You are on page 1of 10

Chemosphere 62 (2006) 171–180

www.elsevier.com/locate/chemosphere

Immobilization of heavy metals in polluted soils
by the addition of zeolitic material synthesized
from coal fly ash
Xavier Querol a,*, Andre´s Alastuey a, Nata`lia Moreno a,
Esther Alvarez-Ayuso b, Antonio Garcı´a-Sa´nchez b, Jordi Cama a,
Carles Ayora a, Mariano Simo´n c
a

b

Institute of Earth Sciences ‘‘Jaume Almera’’ (CSIC) c/Lluis Sole´ i Sabarı´s, s/n, 08028, Barcelona, Spain
Instituto de Recursos Naturales y Agrobiologı´a (CSIC) c/Cordel de Merinas, 40, Apdo. 257, Salamanca 37071, Spain
c
Departamento de Edafologı´a y Quı´mica Agrı´cola de la Universidad de Almeria, Spain
Received 22 December 2004; received in revised form 12 May 2005; accepted 13 May 2005
Available online 21 July 2005

Abstract
The use of zeolitic material synthesized from coal fly ash for the immobilization of pollutants in contaminated soils
was investigated in experimental plots in the Guadiamar Valley (SW Spain). This area was affected by a pyrite slurry
spill in April 1998. Although reclamation activities were completed in a few months, residual pyrite slurry mixed with
soil accounted for relatively high leachable levels of trace elements such as Zn, Pb, As, Cu, Sb, Co, Tl and Cd. Phytoremediation strategies were adopted for the final recovery of the polluted soils. The immobilization of metals had previously been undertaken to avoid leaching processes and the consequent groundwater pollution. To this end, 1100 kg of
high NaP1 (Na6[(AlO2)6(SiO2)10] Æ 15H2O) zeolitic material was synthesized using fly ash from the Teruel power plant
(NE Spain), in a 10 m3 reactor. This zeolitic material was manually applied using different doses (10 000–25 000 kg per
hectare), into the 25 cm topsoil. Another plot (control) was maintained without zeolite. Sampling was carried out 1 and
2 years after the zeolite addition. The results show that the zeolitic material considerably decreases the leaching of Cd,
Co, Cu, Ni, and Zn. The sorption of metals in soil clay minerals (illite) proved to be the main cause contributing to the
immobilization of these pollutants. This sorption could be a consequence of the rise in pH from 3.3 to 7.6 owing to the
alkalinity of the zeolitic material added (caused by traces of free lime in the fly ash, or residual NaOH from synthesis). 
2005 Elsevier Ltd. All rights reserved.
Keywords: Coal fly ash; Zeolite; Immobilization; Metals; Polluted soils; Soil remediation; Aznalcollar mine spill

1. Introduction

*
Corresponding author. Tel.: +34 934095410; fax: +34
934110012.
E-mail address: xavier.querol@ija.csic.es (X. Querol).

High concentrations of heavy metals in soils may
cause long-term risks to ecosystems and humans.
Although heavy metals are released in varying quantities into the soil from parent materials, increasing
environmental contamination has been caused by

