New Technique for Soil Reclamation and Conservation:

In Situ Stabilization of Trace Elements in Contaminated

Soils
Osama Negim

To cite this version:

Osama Negim. New Technique for Soil Reclamation and Conservation: In Situ Stabilization of Trace
Elements in Contaminated Soils. Earth Sciences. Université Sciences et Technologies - Bordeaux I,
2009. English. �NNT : �. �tel-00408020�

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N° d’ordre : 3821

THÈSE
PRÉSENTÉE A

L’UNIVERSITÉ BORDEAUX 1
ÉCOLE DOCTORALE DES SCIENCES ET ENVIRONNEMENTS

Par Osama NEGIM

POUR OBTENIR LE GRADE DE

DOCTEUR
SPÉCIALITÉ : SCIENCE DES SOLS

New Technique for Soil Reclamation and Conservation:

In Situ Stabilization of Trace Elements in
Contaminated Soils

Soutenue le 17 juillet 2009

Devant la commission d’examen formée de :

M. Mikael Motelica-Heino (Professeur, Université d’Orléans) Rapporteur

Mme. Gaëtane Lespes (Professeur, Université de Pau) Rapporteur
M. Richard Fabre (Professeur, Université Bordeaux 1) Président du jury
M. Michel Mench (Directeur de Recherches INRA) Co-directeur de thèse
M. Philippe Le Coustumer (HDR, Université Bordeaux 1) Directeur de thèse
M. Ionan Marigomez (Professeur, Université de Bilbao, Espagne) Examinateur
M. Arnaud Gauthier (Maître de Conférences, Université de Lille) Examinateur
M. Frédéric Huneau (Maître de Conférences, Université Bordeaux 1) Examinateur
M. Fouad Amin (Docteur, Société Italcementi) Invité
 Acknowledgments

First, I wish to express my deepest appreciation to my supervisor Prof. Dr. Ph. Le Coustumer,
GHYMAC, University Bordeaux 1, for his advice, support, encouragement, spent most of his time and
talent to guide in all steps of this work through my study.

I would like to express my deepest thanks to my co-supervisor Prof. Dr. M. Mench, UMR BIOGECO
INRA, University Bordeaux 1, for his advice, support, for the information about site study, for his help
during selecting profiles soil study and for the experimental procedures of soils and plants.

Great thanks and gratefulness are due to Prof. Dr. M. Motelica-Heino, ISTO, UMR, CNRS University
Orléans, for his helpful support and giving freely of his time for finish my work.

I would like to thanks A. Gauthier, UMR, CNRS, University Lille 1 for using atomic
spectrophotometer, E. Lebraud, ICMCB, University Bordeaux1 for using X-ray diffraction (XRD), E.
Sellier, CREMEM, University Bordeaux1 for using scanning electron microscope (SEM) and M.
Lahaye, CeCaMA, University Bordeaux1 for using electron microprobe analysis (EMPA), for their
give me helpful advice to procedures slags analysis.

Special thanks to Dr.F.Huneau, for his helpful support and giving freely of his time for the
experimental procedure of soil analysis and finish my work.

Thanks to Prof. Dr. R. Fabre, Dr.B. Eloifi and Dr. M. Elachachi, GHYMAC, University Bordeaux 1
and give me helpful advice for the experimental procedure of soil analysis. Thanks also to C. Bes,
UMR BIOGECO INRA, University Bordeaux 1 and give me freely of her time for the experimental
procedure of plants.

Special thanks to the all staff members and all my colleages at the laboratory of GHYMAC,
University Bordeaux 1, for their assistance during this work.

Great thanks to Prof. Dr. A. Abd El-Galil and Prof. Dr. M. Ibrahim, Department of Soil and Water,
Faculty of Agriculture, Sohag University, Egypt for their support and encouragement during this work.

Finally, all great thanks to my family and the Egyptian Government for their help, stimulation and
encouragement during this work.
 RÉSUMÉ

Les sols sous contraintes que ce soit du point de vue charges polluantes comme avec
les Métaux Traces (MT) ou bien du point de vue stress hydrique (perte des capacités de
rétention menant à la désertification des sols) concernent de nombreux espaces du territoire
national, de même que la région du pourtour Méditerranéen. Le nombre de sites pollués par
des substances inorganiques affectant de larges espaces est en constante augmentation. Les
stratégies pour leur rémédiation sont variées mais très peu envisagent la dépollution tout en
restaurant les propriétés pédologiques des sols concernés. La rémédiation comme la
restauration des capacités fertilisantes de sols pollués sont un enjeu international. Pour cela, la
stratégie de cette étude porte sur le développement d’outils technologiques innovants basée
sur la phytorémédiation assistée par des matrices duales de sols contaminés par des MT
(Cuivre, Chrome, Arsenic). Ces matrices duales ont une action double concomitante en
permettant une immobilisation ou un piégeage des MT tout en favorisant la repousse végétale
ou la catalyse de la croissance végétale. Le piégeage peut se faire par l’apport d’amendement
ayant des capacités d’échanges (généralement liées à l’existence de phase allophane et/ou
d’un réseau poral important) et de rétention (liées au réseau porale et à l’existence de phases
minérales type phosphates, silice amorphe, oxydes hydroxydes de fer-manganèse).
L’élaboration, à partir de laitiers d’aciéries, d’une matrice susceptible d’adsorber des MT
(aspect dépollution) tout en favorisant la pousse végétale (aspect amendement) nous a permis
de tester ce produit de synthèse. La seconde originalité de cette étude est d’analyser le
potentiel de ces matrices, non seulement à différentes échelles (du pot en passant par le stade
mésocosme et jusqu’au champ), du point de vue impact écotoxique – dépollution de sols
associé à une re-végétalisation. Cette dernière participe également au transfert des charges
polluantes (MT) depuis l’amendement de synthèse ou du sol vers, et dans le réseau racinaire
des radicelles et ainsi favoriser la réhabilitation des propriétés hydriques des sols par le
développement d’un couvert végétale pérenne. On conjugue ainsi un apport dépolluant à celui
de maintient de la potentielle anti-désertification grâce au développement de solutions
innovantes respectueuses de l’environnement sur la base de technologie douce valorisant les
co produits de l’industrie.

