabata-Pendias and Pendias. steel shots and red muds) tested by Brown et al. 2001). 2004. Zn is a rather mobile element (Kiikkila. P. Zinc The high diversity of Zn compounds in soils (Manceau et al.. 2003) ¨ and easily out-competed by other cations (e.. 2004). for example. 2002. carbonates. but due to acid liberation is not recommended in soils containing high concentrations of metal contaminants (Warren et al.. for example.J. like palygorskite (attapulgite) ((Mg.. Kumpiene et al. such as Ca. However. cyclonic ashes. contained less than 10–20% of the total Zn (Manceau et al. considered as As tolerant plants. Other studied amendments seemed to provide less promising results. but increasing soil pH to alkaline region can increase the risk of Cr(III) transformation to Cr(VI) and As(V) to As(III). The Fe sulfate application can successfully immobilize As. Kizilkaya. leaching of Zn and uptake by corn was significantly reduced (Su and Wong. Results indicated that Zn was immobilized as metal-phosphate precipitates with low solubility and high resistance to soil acidification. (2001) observed that the reduced Zn extractability in soil treated with lime stabilized biosolids was lost when soil was acidified to pH < 6. Zn) due to competition for sorption sites. and therefore undesirable.. Ca. 3. 2004). Brown et al. 2004.6. Basta et al.Al)2Si4O10(OH) Æ 4H2O) (Alvarez-Ayuso and Garcia-Sanchez. Panfili et al. By contrast.6%.5. large pH fluctuations and consequent mobilization of one or more of the elements. ¨ A number of studies have been done attempting to stabilize Zn in soil by phosphorus amendments (Basta et al. Hamon et al. However. 2005.

Some similarities are also seen in the response of As and Cr to the amendments.. 1–12. The trace element retention by OM depends on several factors. and have a reverse effect on the retention of As..W. Zn and Pb is strongly pH dependent. A. In most studies.. with lowest mobility being around neutral to slightly alkaline conditions. Standardized leaching tests do not cover all scenarios appearing in the field. 2002. 2003). 2003) as well as lime (McGowen et al. have similar responses to the same amendments. Kumpiene et al. the type of amendments is important. Instead. can increase the element retention capacity of OM by forming ternary clay–metal–organic matter complexes (Arias et al. Redox reactions and microbial processes are usually omitted.. 2002). Palygorskite as a feasible amendment to stabilize heavy metal polluted soils. D. References Table 1 Summary of the reported efficiencies of the amendments Amendment Phosphorus materials Organic matter Clays Alkaline materials Fe oxides Mn oxides As À +/À + À ++ ++ Cu + +/À + + +/À Cr ++ À ++ À Zn + +/À ++ ++ + Pb ++ +/À + +/À + (++) = Very good. It is difficult to make long-term stability predictions based on short-term laboratory tests. All of these elements could be retained in soil amended with phosphorus. E. This element grouping is mainly determined by the dominant trace element charge: Cu. Alkaline materials clearly should be avoided as the mobility of these elements usually increases in the alkaline pH range. Leaching of Cu. A. dominance of low solubility having high molecular weight organic acids versus highly soluble low molecular weight acids. and therefore their reaction to pH changes generally has a reverse pattern.g. 2004. where processes occurring in stabilized soil can be observed for several decades.. Hence. Bolan. 4.. 121–142. . Soil acidification due to phosphoric acid can also be managed by the following application of phosphate rock and calcium phosphates (Melamed et al. 1081–1088. Acknowledgement This work was financially supported by European Union Structural Funds and New Objective 1. Analyzing soil samples taken from such sites that were contaminated several decades ago for chemical. However. Role of assisted natural remediation in environmental cleanup. i. Zn and Pb appear as cations. Geoderma 122. Cu. Other soil constituents. physical.. But field experiments. However. mineralogical and biological development in comparison to adjacent clean soil might give an approximation of what could be expected in the future of the stabilized soil. can greatly modify element mobility.. Alvarez-Ayuso. 337–344.222 J. liming) are necessary. Environmental Pollution 125 (3).. For example. 2004).C. Other factors. Mejuto. recommendations for future monitoring are given as the effects of the amendments are observed only for the first few years after the soil treatment. Natural remediation (attenuation) occurs in moderately contaminated sites and ecosystem recovery slowly takes place despite the remaining elevated trace element concentrations (Lepp and Dickinson. are impractical. Sepiolite as a feasible soil additive for the immobilization of cadmium and zinc. therefore. For example. J. (+) = satisfactory to good..g. Zn and Pb.C.g. (À) = avoidable due to obvious negative effects on the element leaching. Clays and Fe oxides seems to be efficient for all of the elements. Vangronsveld. no suggestions for how to do this are given. Garcia-Sanchez. some answers could be found in nature. 2001). while Fe added to soil in form of sulfides can lower soil pH and have a reverse effect on the leaching of cationic elements. when adding phosphoric acid or iron sulfate to soil. Fly ash stabilized sewage sludge can prevent the leaching of trace elements and their uptake by plants (Su and Wong. Wenzel. / Waste Management 28 (2008) 215–225 tion of amendments. Three elements. e. M. Adriano. Concluding remarks The above reviewed soil amendments and their efficiencies for trace element immobilization in soils are summarized in Table 1. North Sweden Soil Remediation Center. e. iron or clay materials. Alvarez-Ayuso. E. acid liberated in iron sulfate amended soils can be neutralized applying appropriate amounts of lime. 2003a. like redox potential. (+/À) = varying results showing week improvements or both positive and negative effects on the element mobility. This confirms that pH is one of the most important factors having a very strong impact on the element mobility in soil. Chemosphere 48 (10). 2003b.. Although most studies are concluded with the expressed necessity for a long-term stability assessment of the immobilized elements.. fly ashes. Organic matter had the most varying impact on the element mobility. 2003). especially of redox sensitive elements like As and Cr. Barral..e.. Garcia-Sanchez. Clay-type materials can also be alkaline.S. M. such as soil pH and degree of OM humification. W.T. fresh biosolids usually have low degree of humification and therefore contribute to the element mobilization rather than to their retention. Arias. and leaching of metals could be avoided (Warren et al. The Science of The Total Environment 305 (1–3). additional pH-controlling measures (e. particular attention should be paid to changes in soil pH induced by the amendments. J. the impact of OM on the element retention is case specific and any generalizations are difficult to make. while As and mobile Cr(VI) as oxyanions. Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids. ( ) = not found in the reviewed literature.. N. clay. The successful stabilization of multielement contaminated sites depends on the combination of critical elements in soil and the choice of amendments.

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