0045-6535/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2005.05.029

Basta et al. These amendments can lead to the immobilization of metals in a variety of ways... K-chabazite. clays play a significant role in surface complexation because of their higher specific surface (Du et al. Golberg and Glaubig. KM (equivalent to phillipsite). All the methodologies developed are based on the dissolution of Al–Si-bearing fly ash phases with alkaline solutions (mainly NaOH and KOH solutions) and the subsequent precipitation of zeolitic material. Since the initial studies by Ho¨ller and Wirsching (1985).172 X. smelting. This pond is located at Aznalco´llar (Sevilla). alkaline agents. Thirdly. 1971. An area 40 km long and 0. such as mining. with group I or II elements as counter ions.b). Their structure is made up of a framework of [SiO4]4 and [AlO4]5 tetrahedra linked to each other at the corners by sharing their oxygens.. or as minor components co-precipitated in hydroxides (Chlopecka and Adriano. have been recently tested in order to evaluate their ability to immobilize toxic trace metals. 1984). Co. 2001). mixed with soil. and consequently may also favour plant growth. ENDESA) (Querol et al. 2001. 2000. to the polluted soils to diminish the leachable contents of heavy metals during phyto-remediation. Marosits et al. The synthesis conditions were selected from prior studies (Querol et al. Among soil minerals. and other high CEC zeolites have been obtained from coal fly ash. 2003) at many of the most seriously contaminated sites. 1993. A pyrite slurry spill occurred in the Guadiamar river (a tributary river of the Guadalquivir river. Materials and methods 2. 1996). Chemical immobilization prevents the transport of contaminants into deeper soil layers and into groundwater. The alkalinity of the zeolitic product (due to residual NaOH from synthesis. Vangronsveld and Cunningham. Miranda-Trevino and Coles.. and they acquire a negative charge as pH increases owing to the deprotonation of the surface unsaturated bonds.. phosphate rocks. 1994. 1997) to obtain high NaP1 products (Na6[(AlO2)6(SiO2)10] Æ 15H2O) owing to the high CEC values of the NaP1 zeolite (5 meq/g). Ni. 1999). Linde F. NaP1 (Na6[(AlO2)6(SiO2)10] Æ 15H2O). 2001). This study focuses on the application of NaP1 zeolitic material. / Chemosphere 62 (2006) 171–180 human activities. 1995). such as carbonates. Golberg. Boisson et al.. persistent soil pollution was locally detected due to the presence of a small fraction of pyrite mud. fossil fuel combustion. These neoformed phases contain metals as major constituents. Synthesis of zeolitic products Zeolitic products were obtained at pilot plant scale (at CLARIANT SA) by alkaline conversion of coal fly ash from the Teruel power plant (NE Spain. as pH increases cations form stable complexes with the negative radicals on the surfaces. amend- ments increasing the soil pH may also result in As mobilization (Hingston et al.. Zn and As. 1997a. The substitution of Si(IV) by Al(III) in the tetrahedra accounts for a negative charge of the structure which may give rise to a high cation exchange capacity (CEC) (up to 5 meq/g) when the open spaces allow the access of cations (Breck. or synthesized from a wide variety of high Si and Al starting materials. Seaman et al.. environmental risks persist. Despite the natural capacity of soils to reduce solubility and bioavailability of metals (Mitchell.5 km wide (following the Agrio and Guadiamar valleys) was covered by a 30 cm to 3 m thick layer of pyrite slurry. 2000. Secondly. 1998). such as metal-phosphates and carbonates (Chen et al. Therefore. However. since As forms anionic species in solution. where the sulphide ore deposits were extracted. zeolites. Mineral surfaces have a positive charge at low pH values due to the sorption of protons. with high concentrations of trace elements such as Cd. A number of natural or synthetic materials.1. The Teruel fly ash was selected to reproduce the laboratory tests at pilot plant scale by using a low-glass fly ash (see major characteristics of this fly ash in Table 1). After soil reclamation. a number of patents and technical articles have proposed different hydrothermal activation methods to synthesize diverse zeolites from coal fly ash. causing the precipitation of insoluble phases. generally associated with the alkaline activation of glassy volcanic rocks. Querol et al. 2. NE Spain). agricultural practices and waste disposal (Ross. Na-chabazite (herschelite). The experiments were carried out in a 10 m3 . Castaldi et al. Chemical immobilization by means of soil amendments has been recently investigated as a valuable alternative technique for a wide range of contaminated sites (Vangronsveld and Cunningham. Alloway. SW Spain) on 25 April 1998 as the result of the collapse of a dam in a pond containing pyrite slurry and waste water with a high content of potentially toxic elements (Grimalt et al. synthesized from coal fly ash from the Teruel power plant (ENDESA. 1988). some amendments dissolve supplying alkalinity to the acid polluted soil. 1999)... zeolites A and X. metal retention may also take place regardless of pH due to the cation exchange in zeolites (Nissen et al. clay minerals and organic materials. the increase in alkalinity promotes the metal sorption via surface complexation processes. Firstly. Cu. 2005). demanding immediate action. or to the occurrence of free lime in relict fly ash particles) may also contribute to buffer the acidity of the soil.. 1998... Zeolites may be found in natural deposits. Moreover. revegetation of highly polluted sites might be possible after immobilization of phytotoxic trace elements (Vangronsveld et al. Using this procedure. 2000. 1986. 1996. Zeolites are crystalline aluminum-silicates.

The pH was determined potentiometrically in a soil paste saturated with water. The minerals present in the sample were determined by XRD patterns and the proportions quantified by the Rietveld method (Rodrı´guez-Carvajal et al. montmorillonite. Al and Si glass. at 150 C (Querol et al. The zeolitic material synthesized was filtered (55 pneumatic press filters.9 1. illite..5 0.9 16.0 meq/g obtained for the final product points towards a zeolite content of around 45% (when compared with the 5 meq/g obtained for the IQE commercial zeolite). 1995).7 5. The sample was made up of quartz.8 75. In addition to the zeolite.4 0. The experimental parameters used for the synthesis of 1100 kg of this zeolitic material in a single batch were: 2 l of 2 M NaOH/kg fly ash during 24 h. The <2 mm fraction was used with this aim.060 Mineralogy (% from XRD analysis) Quartz Illite Clinochlore Montmorillonite Actinolite Feldspars Gypsum 30 20 5 5 5 25 8 Grain size distribution (%) 250–2000 lm 50–50 lm 50–2 lm <2 lm 45. dried at room temperature and analyzed by means of X-ray diffraction (XRD) with CuKa radiation.2 0. 1987). clinochlore. mullite.2.80 0.X.0 12.. A CEC value of 2. the final product contains relict fly ash particles made up of quartz.5 1.3 23. microcline + albite and gypsum. R-410-A reactor made of 304 stainless steel.8 2. Accurately weighed amounts of each sample were acid digested following a two-step dissolution procedure Table 2 Selected soil properties Properties Soil control pH Organic matter (%) Carbon (%) Nitrogen (%) 3. Contents of C and N were determined in the control soil with an elemental analyzer.6 21.2 1. The CEC of the zeolitic materials was calculated using ammonium solutions following the methodology of the International Soil Reference and Information Centre (ISRIC. 2001).2 1. traces of lime. A semi-quantitative esti- Representative samples of the contaminated soil were collected to determine the main soil properties (Table 2). 90 C during 1 h) and washed with water (at 85 C during 40 min).0 173 mation of the zeolite contents was obtained comparing their CECs with that of a pure NaP1 commercial product (produced by Industrias Quimicas del Ebro.9 0. respectively. / Chemosphere 62 (2006) 171–180 Table 1 Major chemical and physical characteristics of the Teruel fly ash Major oxides (%) SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O P2O5 TiO2 SO3 SiO2/Al2O3 Trace elements (lg/g) As B Ba Cr Cu Li Mo Pb Sr U V Zn Mineral composition (%) Glass Mullite Quartz Anhydrite Lime Hematite Magnetite Feldspar Physical characterisation Grain size (lm) P10% Median P90% True density (g/cm3) Apparent density (g/cm3) Porosity (%) BET SA (m2/g) 48. 2.7 8.6 1. and residual NaOH from synthesis.9 P10% and P90%: percentile 10% and 90%. Organic matter was determined by dichromate oxidation using the Tiurin method (Jackson.0 5. actinolite.4 8.0 0. Soil sub-samples of the <260 lm fraction were used for the total content metal determination.5–3.4 1.8 0.8 . 1960) and particle size distribution was analysed by the pipette method (Gee and Bauder.0 4. Soil properties 79 342 311 107 52 256 15 65 523 20 206 174 62.3 <1. Querol et al.7 2.46 0.7 19. 1986).5 31.1 58. IQE). magnetite.