Mots clés : CCA, Cuivre, Chrome, Arsenic, rémédiation, scories, re-végétalisation

 ABSTRACT

Soil contamination by trace elements is a widespread problem in many parts of

the world. The accumulation of toxic metals in soil is mainly inherited from parent
materials or inputs through human activities. In fact, one of the sources of soil
contaminations is very important resulting from chemical widely used wood
preservative industries in aquatic environments and storing the wood after treatment by
chromated copper arsenate (CCA). Elements such as As, Cu, Cr, and Zn can be found
in excess in contaminated soils at wood treatment facilities, especially when Cu
sulphates and chromated copper arsenate (CCA) were used as a preservative against
insects and fungi, which may result in soil phytotoxicity as well as toxic to plants,
animals and humans. New techniques are being developed to remediate trace elements
in contaminated soils such as phytoremediation and in situ stabilization. In situ
stabilization technique or in situ immobilisation is one of the common practices for
reducing negative effects of metals and metalloids such as As, Cr, Cu, Pb, Cd and Zn in
contaminated soils by adding amendments. Alkaline materials are usually added to
acidic soils to improve soil chemical and physical properties and also to reduce the
mobility and bioavailability of contaminant. Slag, which consists of calcium oxide,
phosphorus oxide, silicon oxide, iron oxide, and other metal oxides, is an alkaline by-
product of metallurgical processes or a residue of incineration processes. Slags have
been successfully used to soil reclamation and soil fertiliser. It has been used as a soil
additive to reduce various metals contaminated soil by precipitation and adsorption on
the surface of metal oxide. The objectives of this Ph.D study were to evaluate the
physical, chemical soil properties and the distribution of trace elements in contaminated
soil. Also to evaluate the characteristics of two different slags samples, a basic slag (BS)
and a basic slag phosphate (BSP) which are alkaline by-products of the French steel
industry and which used as a soil amendments to improve soil properties and for the in
situ immobilisation of copper and metals in chromated copper arsenate (CCA)
contaminated soil.

Key words: CCA, soil reclamation, stabilisation, slag, soil properties, bean plants
 CONTENTS
LIST OF TABLES................................................................................................................................. - 3 -
LIST OF FIGURES............................................................................................................................... - 5 -
CHAPTER 1: GENERAL INTRODUCTION .................................................................................... - 7 -
CHAPTER 2: REVIEW OF LITERATURE .................................................................................... - 10 -
2.1. TRACE ELEMENTS IN SOIL-PLANT SYSTEMS ................................................................. - 10 -
2.1.1. DEFINITION ...............................................................................................................................- 10 -
2.1.2. GEOCHEMISTRY OF TRACE ELEMENTS ......................................................................................- 10 -
2.1.3. PEDOGENESIS AND TRANSLOCATION OF TRACE ELEMENTS IN SOILS .........................................- 12 -
2.2. SOIL CONTAMINATION .......................................................................................................... - 13 -
2.2.1. SOURCE OF CONTAMINANTS .....................................................................................................- 13 -
2.2.2. SOIL CONTAMINATION BY CHROMATED COPPER ARSENATE (CCA) ..........................................- 14 -
2.2.3. CHEMICAL FORM AND MOBILITY OF METALS IN SOILS ..............................................................- 16 -
2.3. SOIL REMEDIATION ................................................................................................................ - 19 -
2.3.1. INTRODUCTION .........................................................................................................................- 19 -
2.3.2. REMEDIATION OF TRACE ELEMENTS CONTAMINATED SOILS USING STABILIZATION TECHNIQUE
................................................................................................................................................... ……- 19 -
2.3.3. DYNAMICS OF TRACE ELEMENTS IN SOILS.................................................................................- 20 -
2.3.4. FACTORS AFFECTING THE IMMOBILISATION TECHNIQUE ...........................................................- 21 -
2.3.5. SOIL ADDITIVES FOR PHYSICO-CHEMICAL IMMOBILISATION OF METALS ...................................- 30 -
2.3.5.1. Alkaline materials ........................................................................................................... - 31 -
2.3.5.2. Phosphate minerals ......................................................................................................... - 33 -
2.3.5.3. Aluminosilicates minerals ............................................................................................... - 36 -
2.3.5.4. Iron and manganese Oxides and hydroxides .................................................................. - 37 -
2.3.5.5. Coal fly ashes .................................................................................................................. - 39 -
2.3.5.6. Organic amendments ...................................................................................................... - 40 -
2.3.6. REMEDIATION OF TRACE ELEMENTS IN CONTAMINATED SOILS USING SLAGS AS SOIL AMENDMENTS
...........................................................................................................................................................- 41 -
2.3.6.1. Definition ........................................................................................................................ - 41 -
2.3.6.2. Production and application of slag in different fields ..................................................... - 41 -
2.3.6.3. Chemical composition of various slags........................................................................... - 42 -
2.3.6.4. Slags sorption properties ................................................................................................ - 44 -
2.3.6.5. Effect of slags addition on soil properties ....................................................................... - 45 -
2.3.6.6. Effect of slags addition on plant production ................................................................... - 46 -
CHAPTER 3: RESEARCH OBJECTIVES ...................................................................................... - 48 -
CHAPTER 4: MATERIAL AND METHODS ................................................................................. - 51 -
4.1. LOCATION....................................................................................................................................- 51 -
4.2. FIELD STUDY AND SOIL SAMPLING ...............................................................................................- 52 -
4.3. METHODS OF ANALYSIS ...............................................................................................................- 52 -
4.3.1. Soil physical and chemical analysis ................................................................................... - 52 -
4.3.2. Slag analysis ...................................................................................................................... - 54 -
4.4. REMEDIATION TECHNIQUES .........................................................................................................- 56 -
4.4.1. Soil properties .................................................................................................................... - 56 -
4.4.2. Pot experiments.................................................................................................................. - 57 -
4.4.2.1. Effect of basic slag addition on soil properties, growth and leaf mineral composition of
beans in a Cu-contaminated soil .................................................................................................. - 57 -
4.4.2.2. In situ remediation of CCA - contaminated soil by basic slag phosphate (BSP) ............ - 58 -
CHAPTER 5: SOIL PHYSICO-CHEMICAL PROPERTIES AND TRACE ELEMENTS
DISTRIBUTION IN SOIL.................................................................................................................. - 62 -