pH and leachable concentrations (DIN 38414S4) of major and trace elements of the samples obtained in the 27/04/2000 and 23/03/2001 sampling periods (1 and 2 years after the addition of NaP1-TE).5 to 7. 25 ml of suspension were filtered through a 0. The mixture was stirred for 2 h to reach equilibrium.5 is stirred for 2 h using 1 M NH4NO3 as extracting agent. Metal concentrations in the extracts were analyzed by AAS. the mobility of metals as a function of time was studied as water was added. Column tests In addition to the above closed leaching procedures. Sampling of treated and control soils was carried out in 27th April 2000 and 23rd March 2001. The contents of major and trace elements in the solutions obtained from the total sample digestion were analysed by (a) inductively coupled plasma atomic emission spectrometry (ICPAES) for major and selected trace elements (Ca. 3. P. ranging from 3. V and Zn). indicating high As soil pollution and need of its remediation. 1995) the total concentration of As surpasses greatly the standard intervention value (55 mg/kg). and the conductivity. Cu. Cd. According to the Dutch legislation concerning soil and groundwater contamination by toxic substances (Netherlands Ministry of Housing. Mo.1. using glass columns packed with 100 g of either untreated soil (con- Table 3 gives the results of the bulk content of major and trace elements in the original soil. Sr.5. a series of batch experiments were conducted at room temperature (21 ± 2 C) to examine the variation of metal aqueous concentration (Fe.5 was maintained constant by adding different amounts of 1 M Na2CO3.45 mm Millipore filter and ICP-MS was used to analyse the contents of trace elements.174 X. The columns (3 · 15 cm) were leached with 400 ml (560 mm annual rainfall in this area) of de-ionized water under a saturated flow regime. Co. Ni. The DIN V 19730 (1993) procedure was used to this end.1. Cr. on 29th April 1999. Experiments consisted of mixing 1 g of soil sample (grain fraction between 30 and 100 mm) into 100 ml of desired pH solution. Five replicates were sampled from each field to tests the representativity of the sampling. Fe. Cu. Bulk and leachable metal concentrations 2. Zn. trol) or soil amended with zeolite (15 000 kg/ha.4. Pb. The contents of major and trace elements in the leachates were analysed by ICP-AES and ICP-MS. A control plot was kept as a reference. Effect of pH variation To assess the variation of the soil retention capacity with pH regardless of zeolite exchange processes. Furthermore.3. Soil treatment with zeolite In order to test the immobilization potential of the zeolite material for the leachable trace elements. Co. Afterwards.4. Nevertheless. The top 15 cm of soil from each field were sampled by collecting two continuous 20 cm wide channel soil samples connecting the corners of the square fields diagonally. Metal concentrations in the leached fractions were determined by atomic absorption spectrometry (AAS). Th. collecting successive leached fractions of 25 ml using a fraction collector (Foxy Jr. Physical Planning and Environment. Ti. before and after treatment.5. Na. Ba. Relative standard deviations (RSD) of different analyses were lower than 40% for most elements as later will be shown. Al. Mg. Cd. S. 24 h in a PVC container). the conductivity and pH were measured in the leachates using conventional procedures. the zeolitic product was dosed in proportions of 10 000. Al. Tl. 2 years after the flood). stirring under room temperature. Ba. Leaching studies 3. 25 000 kg/ha). while pH higher than 5. and Zn) and (b) inductively coupled plasma mass spectrometry (ICP-MS) for most of the trace elements (As. Cu. Querol et al. 2. Ni.2. Results and discussion 2. in an open leaching test. / Chemosphere 62 (2006) 171–180 (a HNO3 extraction followed by a HNO3:HF:HClO4 extraction) (Querol et al. therefore the risk of leaching and groundwater contamination with this element is really low in such .15%. 2.. Solution pH in the range of 3. Batch tests Accurately weighed amounts of each soil sample of the <260 lm fraction were leached following the DIN 38414-S4 (1984) procedure with the aim of determining the levels of water extractable elements (100 g of sample in 1 l MilliQ grade water. The soil material collected was mixed and riffled to obtain a final sample of 10 kg which was transported to the laboratory for analysis.5–5.. Mn. Ni and Mn) as a function of pH. ISCO). the readily extractable metal fraction was determined in the soil. the percentage of As extractable with water appears very low (<0. Analytical accuracy was checked with SARM 19 and 1633b reference materials and yielded analytical errors <3% with the exception of P and K (with 10%).5 was made up of HCl solutions.4. 1995). 2. In this method a soil mixture with a soil: extractant ratio of 1:2. In order to confirm possible ion exchange processes. 15 000 and 25 000 kg/ha and manually mixed with the 25 cm top soil in three experimental plots (20 m2 each) around the Vicario farm (Sanlucar la Mayor village).