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 5.1. SOIL PHYSICAL PROPERTIES .........................................................................................................- 62 -
5.2. SOIL CHEMICAL PROPERTIES ........................................................................................................- 63 -
5.3. TRACE ELEMENTS CONTENT AND DISTRIBUTION IN SOIL PROFILES ..............................................- 65 -
5.3.1. Copper content in the soil profiles ..................................................................................... - 68 -
5.3.2. Relationships between trace elements contents and soil parameters ................................. - 68 -
5.3.3. Relationship between copper concentration and physico-chemical soil parameters ......... - 71 -
5.3.3. 1.Relationship between copper concentration and particle size distribution soil .............. - 72 -
5.3.3. 2.Relationship between copper concentration and soil organic matter ............................. - 73 -
5.3.3. 3.Relationship between copper concentration and pH soil ................................................ - 74 -
5.4. CONCLUSION ...............................................................................................................................- 75 -
CHAPTER 6: SLAG CHARACTERISATION ................................................................................ - 77 -
6.1. CHEMICAL COMPOSITION OF THE SLAG SAMPLES .........................................................................- 77 -
6.2. POLARIZING MICROSCOPE ............................................................................................................- 78 -
6.3. X – RAY DIFFRACTION ANALYSIS .................................................................................................- 81 -
6.4. SCANNING ELECTRON MICROSCOPE (SEM/EDS) .........................................................................- 83 -
6.5. ELECTRON MICROPROBE ANALYSIS (EPMA) ...............................................................................- 87 -
CHAPTER 7: EFFECT OF BASIC SLAG ADDITION ON SOIL PROPERTIES, GROWTH AND
LEAF MINERAL COMPOSITION OF BEANS IN A CU-CONTAMINATED SOIL ................ - 88 -
7.1. INTRODUCTION ............................................................................................................................- 88 -
7.2. MATERIAL AND METHODS ...........................................................................................................- 91 -
7.2.1. Basic slag characterisation ................................................................................................ - 91 -
7.2.2. Pot experiment ................................................................................................................... - 92 -
7.2.3. Statistics ............................................................................................................................. - 92 -
7.3. RESULTS AND DISCUSSION ..........................................................................................................- 93 -
7.3.1. Soil parameters .................................................................................................................. - 93 -
7.3.2. Plant analysis ..................................................................................................................... - 95 -
7.3.2.1. Plant yield ....................................................................................................................... - 95 -
7.3.2.2. Foliar elemental concentrations and accumulations ...................................................... - 97 -
7.3.2.2.1. Foliar nutrients concentrations and accumulations .................................................... - 97 -
7.3.2.2.2. Foliar trace element concentrations and accumulations ............................................. - 99 -
7.4. CONCLUSION .............................................................................................................................- 101 -
CHAPTER 8: IN SITU REMEDIATION OF TRACE ELEMENTS IN CHROMATED COPPER
ARSENATE (CCA)-CONTAMINATED SOIL USING BASIC SLAG PHOSPHATE (BSP) ... - 102 -
8.1. INTRODUCTION ..........................................................................................................................- 102 -
8.2. MATERIAL AND METHODS .........................................................................................................- 106 -
8.2.1. Characteristics of the soil amendment ............................................................................. - 106 -
8.2.2. Pot experiment ................................................................................................................. - 107 -
8.2.3 Statistical analysis ............................................................................................................ - 108 -
8.3. RESULTS AND DISCUSSION ........................................................................................................- 108 -
8.3.1. Effect of BSP on soil properties ....................................................................................... - 108 -
8.3.2. Plant analysis ................................................................................................................... - 111 -
8.3.2.1. Effect of BSP on shoot biomass..................................................................................... - 111 -
8.3.2.2. Effect of BSP on root biomass....................................................................................... - 112 -
8.3.2.3. Effect of BSP on concentrations and accumulations of elements in plants ................... - 113 -
8.4. MINERALOGICAL FORM OF COPPER IN THE PARTICLE-SIZE FRACTIONS OF THE SOIL ..................- 120 -
8.4.1. Copper in the particle-size fractions of the contaminated soil......................................... - 120 -
8.4.2. Copper in the particle-size fractions of the BSP- soil ...................................................... - 124 -
8.5. CONCLUSION .............................................................................................................................- 126 -
SUMMARY........................................................................................................................................ - 127 -
RÉSUMÉ ............................................................................................................................................ - 136 -
REFERENCES .................................................................................................................................. - 146 -
APPENDIXES ................................................................................................................................... - 170 -

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 LIST OF TABLES

Chapter 2
Table 2.1: Trace elements concentrations in rocks (mg/kg) ....................................... - 12 -
Table 2.2: Chromated copper arsenate (CCA) formulations (oxides basis %) .......... - 14 -
Table 2.3: Production of steel slags in the different countries ................................... - 42 -
Table 2.4: Chemical compositions of various slags % ............................................... - 43 -

Chapter 4
Table 4. 1: Physical and chemical methods in soil analysis ....................................... - 53 -
Table 4. 2: Physico-chemical properties of contaminated and control soils .............. - 57 -

Chapter 5
Table 5.1: Some physical properties of the soil samples profiles in the study area ... - 63 -
Table 5.2: Some chemical properties of the soil samples profiles in the study area .. - 64 -
Table 5.3: Trace elements contents and distribution in the soil samples profiles ...... - 66 -
Table 5.4: Linear correlations coefficients between physico-chemical properties and
trace elements contents in soil study .................................................................. - 71 -

Chapter 6
Table 6.1: Chemical composition of both slag samples ............................................. - 78 -
Table 6.2: The principal crystalline phases of BS and BSP analysis ......................... - 82 -
Table 6.3: SEM analysis of both slag (BS and BSP) ................................................. - 84 -

Chapter 7
Table 7.1: Characterisation of the BS ......................................................................... - 91 -
Table 7.2: Elemental concentrations in the primary leaves of beans ......................... - 98 -
Table 7. 3: Elemental accumulation in the primary leaves of beans (µg plant-1) ....... - 99 -

Chapter 8
Table 8. 1: Chemical characteristics of BSP ............................................................ - 106 -

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Table 8. 2: Basic slag phosphate (BSP) added to the soil treatments ....................... - 108 -
Table 8. 3: Elemental concentrations in the primary leaves of beans ...................... - 114 -
Table 8. 4: Elemental accumulation in the primary leaves of beans (µg plant-1) ..... - 114 -
Table 8. 5: Forms of metals in the silt fractions for each treatment ......................... - 122 -
Table 8. 6: Forms of metals in the clay fractions for each treatment ....................... - 123 -

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 LIST OF FIGURES

Chapter 2
Figure 2.1: Application of steel slag in different fields ...........................................................- 42 -

Chapter 4
Figure 4.1: Location of the studied soil profiles .....................................................................- 52 -

Chapter 5
Figure 5.1: Vertical distribution of trace elements in the soil profiles ....................................- 67 -
Figure 5.2: The principal plan component analysis performed for trace elements concentrations
and physico-chemical soil properties of the soil samples ...............................................- 70 -
Figure 5.3: Relationship between copper and clay contents in soil samples...........................- 73 -
Figure 5.4: Relationship between copper and OM contents in soil samples ...........................- 74 -
Figure 5.5: Relationship between copper contents and pH in soil samples ............................- 75 -

Chapter 6
Figure 6.1: Thin section image of BS under polarised light ...................................................- 79 -
Figure 6.2: Thin section image of BSP under polarised light .................................................- 80 -
Figure 6.3: XRD spectrogram of BS and BSP analysis ..........................................................- 83 -
Figure 6.4: Comparison SEM analysis between BS and BSP .................................................- 84 -
Figure 6.5: X-EDS of BS ........................................................................................................- 85 -
Figure 6.6: X-EDS of BSP ......................................................................................................- 85 -
Figure 6.7: SEM images of BS................................................................................................- 86 -
Figure 6.8: SEM images of BSP .............................................................................................- 86 -
Figure 6.9: EPMA image of BS and BSP ...............................................................................- 87 -