2 <0.01 169 0.2 <0.7 0.01 18 0.01 0.09 8 ND 0.3 0.01 ND 0.01 0.01 <0.7 0.02 ND ND ND 0.01 1.01 0. total and leachable content in mg/kg of major and trace elements of the samples obtained in the 27/04/2000 and 23/03/2001 sampling periods (1 and 2 years after the addition of NaP1-TE) kg/ha Bulk content Leachable content 0 0 27/04/2000 Mean As Ba Cd Co Cr Cu Mo Ni Pb Sr Th Ti Tl V Zn 15 000 25 000 SDT Mean 0 SDT 10 000 15 000 25 000 SDT Mean SDT Mean SDT Mean Mean SDT Mean SDT Mean SDT Mean SDT 61 485 12 441 46 225 5525 605 14 952 486 12 042 1770 1633 5785 431 83 417 126 4324 2000 3.1 ND 0.5 ND 0.02 0.2 0.5 0.06 X.06 ND ND 0.01 0.4 0.01 73 0.01 <0.01 0.1 0.04 0.1 <0.2 <0.02 8 0.01 2.3 ND 0.01 0.1 0.2 ND 0.32 <0.1 <0.01 0.01 0.01 2.1 0.2 0.02 0.1 0.2 0.09 <0.02 0.03 0.04 <0.9 33 3920 2 179 145 79 1 4041 10 ND 4 218 1 10 14 23 <1 138 1360 7.02 0.01 <0.9 ND 0.9 <0.01 0.8 <0. Querol et al.2 0.01 4.2 <0.01 0.01 <0.02 ND 0.06 ND 0.6 2.9 205 4538 61 272 137 14 1 4692 10 ND 11 158 16 13 5 6 <1 104 1270 4.2 ND 0.05 0.0 <1 1618 <1 55 4 86 <1 1106 ND ND ND 105 ND 3 1 21 ND 43 650 8.08 0.03 0.2 0.01 0.4 1.03 0.01 0.01 1.03 0.02 0.4 7 2598 1 130 21 340 1 2130 ND ND 1 169 <1 7 5 85 <1 83 870 7.01 0.01 147 0.3 0.1 1.05 0.0 <1 1130 <1 59 1 137 <1 724 ND ND ND 76 ND 4 <1 30 ND 30 147 290 2 10 59 105 1 23 375 99 9 2271 2 83 276 56 26 1 1 10 11 1 4 126 12 3 1035 1 11 28 0.01 0.7 0.01 <0.01 0.03 0.02 ND ND 0.02 0.1 <0.02 0.8 0.7 ND 0.01 0.01 0.02 0.2 0.01 0.01 110 0.5 110 3293 30 247 145 268 1 3502 10 ND 7 115 8 11 5 112 <1 78 2200 3.1 127 2594 26 145 120 22 <1 2644 ND ND 9 144 2 8 12 6 ND 90 900 8.1 <0.1 ND 0.7 <0.2 <0.2 <0. (lS/cm) pH Al Ca Fe Mg Mn Na P S 23/03/2001 10 000 Based on DIN test using a solid/extractant ratio of 100 g/l.04 1.01 <0.3 0.02 0.01 1.01 0.01 ND 0.02 0.01 1.6 <0.4 ND 0.02 ND 0.01 0. pH.01 3.07 ND ND 31 0.01 0.6 <0.01 0.5 ND 0.01 0.01 1.4 0.01 0.06 ND <0.1 ND ND 23 0.05 0. ND indicates no detected.2 0.1 <0.01 <0.01 <0.06 ND 0.5 <0.01 0.2 ND 1. / Chemosphere 62 (2006) 171–180 Cond.04 ND ND 0.01 <0.5 <0.04 0.02 0.2 0.2 <0.01 0.1 0.1 0.6 2.1 0.03 0.04 0.3 <0.8 0.03 0.14 <0.1 0.51 <0. 175 .04 0.06 ND ND 47 0.4 7 1296 1 106 2 537 2 1098 ND ND 1 87 <1 8 1 116 <1 45 2200 3.Table 3 Conductivity.4 0.01 1.8 <0.3 0.1 11 <0.1 0.04 ND <0.2 ND 0.8 2.4 0.01 1.01 0.01 0.01 0.2 0.4 2.02 0.04 ND ND ND 0. Doses in kilogram of zeolite added per hectare of soil (kg/ha).1 <0.2 ND 0.7 0.01 2.1 <0.1 <0.01 <0.05 0.2 0.2 <0.02 0.