Chapter 7
Figure7.1: Effects of BS addition on the soil pH ....................................................................- 94 -
Figure7.2: Effects of BS addition on the soil EC ....................................................................- 94 -
Figure7.3: Effect of BS on the shoot yield of beans (g DW plant-1) for each treatment .........- 96 -
Figure 7.4: Effect of BS on the root yield of beans (g DW plant-1) for each treatment ..........- 96 -

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Chapter 8
Figure 8.1: Effects of BSP on the soil pH .............................................................................- 110 -
Figure 8.2: Effects of BSP on the soil EC .............................................................................- 110 -
Figure 8.3: Effect of BSP on the shoot yield of beans (g DW plant-1) for each treatment ....- 112 -
Figure 8.4: Effect of BSP on the root yield of beans (g DW plant-1) for each treatment ......- 113 -
Figure 8.5: XRD diffraction patterns of the silt fractions for each treatment .......................- 121 -
Figure 8.6: XRD diffraction patterns of the clay fractions for each treatment......................- 121 -

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 CHAPTER 1: General Introduction

Soil contamination by trace elements is a widespread problem in many parts of

the world. The accumulation of toxic metals in soil is mainly inherited from parent rock
materials or inputs through human activities (He et al., 2005). One of the sources of soil
contamination which is very important results from the chemical widely used wood
preservative industries in aquatic environments and storing the wood after treatment by
chromated copper arsenate (CCA). Elements such as As, Cu, Cr, and Zn can be found in
excess in contaminated soils at wood treatment facilities, especially when Cu sulphates
and chromated copper arsenate (CCA) were used as a preservative against insects and
fungi, which may result in soil phytotoxicity (Kumpiene et al., 2008). The rain is
playing a key-role in leaching these metals from the recently treated timber and lumber
stored at the treatment facility. Under conditions of storage the timber, the soils contain
high concentrations of CCA (Buchireddy et al., 2008). Therefore, it is very important to
reduce or immobilise these metals in contaminated soils. Currently there are several
technologies that can be used to clean up or remove the soils and the mining wastes
contaminated by toxic metals, such as thermal treatments, biological and
physical/chemical procedures. These removal technologies are generally costly to
practice and destructive to the application sites and only partially effective for the total
removal (efficient clean up) of toxic metals or for the sufficient reduction of their
mobility and bioavailability (Raicevic et al., 2005).

In the past few decades, new techniques are being developed to remediate trace
elements in contaminated soil, sediments and groundwaters such as phytoremediation
and in situ stabilization. The stabilization techniques or in situ immobilisation aim at
decreased the labile pool of metals and metalloids such as As, Cr, Cu, Pb, Cd and Zn by
the incorporation of amendments. This technique is also able to enhance one or several
processes such as metal adsorption through increased surface charge, formation of
organic and inorganic metal complexes, sorption on Fe, Mn, and Al oxides, and
precipitation. It is considered as a simple and cost-effective approach for the treatment

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of metals in contaminated soils, particularly when these soils are difficult or costly to be
removed or treated ex situ. It can be used for in situ and ex situ applications to reclaim
and re-vegetate industrially devastated areas and mine-spoils and restore the physical,
chemical and biological soil properties and also reduce the contaminant mobility and
bioavailability with various chemical and mineralogical agents such as industrial by-
products ( Mench et al., 2000; Oste et al., 2002; Bolan and Duraisamy, 2003; Adriano
et al., 2004; Pérez de Mora et al., 2005; Raicevic et al., 2005 ; Kumpiene et al., 2006;
Kumpiene et al., 2008 ). Alkaline materials are usually added to acidic soils to
ameliorate the soil chemical and physical properties and reduce the mobility and
bioavailability of metallic contaminants. Several application studies have demonstrated
the in situ immobilisation of contaminated soils and groundwaters by using inexpensive
soil amendments. The amendments can significantly reduce the mobility of metals in
soil, metal uptake by plants and metal phytotoxicity.

Several alkaline slags have been used for amending acid soils. Slag, which
consists of calcium oxide, phosphorus oxide, silcon oxide, iron oxide and other metal
oxides, is an alkaline by-product of metallurgical processes or a residue of incineration
processes. Slag have been successfully used in different fields of application such as
fertiliser (phosphatic fertiliser), road construction (e.g. asphaltic or unbound layers),
civil engineering work, and production of metallic iron and iron concentrate, soil
reclamation and water refinement (Geiseler, 1996; Shen Li, 1999; Ortiz et al., 2000;
Motz and Geiseler, 2001; Shen and Forsberg, 2003; Charles and Nemmer, 2006). It has
been used as a soil additive to remove various metals contaminated soil by precipitation
and adsorption on the surface metal oxide (Mench et al., 1994a,b; Besga et al., 1996;
Dimitrova, 1996; Dimitrova and Mehandjiev, 1998; Mench et al., 1998; Barbosa Filho
et al., 2004; Carvalho-Pupatto et al., 2004; Bes and Mench, 2008; Kim et al., 2008).

The submitted Ph.D studies the following parts:

First, to study physico-chemical soil properties and the distribution of trace elements in
soil, to evaluate the relationship between the metals in contaminated soils and several
soil parameters such as the particle size distribution, the organic matter content, the soil
pH and the cation exchange capacity.

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Second, to evaluate two different slag samples used as soil additives, basic slag (BS)
and basic slag phosphate (BSP) which were obtained from the French steel industry.
The chemical and mineralogical properties of both slags were investigated by using
several analytical techniques: the chemical composition was determined by an atomic
adsorption spectrophotometer, mineralogical analysis was performed by X-ray
diffraction (XRD), the microstructure was observed by optical microscope, scanning
electron microscope (SEM) coupled with energy dispersive (EDX) and electron
microprobe analysis (EMPA).

Third, BS compounds may influence the composition of soil solution through acid-
base, precipitation and sorption reactions and also the foliar concentrations through
changes in soil solution, competition for root uptake and root-to-shoot transfer. The
compounds contents in BS make it a potential liming agent to increase the precipitation
and sorption of trace elements such as Cu and a potential fertilizer promoting plant
growth and improving the physico-chemical properties of the soil such as soil electrical
conductivity (EC) and pH soil. Therefore this study aimed at investigating BS addition
into a soil mainly Cu-contaminated from a wood treatment facility in which the addition
of BS may improve soil characteristics such as pH and EC and reduce the labile pool of
trace elements in soil for root-to-shoot transfer in beans plants.

Fourth, BSP is used as a soil remediation technique for improve physico-chemical soil
properties and also for in situ immobilisation of copper and CCA in contaminated soils
by increased the precipitation and adsorption on the surface metal oxide of the BSP thus
changing the availability and mobility of these trace elements. The objectives of this
study were (1) to determine the influence of the addition of BSP into a strongly Cu-
contaminated soil to improve the soil properties such as soil pH and EC (2) to evaluate
the effect of different BSP addition rates on the plant yield production and the foliar
elemental concentrations of both nutrients and trace elements of primary leaves, (3) to
determine the potential of BSP to reduce copper and CCA in contaminated soils as well
as to reduce the metal toxicity uptake by beans plants, (4) to study the mineralogical
form of copper in particle size fractions of the soil treatments were determined by X –
ray powder diffraction analysis (XRD).