The mobility of these elements drastically decreased down to <1% after 1 and 2 years of the NaP1-TE zeolite addition with relatively low doses (15 000 and 25 000 kg/ha). pH and conductivity (27/04/2000) (a) and water extractable proportions for metals (% of element leachable in water with respect to the total content) as a function of the zeolite dosing after 1 and 2 years (27/04/2000 (b) and 23/03/2001 (c). V and Zn. 1. . 17–40% for Cr. Tl and Mo.9 after 1 and 2 years of the remediation activities. The buffering of the acidity of the soils may also result in the precipitation of some of the metals or in the adsorption of cations on clay surfaces.5 and 8. Cu and Zn. As. elements occurring in the pyrite slurry. P. The results demonstrated that 2 years after the flood. In the field. such as Cd. 28% Co. 15 ± 2 and 20 ± 2 lg As/l and <1 lg/l of Cd. with the exception of Zn and V with relative standard deviations from 20% to 65%. 165 ± 22 and 220 ± 27 lg Ni/l. pH Conductivity 8 2500 2000 1500 4 1000 2 500 0 0 5000 10000 a Leachable (%) 15000 25000 0 30000 March 2001 60 Cd Co 40 Cu Mn 20 Ni Zn 0 Cd Co 40 Cu Mn 20 Ni Zn 0 0 b 20000 Zeolite dose (kg/ha) April 2000 60 (µS/cm) pH 6 5000 10000 15000 20000 Zeolite dose (kg/ha) 0 25000 c 5000 10000 15000 20000 25000 Zeolite dose (kg/ha) Fig. Fig. Relative standard deviations (RSD) for bulk concentrations of major and trace elements in the replicates sampled in the reference soil reached values of 3% for Al and Na. 9 ± 2 and 10 ± 2 lg Ni/l. Co. Cu. respectively). 56 ± 4 and 80 ± 3 lg Cd/l. Co. 4 ± 2 and 60 ± 4 lg Pb/l. Although we recognize that the major pollution problem is As.0 as a consequence of the alkalinity of the zeolitic material. whereas the treated soils reached a pH of up to 7. RSDs of replicates for the leachable contents of trace elements in the reference soil varied from 3% to 17% for most elements. and 45–100% for Ti. although below the standard intervention values (12. Cu. The total concentrations of Cd. Concentrations of metals in leachates obtained with the DIN procedure (solid/extractant ratios of 100 g/l) applied to the control samples for the two sampling periods reached 14 692 ± 1758 and 16 900 ± 2331 lg Zn/l. 7% Cu and Ni. Querol et al. Ba. 8–15% for Ca. the water extractable contents are reduced down to 37 ± 13 and 10 ± 6 lg Zn/l. respectively) are close to them. 28 ± 8 and 20 ± 6 lg Cu/l. S. 282 ± 40 and 280 ± 36 lg Co/l. In the amended soils these RSD values are only slightly increased (7–20% for most elements). Pb. the control field had a pH of 3. 1. 1). with a zeolite dosage of 25 000 kg/ha. and Zn. suggesting that their control should be suitable as well. / Chemosphere 62 (2006) 171–180 and 53% Zn (Fig. 805 ± 69 and 1130 ± 798 lg Cu/l. Fe. 1b and c shows the percentage of water extractable concentrations (% element leachable in water with respect to the total content) for six elements depending on the zeolitic inputs of the doses of the zeolitic product. Ni.176 X. 190 and 720 mg/kg. Cd. Prior studies of heavy metal sorption from acid mine waters using NaP1 and 4A zeolites synthesized from fly ashes have demonstrated that the combination of the precipitation and ion exchange processes accounts for the following affinity of the elements with respect to the zeolite addition: Fe3+ = Al3+ > Cu2+ > Pb2+ > Cd2+ = conditions. Mn. especially in the case of Cu. Mg. Co and Pb. Sr. were leached in a very high proportion. and 20 ± 2 and 40 ± 14 lg As/l. Ni. we selected these polluted soils to test the effect of the zeolite dosage on the reduction of levels of leachable metals. In the control soil the leachable contents of these elements reached 45% Cd. As shown in Table 3 and Fig. Th.5 and 3.

The experimental fields with the addition of the zeolitic product showed significant plant growth.. Cu. Ni and Zn (>50%) were leached in the first two fractions (50 ml). In the case of Cu. As shown in Fig. 2. Lamarckia aurea and Mentha piperita. with respect to the control field. indicating that the water reachable fraction of the metals was almost completely leached (for the current stage of the weathering of sulphide phases).6% of Co. 0. 2) suggest a less effective leaching. the leached fractions of metals account for 1. Co. Oxalis pes-caprae.2% for Cd. 16% for Co. Thus the amendment considerably reduced the leached metal amount. 9% for Cu. Moreover. Co. 4% for Ni and 19% for Zn. 2. percolation curves (Fig. and Ni. 0.1% of the total content of Cd. and <0. 3. Ni and Zn. It should therefore be pointed out that the zeolitic product can selectively uptake metals in a high Ca and Mg media.1% of Cu. Most of the eluted amounts of Cd. probably as a consequence of the heavy metal sorption and the pH buffering effect of the zeolitic material. Querol et al. 600 .X. The leaching rate decreased along the percolated water volume. the percolation curves tend to reach the ‘‘plateau’’. The following plant species were identified: Lupinus angustifolious. Soil percolation tests The results of the open leaching tests (column tests) applied to the control soil and to the soils amended with zeolite (at doses of 15 000 and 25 000 kg/ha) are presented in Fig.03% for Co and Zn. the cumulative 18 15 12 Cd Leached % Leached % 15 9 6 3 9 6 0 0 200 400 600 0 10 200 400 8 Cu 6 4 2 4 Ni Ni 3 2 1 0 200 400 600 0 0 200 400 Water volume (ml) 25 Leached % 600 5 Leached % Leached % Co 12 3 0 0 177 20 Zn Zn Soil (control) 15 Soil (15 tonne/hectare) 10 Soil (25 tonne/hectare) 5 0 0 200 400 600 Water volume (ml) Fig.2. 2001a. 0. / Chemosphere 62 (2006) 171–180 Tl+ > Zn2+ > Mn2+ > Ca2+ = Sr2+ > Mg2+ (Moreno et al. In the case of the control soil.b). For the highest zeolite dose (25 000 kg/ha) these proportions are reduced to 0. probably because of its lower mobility due to its strong sorption on clays when pH is increased (McBride. even at the lowest zeolite dose applied to soil. percentages of the metal leached with respect to the total metal content are 13% for Cd. Cumulative curves of metal cations leaching in the soils. Co. to about 1–10%. 1994). 2 for Cd. In the case of the soil amended with the zeolite dose of 15 000 kg/ha.6% of Ni and 0. Subsequently there was a progressive decrease in the leached amounts.9% of Zn.