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 CHAPTER 2: Review of Literature

2.1. Trace elements in soil-plant systems

2.1.1. Definition

The major elements O, H, Si, Al, Fe, Ca, Na, K, Mg, Ti and P constitute over
99% of the total elements content of the earth’s crust (Alloway, 1995; Baize, 1997). A
trace element is an element present at a level < 0.1% in natural materials. Trace
elements include metals and metalloids (both metallic and non-metallic properties, e.g.,
As and B), micronutrients (chemical elements needed in small quantities for plant
growth, i.e., < 50 mg/g in the plant) and trace inorganic (Sparks, 2003). Heavy metals is
the generic name given to the group of elements with an atomic density greater than 6
g/cm3 ; their concentration in soil and water varies from less than 1000 ppm to a few
ppb with the exception of manganese which is found in soils from 20 to 10000 ppm
(Alloway, 1995). In general, trace elements which are present at very low
concentrations in agroecosystems include copper (Cu), zinc (Zn), manganese (Mn), iron
(Fe), molybdenum (Mo) and boron (B); they are essential metals in small concentrations
to plant growth. Some trace elements, such as cobalt (Co) and selenium (Se) are not
essential to plant growth but are required by animals and human beings (He et al.,
2005). Other trace elements such as cadmium (Cd), lead (Pb), chromium (Cr), nickel
(Ni), mercury (Hg), and arsenic (As) have toxic effects on living organisms and are
often considered as contaminants. In addition trace elements are toxic to plants, animals
and humans due to extremely high concentrations in the parent materials and
anthropogenic inputs (Bolan et al., 2003; He et al., 2005).

2.1.2. Geochemistry of trace elements

The earth crust is made up of 95% igneous rocks and 5% sedimentary rocks
(80% are shales, 15% sandstones and 5% limestone). Sedimentary rocks are more
important than igneous rocks as soil parent materials. They are formed by the

- 10 -
lithification of sediments comprising rock fragments or resistant primary and secondary
minerals such as clays or chemical precipitates including calcium carbonates. The
concentration of trace elements in sedimentary rocks is depending on the mineralogy
and adsorptive properties of the sedimentary material (Alloway, 1995; He et al., 2005).
The biochemical weathering processes leads to the destruction of parent materials and to
the transfer of elements from the minerals into solutions. These processes include
dissolution, hydration, hydrolysis, oxidation, reduction and carbonatisation of minerals
(Kabata-Pendias, 2001). Trace elements occur as trace constituents of primary minerals
in igneous rocks which crystallize from molten magma. They become incorporated into
these minerals by isomorphously substituting in the crystal lattice for ions of one of the
major element at the time of crystallisation. This substituation is governed by the ionic
charge, ionic radius and electronevativity of the major element and of the trace element
replacing it (Alloway, 1995).

In general, trace metals, including Cu, Zn, Cr, Co and Mn occur mainly in the
weathered processes constituents of igneous rocks such as augite, hornblende and
olivine. Also the sedimentary rock and sandstones are composed of minerals that are
resistant to weathering and usually have little amounts of trace elements. The high
amount of trace elements including Cu, Zn, Mn, Pb, and Cd occur from shales, which
are derived from fine sediments of inorganic and organic origin. In addition, soils
derived from the weathering of coarse-grained materials such as sands and sandstones
and also from acid igneous rocks including rhyolites and granites tend to contain
smaller amounts of nutritionally essential metals such as (Cu, Zn, and Co) than those
derived from fine-grained sedimentary rocks such as clays and shales, and from basic
igneous rocks. This is possibly due to their ability to adsorb metal ions (He et al., 2005).
The main concentration of metals in igneous and sedimentary rocks is given in Table
2.1. Trace metals such as Cu, Zn, Cd, and Pb are often associated with sulfur and
sulfides. Under superficial environmental conditions, sulfites are quickly oxidized and
Cu, Zn, Cd, and Pb are released and separated from sulfur at an early stage of mineral
weathering (He et al., 2005). During soil development, Cu, Zn and Cd tend to
concentrate in Mn oxides, whereas Pb is more likely enriched in the oxides and
hydroxides of Fe. While under reducing conditions, Fe and Mn oxides are slowly

- 11 -
dissolved and sulfides of these elements are formed if there is sufficient sulfur available.
In general, trace metals are presented in the form of carbonates, oxides, sulfides, or salts
in most soils (He et al., 2005).

Table 2.1: Trace elements concentrations in rocks (mg/kg)

Trace elements Earth’s crust Igneous rock Sedimentary rock

As 1.5 1-1.5 1-13

Cd 0 .1 0.09-0.13 0.02- 0.22
Co 20 1-110 0.1-19
Cr 100 4-2980 11-90
Cu 50 13-90 5.5-39
Mn 950 400-1500 460-850
Ni 80 0.5-2000 7-68
Pb 14 3-24 5.7-23
Zn 75 52-100 20-120
Source: Alloway (1995)

2.1.3. Pedogenesis and translocation of trace elements in soils

Pedogenesis or soil formations are the processes resulting from the interaction of
environmental conditions and biological activity on the surface of weathered rock
material (Alloway, 1995). Several factors cause soil formation such as climate,
vegetation, parent material, topography, time and anthropogenic activity (recultivation,
degradation) (Kabata-Pendias, 2001). Pedogenesis processes relating to the behaviour of
trace elements in the soil are those affecting:

(a) Trace elements composition of the soil inherited from the parent material by
weathering.

(b) The translocation and accumulation of soil constituents which absorb metals such as
clays, hydrous oxides and organic matter.

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 Other pedogenesis processes which are very important in relation to the
behaviour of trace metals in soil include processes such as leaching, eluviations,
salinisation, calcification, podzolisation and ferralitisation. The concentration of ions in
the soil solution is determined by the interacting processes of oxidation, reduction,
adsorption, desorption and precipitation. The concentrations of many contaminants tend
to accumulate in the soil surface. Then, they are either adsorbed with varying strengths
on the colloids in soil porewaters at the surface of the topsoil or are washed down
through the surface layer into the soil profile. This can possibly reduce their
bioavailability to plants (Alloway and Ayres, 1997). In addition trace elements such as
Ag, As, Cd, Cu, Hg, Pb, Sb and Zn are found concentrated in the surface layers as a
result of cycling through vegetation, atmospheric deposition and adsorption by the soil
organic matter. On the other hand, the elements are concentrated in the deepest layers of
the soil profiles such as, Al, Fe, Mg, Ni, Ti, V and Zr tend to associated with
accumulations of translocated clays and hydrous oxides (Alloway, 1995).