the depletion in the leached metal amounts observed as pH is increased must be due to an alternative process. 1978). Therefore.b). One explanation for this could be the decrease in the As sorption capacity of soil when pH is raised (up to 7. Scorodite is metastable above pH 2 and tends to dissolve incongruently (Robins. The rise in the pH values due to the zeolite addition may account for the reduction in the As sorption capacity of the soil... thereby eliminating or considerably minimizing the risk of groundwater pollution. 2002). Singh et al.178 X. Garcia-Sanchez et al. / Chemosphere 62 (2006) 171–180 curves took on a more concave form. the decrease in the Fe concentration could not be simulated by using the sorption model. 1998.02% for the dose of 15 000 kg/ha. Fig.. these values are equivalent to a concentration of <22 lg/l. With respect to trivalent metals (Fig. 1994). 1998. Querol et al. most of the retained metal load is not sorbed by the zeolitic material in an exchangeable form. Nishimura and Tozawa.4–8.10 control 0. carbonates or sulfates was ruled out since these phases were always under-saturated in the solution. On the other hand. DIN-leaching tests performed for the zeolitic material alone showed that 17 mg/kg of As could be released from the relict fly ash particles with pure water. Smith et al. Therefore. To confirm this hypothesis. Cumulative curves of As leaching in the soils. (2005) have proposed a surface complexation model accounting for metal adsorption on illite since this phase is the predominant clay in the soil and has a high specific surface (Du et al. 4 shows the decrease in concentration of aqueous metals in soil solution (1 g/100 ml) as the pH is increased from 3. 4a and b show that the experimental depletion of divalent metals matches the results obtained from the surface complexation model. The major mechanism of As release from sulphide assemblages is by means of oxidation of arsenopyrite (Dove and Rimstidt. There is a marked correlation between the degree of As leaching and the rate of dosage of zeolitic material. oxyhydroxides and soils provide evidence of large adsorption capacities of oxyhydroxides with a maximum 0. The amounts of As leached are relatively higher for the soil samples amended with zeolite.06% for 25 000 kg/ha. It has been deduced that most metals are chemically immobilized due to surface complexation (and hydroxide precipitation for Fe and Al) as pH is increased. Decrease in Al concentrations could be modeled with the surface complexation on illite. which are easier to displace from metal binding sites (McBride. reaching even the ‘‘plateau’’ at the highest amendment dose indicating that.0) by zeolite addition.. pH neutralization tests with soil samples were conducted in the absence of zeolite. Cama et al. Thus. obtaining 0. as well as the results of the batch experiments carried out with alkaline solutions. Metal adsorption onto illite surfaces and precipitation of some hydroxides could account for the metal retention. low pH causes the protonization of surface. transforming –OH to –OHþ 2 groups.08 As leached (%) 15 tonne/hectare 25 tonne/hectare 0.04 0. 3. 25 000 kg/ha) after the NH4NO3 extraction for the sampling of 27/03/00 demonstrated that the metal amounts extracted from zeolite are lower than 1% for all the metals studied except for Co (12%). 1956. Raven et al. Metal de-sorption test The heavy metal load still retained by the treated soil samples (15 000 kg/ha. in this case. 4c). 1997. suggest that. 1996. Both the low NH4-exchangeable metal amounts. the low extraction values indicate a low mobility for As in the soil.3. 1985). but could be simulated by ferrihydrite precipitation.003% of the total As in the control soil. Although a continuous leaching is deduced from the As percolation curves. highly concentrated solution of Fe3+ and AsO3 4 (Chukhantsev. An additional explanation for the increase of As mobility due to zeolite addition is that the zeolite is a source of As.06 0. the amount of As leached in the untreated soil (Fig.00 0 100 200 300 400 Water volume (ml) Fig. 1988. hydroxides. Fig. 3) accounts for only 0. Given the solid/extractant ratio of 100 g/400 ml used in the column leaching tests.. under the conditions and at the concentrations of the soil remediation treatment. Several studies on the As adsorption on oxides. 1997a. the zeolite addition has more effect on the immobi- . 3. and 0. scorodite (FeAsO4 Æ 2H2O) may precipitate from an acidic. To explain this phenomenon. In the light of these results it could be concluded that zeolite amendment decreases the leaching of metals. the leachable fraction of metal was completely extracted.5 to 7.5 in the soil sample. Subsequently. The low pH (around 3–4) of soil samples favours As adsorption on Fe oxyhydroxides by means of ligand exchange. although precipitation of gibbsite could not be discarded at pH higher than 5. 1987).02 0. 500 adsorption around pH 3–5 (Golberg and Glaubig. Manning and Goldberg. Precipitation of divalent metal solid phases such as oxides.

zinc and cadmium in smelter-contaminated soils using biosolids and rock phosphate. Heavy Metals in Soils. J. Snethen. Blackie Academic & Professional. lization of these metals by the subsequent increase in pH than by the zeolite cation exchange capacity. Ion exchange reactions in zeolites. Querol. Santona. Kopponen. J. Plant Anal. its use in the remediation of this polluted soil has two clear advantages with respect to other alkaline agents: (a) the induced soil pH increase is moderate and therefore the risk of mobilization of elements soluble in basic conditions is less than when using more alkaline agents and. J. Moreno.. [cations] (mol/l) 4E-05 3E-05 2E-05 Zn expt Zn ads Mn ads Mn expt Cu ads Cu expt 1E-05 (x10) 0E+00 a 6E-07 [cations] (mol/l) 5E-07 4E-07 3E-07 Co expt Co ads Ni expt Ni ads Cd ads Cd expt 2E-07 1E-07 b (x10) Acknowledgments 0E+00 The present study was supported by the BRITEEURAM Program from the 4th Framework of R&D of the European Union (SILEX. similar results in metal retention can be expected if other alkaline amendments. Chapter 7 of Zeolite Molecular Sieves. 30. Koe. are used.T. 1995. Castaldi.. 2005). possesses an important exchange capacity that could reduce the soluble metal concentration if necessary. Immobilization of trace metals and arsenic by different soil additives: evaluation by means of chemical extractions.. Zn) decreased around 95–99% when zeolite doses of 25 000 kg/ ha were applied to soil. 1052–1056. Variation of aqueous metal concentrations as a function of pH. 1222–1230. Boisson. Gradwohl.L. the amount of illite present in soil seemed enough to almost eliminate the pollutant leachability. After such a treatment the leachability of most metals (Cd. such as lime. T.J. N. / Chemosphere 62 (2006) 171–180 contamination by trace elements. Qual. Although in case. K. Chemical immobilization of lead. (b) the zeolitic material. 6E-05 Al expt 5E-05 [Al &Fe] (mol/l) 179 (gibbsite) Al prep Al ads 4E-05 Fe expt 3E-05 Fe (ferrihydrite) 2E-05 1E-05 0E+00 c 3 4 5 6 7 8 pH Fig. 365–387. Vangronsveld. 2005. BRPR-CT98-0801) and by the Spanish CICYT (AMB99-1147-C02-02). Metal adsorption on clays from a pyrite contaminated soil. 131.. B. J. Florida. J. the cation exchange process on the zeolite is low. in addition to the buffering capacity. D. and Use.. Mench. A. Ni. R. respectively) are also plotted. in this case.. J. 30. Concentrations of Cu and Co have been enlarged by one order of magnitude for inclusion in the plot. 2005. favoring metal adsorption onto illite surfaces and precipitation of metal hydroxides. Basta. Breck.W. P. Krieger Publishing Company. Glasgow. Conclusions The zeolitic material synthesized from coal fly ash appeared as an effective amendment to attenuate the soil References Alloway. to Clarian SA for the pilot plant scale experiment carried out to provide the zeolitic material and to IQE SA for providing the pure commercial zeolite for comparison. Cu. Chemistry.X.. Environ... M. Schroder.. 4... Melis... M. Heavy metal immobilization by chemical amendments in a polluted soil . N. The Al and Fe concentrations in equilibrium with hydroxides (gibbsite and ferridryte. Robert E. C. X. Structure.. We are indebted to the power generation company ENDESA for supplying the fly ash sample from the Teruel power plant.. The symbols are experimental (expt) values and the curves represent the values calculated (ads) with a surface complexation model (Cama et al. 1984. Ayora.L. Environ. Thus. L. The soil pH increase caused by the zeolite addition seems to be the factor responsible for metal immobilization.. Querol et al. Commun. 2001. Malabar.. P. Soil Sci.. Cama. Co. 1999.. TIC: 245213. 4. Eng. Ruttens.