2.2. Soil contamination

2.2.1. Source of contaminants

Soil contamination by trace elements is a widespread problem in many parts of

the world. The accumulation of toxic metals in soil is mainly inherited from parent
materials or inputs through human activities (anthropogenic inputs) (He et al., 2005).
The sources of anthropogenic inputs of trace metals to the soils and the environment
include several processes such as metalliferous mining and smelting, agricultural and
horticultural materials, sewage sludges, fossil fuel combustion, metallurgical industries,
use and disposal of metal commodities, electronics- manufacture, use and disposal of
electronic commodities, chemical and other manufacturing industries, waste disposal,
sports shooting and fishing, warfare and military training (Alloway, 1995). On the other
hand, the concentrations of trace elements in soils can be higher than those found in the
parent materials causing by the use of agricultural practices such as fertilizers, organic
manures, industrial and municipal wastes, irrigation, and wet and/or dry deposits (He et
al., 2005). Both industrial and agricultural activities are the most important to produce

- 13 -
trace metals in soils in many parts of the world and also contribute to increase the
concentration of these elements in the surface soil (Kabata-Pendias, 2001; He et al.,
2005). The main source of contaminated soil agricultural include the impurities in
fertilisers which contains trace amounts of trace elements (Cd, Cr, Mo, Pb, U, V, Zn),
sewedge sludge(Cd, Ni, Cu, Pb, Zn), manures from intensive animal production(Cu, As,
Zn), pesticides(Cu, As, Hg, Pb, Mn, Zn), refuse derived composts(Cd, Cu, Ni, Pb, Zn)
and wood preservatives(As, Cu, Cr) (Alloway, 1995).

2.2.2. Soil contamination by chromated copper arsenate (CCA)

One of the important sources of soil contamination results from chemical

widely used wood preservative industries in aquatic environments and storing the wood
after treatment by chromated copper arsenate (CCA). CCA belongs to a group of
inorganic waterborne preservatives including chromated copper boron, ammoniacal
copper arsenate, acid copper chromate, ammoniacal copper zinc arsenate and
ammoniacal copper quaternary. CCA is a mix of copper, chromium, and arsenic
formulated as oxides or salts. Depending on the proportions of metals, there are three
waterborne formulations, referred to as types A, B and C (Table 2.2). In addition, Type
C is the most commercially popular and used almost exclusively (Cooper, 1994;
Balasoiu et al., 2001; Hingston et al., 2001).

Table 2.2: Chromated copper arsenate (CCA) formulations (oxides basis %)

Type CuO CrO3 As2O5
CCA-A 18.1 65.5 16.4
CCA-B 19.6 35.3 45.1
CCA-C 18.5 47.5 34.0

Source: (Cooper, 1994; Balasoiu et al., 2001; Hingston et al., 2001).

This group has largely replaced alternative organic preservative types such as
creosote, coal tars and pentachlorophenol for aquatic use (Hingston et al., 2001). CCA
has proven ability to protect wood from damage caused by moisture, bacterial and

- 14 -
fungi, wood attacking insects, including termites, and marine borers (Buchireddy et al.,
2008). Since the 1940’s, the application of CCA has been used to pressure treat lumber
used for decks, playgrounds and other outdoor uses. In addition, since the 1970’s, the
majority of the wood used in residential settings was CCA-treated wood (US EPA,
2008).

CCA-treated wood is a widespread problem in many parts of the world and a

concentrated source of toxic metals to a wide range of organisms, from single celled
algae to humans (Cox, 1991). The toxicity of copper, chromium, and arsenic is highly
dependent its chemical form and concentration. Hexavalent chromium is known to be
carcinogenic and mutagenic but during the fixation process hexavalent chromium is
reduced to trivalent chromium by organic matter and may be less harmful, while
pentavalent arsenic is considered to be more prevalent and less toxic than trivalent
arsenic (Hingston et al., 2001). Copper is the most important fungicide and forms a
major fungitoxic component of four wood preservatives: CCA, ammoniacal copper zinc
arsenate, copper azole, copper naphthenate and copper quinolinolate (Kartal and
Imamura, 2003; Kartal, 2003). In Europe, the amounts of CCA remaining in the wood
for many years and the disposal of scrap wood are a growing problem. For example, in
Germany and France, the total amount of wood waste is around 3-4 million tons per
year, of which 2.1-2.4 million tons is toxic (Helsen et al., 1998).

Elements such as As, Cu, Cr, and Zn can be found in excess in contaminated
soils at wood treatment facilities, especially when Cu sulphates and CCA were used as a
preservative against insects and fungi, which may result in soil phytotoxicity
(Kumpiene et al., 2008). After impregnation of the wood with a CCA solution, the
metal compounds are fixed to the cell walls of the wood matrix. The rain is playing a
key-role in leaching these metals from the recently treated timber and lumber stored at
the treatment facility. Therefore, under conditions of storage of the timber, the soils
contain high concentrations of CCA (Buchireddy et al., 2008).

- 15 -
2.2.3. Chemical form and mobility of metals in soils
Copper

Copper (Cu) is an essential micronutrient for plants. However, it is also highly

phytotoxic at higher concentrations, typically above 30 mg/kg (Alloway, 1995; Song et
al., 2004). Copper contamination of soils is a widespread as a result of mining,
smelting, land applications of sewage sludge, use of Cu as fungicides, algicides,
chromated copper arsenate (CCA) pressure treated lumber, copper pipes and other
industrial activities (Evanko and Dzombak, 1997; Song et al., 2004). Copper is
distinctly soluble under oxidised condition than under reduced ones in the pH range 5.4-
6.5 (Bhattacharya et al., 2002). In addition, the cupric ion Cu2+ is the most common
mobile metal in the surface environment below pH 6.9 (Alloway, 1995; Kabata-
Pendias, 2001). Therefore, increasing pH soil caused Cu to be strongly adsorbed at the
colloidal surfaces by decreasing the exchangeable form. It has also been suggested that
in for a pH higher than 7, copper tend to precipitate in the form carbonate and hydroxide
(Gagnon, 1998). Thus, Cu (OH)2 is the major solution species above pH 7 (Alloway,
1995). In addition, in aerobic conditions, the form CuCO3 is the dominant soluble
copper species followed by cupric ion, Cu2+, and hydroxide complexes, CuOH and Cu
(OH)2, while in anaerobic environments, when sulfide is present the form CuS is the
dominant soluble species (Evanko and Dzombak, 1997).

Copper mobility in soils depends on several factors, including the Cu-complexing

ability of the solid phase, the Cu-complexing ability of the dissolved organic matter
(DOM) and the molecular weight of the DOM fractions (Han and Thompson, 2003). Cu-
DOM complexation increases approximately 10-fold per pH unit (Lu and Allen, 2002).
Organic matter is the most important factors controlling the mobility and availability of
copper. Adamo et al. (1996) suggested that copper was strongly associated with organic
matter and was homogeneously distributed on the clay fraction surface. Copper, however,
has a high affinity for soluble organic ligands and the formation of these complexes may
greatly increase the Cu mobility in the soils. In addition, copper forms are strong solution
complexes with humic acids. Thus, the affinity of Cu for humates increases as the pH
increases and the ionic strength decreases (McLean and Bledsoe, 1992).