Environmental quality standards for soil and water.. 9. Clay Sci. Am. G. Rupaiwar. The mine tailing accident in Aznalcollar. Institut fu¨r Normung. Fundamentals of Soil Behavior. J.J. Ayora. 1988.. S. Dove. Chlopecka. Ferna´ndez-Pereira. A. 63. 1986. Microchem. calcium and magnesium arsenates. 1994. Loeppert. Inc.. Adsorption of copper at aqueous illite surfaces..L.. G. Marosits. 2003. 1999. J. Liu. Technol. 64. Manning. E. Janssen-Jurkonicova. IIL Internal Report 87R014T. Soc.B. Naidu.. M. Mitchell. R. 33. Am. Rimstidt.. Metall. A. structure and influence of metal retention on pH.. WI. Arey.L.A.G.. 94. Asp. A Physicochem... Environ. 187. TX. 131–140..M. Quirk. Vangronsveld. Synthesis of Na zeolites from fly ash in a pilot plant scale. Prasad. Sci. R. 30. 265–269...C. 1971. 23. Environ. Adriano. 1984. Robins. Technol...). Chemosphere 60. Am. Particle size analysis. 1998. Berlin. Moreno. H.. Ed. C.. Am. 67. Plana. 133–139. International Soil Reference and Information Centre. Colpaert.... 72. 1997a... Netherlands Ministry of Housing. H. Mimicked in-situ stabilization of metals in a cropped soil: bioavailability and chemical form of zinc.. Anne. Rodrı´guez-Carvajal. Golberg. 149–195.D.. Soil Sci. John Wiley & Sons Ltd. 1985.M. 35. 842–844..C. A. Bauder. Acid-base properties of aqueous illite surfaces. C. Nishimura.W. Mineral. J. 2000. Chemical modelling of arsenate adsorption on aluminium and iron oxide minerals. New York. In: Surface Chemistry of Oxides. V. Tozawa. Anal. W. 9. Environmental Chemistry of Soils. 2000. Rodriguez. Cunningham. Domingo. Examples of potential environmental applications. 2001. E. A. D. Inc. Alastuey. 50. M. / Chemosphere 62 (2006) 171–180 and influence on white lupin growth. A. Miner. 162. Heidelberg.H. Sci. FeAsO4 Æ 2H2O. J. S. Discussions of the Faraday Society.M.. 2002.. Q. 1995. S. Nissen. (Ed. T.. Querol. Netherlands Ministry of Housing. Medinaceli. Ferna´ndezPereira. Sci. J.). K. Garcia-Sanchez.. Environ. E. Coles. Z... Arsenite and arsenate adsorption on ferrihydrite: kinetics. Ferrer. 37. J. Du. J. 1996. X. C. Arsenic(III) and arsenic(V) adsorption on three California soils.. F..W.K. 1995. 20–26. 1997b. Tang. E. Chemosphere 41.K. Institut fu¨r Normung. Whateley. Polya´k. Coal Geol. Clay Miner. Ayora. Springer-Verlag. Querol.P.. New Jersey.G. K.. W.. Bull. Fortschr.. Wirsching. 565–571.. Fuel 80. A. Miranda-Trevino. 242.1–9. F. 1986. Colloids Surf... Lopez-Soler. Adsorption technique for the treatment of As(V) rich effluents.. X.. McBride. Agronomy and Soil Sci. Seaman.C..V. Part 1. Smith. 886–895. The Faraday Soc. Soil Sci. Forsling. Wiley. 2000. Querol et al. A.. Uman˜a. Grimalt. R.D.. Hlavay. 994–1002. 21–43.W.. 3– 11. Leidschendam. Chukhantsev. 255–271... Environ.K. Inc. J. Environ. J. Total Environ. 1987. The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils. Metal-Contaminated Soils: In Situ Inactivation and Phytorestoration. S. 1154–1157.. Soc. Appl. On the solubility products of ferric. Janssen-Jurkonicova. Am... Ho¨ller.. Kaolinite properties. Inst.. 1987. F. (URSS) 11. 1994.. J.. Physical Planning and Environment. Hingston. J. Sun. Landes Company. Lee. P. M. Vangronsveld. Publ. E. Alston. Anion sorption on a calcareous.C. Eng. P.A. Querol.. M. FAO-UN. J. 365– 371. Sun. Q. 334–343. Z. Ross. 49–56. M. 1995. 1978. X. 838–844.. Pollut. Mineral. Jackson. X. Procedures for soil analysis. F. DIN V 19730 1993. 127. Chem. J. Application to its immobilization in two polluted mining soils. Madison.. C..180 X. Georgetown.C.. ISRIC. Grenoble. Toxic Metals in Soil–Plant Systems... 1996...M.J.B. A. 2001b. Singh. Sci. N. 857–865.. Arsenic in the soil environment. Berlin. 3526–3534. 1997.. Adv. montmorillonite soil-arsenic. M. 1998. 52. R. K. Colloid Interface Sci. J. Moreno. and adsorption envelopes. 1996. 2001. Gee. Lo´pez-Soler. H. Chen. Raven. Jain. DIN 38414-S4. R.. 1960. Technol. D. A. Alastuey. 1985. D. Macpherson. Alastuey.C. pp. 219–226. A. Physical Planning and Environment. M. 70.. 793–799... Agron. Technical paper 9.. In: Tompkins.. Bertsch. 187. J. Competitive adsorption of negatively charged ligands on oxides surfaces.J.G. Immobilization of nickel and other metals in contaminated sediments by hydroxyapatite addition. Posner.. 235–242.. Glaubig. 460–469..O. J.... Prentice-Hall. Synthetic zeolites as amendments for sewage sludge-based compost. Synthesis of Na-zeolites from fly ash. Reclamation of a bare industrial area contaminated by nonferrous metals: physicochemical and biological evaluation of the durability of soil treatment and revegetation.. Edwards. In: Klute.. 1993.J. Tang. Zeolites formation from fly ash. J.... J. Plana. J.. New York.C. Utilisation of zeolites synthesized from coal fly ash for the purification of acid mine waters.. Eng. Solubility and stability of scorodite FeAsO4 Æ 2H2O: discussion. Querol. London. A. Soil Chemical Analysis. Goldberg. Pannetier. 52. van Tichelen.13.. J. Am. The solubility and stability of scorodite. Oxford University Press. Colloid Interface Sci.S. B. Sorption of As(V) by some oxyhydroxides and clays minerals. Institute Max Von Laue Paul Langevin. Tuncali. A. R. 187–194. Soil Sci. Soc. J. J.. Miner. Du. 232–242. Forsling. Qual. Turkey. Ferna´ndez-Turiel... Agronomy Series no. Chichester. Dress. K. Geological controls on the mineralogy and geochemistry of the Beypazari lignite. Lepp.. Fuel 76. S. second ed. E. J.M. equilibrium. Central Anatolia.. 3294– 3303. G. X. 1998.P.R. Valero. 1297–1300.S.... 34.. A. . Chemosphere 41. 2001a. The Netherlands. F. Querol.. J. J. 1956.. L. Garcı´aRojo.. A system for time-resolved data analysis (Powder Diffraction Pattern). 344– 349. N. Berlin. C. Investigation on the chemical bonding of copper ions on different soils samples. U.. Environmental applications of pure zeolitic material synthesised from fly ash. Englewood Cliffs. The solubility products of a series of arsenates. 30. M.. N. 1997. 111..A. 32. (Ed. Methods of Soil Analysis. Z. 221–231. Int. 383–411. Environ. Alvarez-Ayuso. pp.G. Golberg.