- 16 -
 Copper is retained in soils through exchange and specific adsorption mechanisms
(McLean and Bledsoe, 1992). The adsorption of Cu ion species is depending on the
surface charge of the absorbents. High amounts of adsorbed Cu were found for Fe and
Mn oxide, amorphous Fe and Al hydroxides and clay. In addition, the Cu ions can also
readily precipitate with various anions such as sulfide, carbonate, phosphates and Al and
Fe hydroxide which have a great affinity to bind a part of the soil Cu (Kabata-Pendias,
2001). Kumpiene et al., (2008) reported that the mechanism of copper retention were
precipitation of Cu carbonates and oxy-hydroxides, ion exchange and the formation of
ternary cation-anion(SO4, PO4) complexes on the surface of Fe and Al oxy-hydroxides.

Chromium

Chromium (Cr) is one of the less common elements and does not occur naturally
in the elemental native form but only in compounds (Evanko and Dzombak, 1997).
Chromium exists in two states depending on pH and redox conditions of the soil: the
trivalent chromium, Cr(III) and the hexavalent chromium, Cr(VI) (McLean and
Bledsoe, 1992). Most of trivalent chromium is present in the mineral chromate
(FeCr2O4) (Kabata-Pendias, 2001). Cr(VI) is the form commonly found at contaminated
sites and it is more toxic and mobile than Cr(III) ions (McLean and Bledsoe, 1992;
Evanko and Dzombak, 1997). In soils, Cr(VI) is as chromate ion, HCrO4- predominant
at pH under 6.5, or CrO42-, predominant at pH above 6.5, and as dichromate, Cr2O72-
predominant at higher concentrations (higher than10mM) and at pH 2-6 (McLean and
Bledsoe, 1992). In addition, Cr(III) is slightly mobile only in very acid media and at
above pH 5.5, it is completely precipitated, while Cr(VI)( HCrO4- and CrO42-) is very
unstable in soils and is easily mobilised in both acid and alkaline soils (Kabata-Pendias,
2001).

Chromium mobility in the soil is depends on the sorption properties of the soil,
including the clay content, iron oxide content and the amount of organic matter present.
Under aerobic conditions Cr (VI) is the dominant form of chromium in shallow aquifers
while, under anaerobic conditions Cr (VI) is reduced to Cr(III) by soil organic matter,
sulfide and Fe2+ ions (Evanko and Dzombak, 1997). Thus the reduction of Cr in soils is

- 17 -
accelerated by the presence of organic matter and divalent iron (Kumpiene et al., 2008).
In addition, the decreased of Cr in contaminated soil may be caused by the presence of
iron oxide which reduced Cr (VI) to Cr,Fe(OH) by precipitation (Fendorf, 1995). In
general, the application of liming, phosphate and organic matter can be effective in
reducing chromate toxicity in chromium contaminated soils (Kabata-Pendias, 2001).
Cr(III) forms solution complexes with NH3, OH-, Cl-, F-, CN-, SO42-, and soluble
organic ligands (Evanko and Dzombak, 1997). Chromate and dichromate also adsorb
on soil surfaces, especially iron and aluminum oxides. Moreover CrO42- is easily sorbed
by clays and hydrous oxides (Kabata-Pendias, 2001).

Arsenic

Arsenic (As) is an element that occurs in a wide variety of minerals, mainly as

As2O3, and can be recovered from processing of ores containing mostly copper, lead,
zinc, silver and gold (Evanko and Dzombak, 1997). The form of arsenic in the soil is
arsenate, As(V) (AsO43-), or as arsenite, As(III) (AsO2-), depending on the pH and redox
conditions. The pH and the oxidation-reduction are the most important processes
affecting the fate of arsenic in soils. Thus, at high redox levels, As(V) is dominant,
usually in the form of arsenate (AsO43-) in various compounds: H3AsO4, H2AsO4-,
HAsO42-, AsO43- and arsenic mobility is low (McLean and Bledsoe, 1992; Evanko and
Dzombak, 1997). The complex anions AsO2, AsO43-, HAsO42- and H2AsO4- are the
most common mobile forms of As, being sorbed at the pH range from 7 to 9 (Kabata-
Pendias, 2001). Under reducing conditions, As(III) dominates, existing as arsenite
(AsO33-) and its various forms: H3AsO3, H2AsO3-, HAsO32- depending on the pH
(McLean and Bledsoe, 1992; Evanko and Dzombak, 1997).

Arsenic mobility in soils is mainly controlled by adsorption/desorption processes

and co-precipitation with metal oxides such as Fe and Al (Kumpiene et al., 2008). As
minerals and compounds are readily soluble; however As migration is limited due to the
strong sorption by clays, hydroxides, and organic matter (Kabata-Pendias, 2001). The
most common As mineral is a sulfo-arsenopyrite (Kabata-Pendias, 2001). Therefore
arsenite As(III) can adsorb or co-precipitate with metal sulfides and has a high affinity

- 18 -
for other sulfur compounds (Evanko and Dzombak, 1997). Arsenate form As(V) is
insoluble and precipitates with iron, aluminum, and calcium which are important in
controlling arsenate mobility (McLean and Bledsoe, 1992). In addition As(V) can also
co-precipitate with or adsorb onto iron oxyhydroxides under acidic and moderately
reducing conditions (Evanko and Dzombak, 1997). Adsorption of arsenate by Al(OH)3
was reported by Xu et al. (2008) and who found that both the amount of arsenate
adsorbed by the amorphous Al(OH)3 and the mole fraction of arsenate remaining
adsorbed on the amorphous Al(OH)3 after desorption were substantially greater than
those in the crystalline Al(OH)3 system.

2.3. Soil remediation

2.3.1. Introduction

The mobility and exchangeable fraction of trace elements in soils are the most
important associated parameters to toxicity and bioavailability in contaminated soils.
Therefore it is very important to remove or reduce trace metals in contaminated soils by
the application of assisted natural remediation processes. Currently there are several
technologies that can be used to clean up or remove metals from contaminated soils and
mining wastes, such as thermal treatments, biological and physical/chemical
procedures. These removal technologies generally require the removal of contaminated
soil, its subsequent treatment and either replacement it on-site, or disposal in specific
landfills which is costly to practice and destructive to the application sites and only
partially effective for the total removal of toxic metals or for the sufficient reduction of
their mobility and bioavailability (Raicevic et al., 2005).

2.3.2. Remediation of trace elements contaminated soils using

stabilization technique

In the past few decades, stabilization techniques for the in situ immobilisation of
trace metals in contaminated soils are being developed to improve the quality of
contaminated soils. These techniques can be used in situ and ex situ to reclaim and re-

- 19 -
vegetate industrially devastated areas and mine-spoils, restore the physical, chemical,
and biological soil properties, and reduce the contaminant mobility and bioavailability
with various chemical and mineralogical agents. In situ stabilization of trace metals in
contaminated soil by adding amendment is one of the common practices for reducing
negative effects of contaminants such as As, Cr, Cu, Pb, Cd and Zn in contaminated
soils.

In situ remediation techniques or in situ immobilisation which is generally non-

disruptive for the natural landscape, hydrology and ecosystems are excavation,
treatment, and disposal methods. It is considered as a simple and cost-effective
approach for the treatment of metals in contaminated soils, when these soils are difficult
or costly to be removed and treated ex situ. In situ immobilisation aim at enhancing
natural attenuation mechanisms such as (ad)sorption, through increased surface charge,
precipitation, complexation and redox reactions that occur naturally in the soils to
reduce the mobility and bioavailability of the toxic elements in contaminated soils. In
addition the main goal of this technique is not to reduce the total content of
contaminants but help to lowers the fraction of toxic elements or compounds, which are
potentially mobile or bioavailable (Mench et al., 2000; Oste et al., 2002; Bolan and
Duraisamy, 2003; Adriano et al., 2004; Pérez de Mora et al., 2005; Raicevic et al.,
2005; Kumpiene et al., 2006; Kumpiene et al., 2008). On the other hand, the main
advantage of the application of stabilization techniques is the simple mixing of several
amendments with soil to reduce the mobility and bioavailability of trace elements in
contaminated soils while the disadvantage of this approach is that the final product of
remediation, which contains the immobilized contaminant, although existing in inactive
form, still remains in the soil (Raicevic et al., 2005).

2.3.3. Dynamics of trace elements in soils

The soil is a dynamic system with various soil properties. In soils, trace metals
interact with soil minerals and its organic constituents. However the fate of metals in the
soil environment is dependent on both soil properties and environmental factors (Bolan

- 20 -
et al., 2003; Adriano et al., 2004). The dynamics of trace metals in soils depend on the
physico-chemical and biological interactions with inorganic and organic soil
constituents (Adriano, 2001). The physico-chemical processes aim at retaining trace
metals in soil largely by (ad)sorption, precipitation and complexation reactions.
Sorption is defined as the accumulation of matter at the interface between the solid
adsorbent and the aqueous phase. This can include ion exchange, formation of surface
complexes, precipitation and diffusion into the solid (Adriano et al., 2004). In many
situations, the adsorption is believed to be the precursor for subsequent precipitation and
it is difficult to separate the boundary between adsorption and precipitation processes
(Bolan et al., 2003).

2.3.4. Factors affecting the immobilisation technique

Several factors affect the bioavailability and immobilisation of trace metals in

soils. The main following factors controlling the mobility of trace metals in soils will be
discussed in detail.

Effect of the soil pH

The soil pH is an indication of the acidity or alkalinity of the soils. The soil pH
is affected by the changes in redox potential which occurs when soils become
waterlogged under periodically-reducing conditions causing a pH increase whereas
oxidation brings a decrease in pH. The soil pH usually increases with depth in humid
regions where bases are leached down the soil profile and also decreases with depth in
arid environments causing by the evaporation of salts and accumulates in the surface
horizon (Alloway, 1995). The effect of soil pH is important on the solubility of minerals
or nutrients. Most minerals and nutrients are more soluble or available in acid soils than
in neutral or slightly alkaline soils. Thus, extremely and strongly acid soils (pH 4.0-5.0)
can have high concentrations of soluble aluminum, iron and manganese which may be
toxic towards the growth of some plants. Generally, the pH range of approximately 6 to
7 promotes the most ready availability of plant nutrients. In addition, the pH of the soil

- 21 -
system is a very important parameter, directly influencing sorption/desorption,
precipitation / dissolution, complex formation and oxidation-reduction reactions.
Maximum retention of cationic metals occurs at pH above7 and maximum retention of
anionic metals occurs at pH below 7 (McLean and Bledsoe, 1992).

Several studies on adsorption and immobilisation of metals by soil and soil

additives have shown that the pH is a master variable. The pH affects several
mechanisms of metal retention by soils either directly or indirectly. Many adsorption
sites in soils are pH dependent, i.e. Fe and Mn (hydro)oxides, organic matter,
carbonates and the edges of clay minerals (McLean and Bledsoe, 1992). As the pH
decreases, the number of negative sites for cation adsorption decreases, while the
number of sites for anion adsorption increases. Also as the pH becomes more acidic,
metal cations also face competition for available permanent charged sites with Al3+ and
H+ (McLean and Bledsoe, 1992). Under alkaline conditions, all trace metals whether
under hydroxide, oxide, carbonate, and phosphate form precipitate (Lindsay, 1979). The
dissolution of lead, copper, nickel, and zinc precipitates are strongly dependent on the
pH and with retention dramatically increasing above pH 7.0 to 7.5 (Harter, 1983). The
sorption of Cu, Zn, and Cd as a function of pH was examined in acid soils. Copper
sorption increased with increasing pH and Cu was preferentially sorbed over Zn and Cd
(Kuo and Baker, 1980).

The stability of metal complexes is pH-dependent with little association in acidic

media. The adsorption of Cu by montmorillonite is reduced in the presence of water-
soluble ligands extracted from sludges and various other organic materials (Baham and
Sposito, 1986). This behaviour is the opposite of the typical relationship between
metal adsorption and pH (McLean and Bledsoe, 1992). McBride and Blasiak (1979)
studied the effect of pH on Zn2+ and Cu2+ solubility in an acid mineral soil and results
indicate the probable involvement of hydrous oxides of iron, aluminum, or manganese
in the adsorption process; the authors also found that the adsorption on permanent
charge sites of clays or complexation with organic matter could not account for the

- 22 -
apparent fixation of Zn2+ in a non-exchangeable form in the pH range of 5 to 7, while
Cu2+ showed more evidence of being controlled by organic complexation mechanisms.

The soil pH dependence of adsorption reactions of cationic metals is due, in part,

to the preferential adsorption of the hydrolysed metal species in comparison to the free
metal ion. The proportion of hydrolysed metal species increases with pH. Cavallaro and
McBride (1980) found that copper adsorption by soils showed stronger pH dependence
than Cd. This result is consistent with the hypothesis that hydrolysis of Cu at pH 6
increases its retention by soil, while cadmium does not hydrolyse until pH 8. Stahl and
James (1991) also showed that zinc was retained in an exchangeable form at low pH in
soil materials with varied mineralogy and sesquioxide contents (Fe and Mn oxide) but
the non-exchangeable as the pH was increased above 5.5. These changes in mechanism
of sorption are due to the hydrolysis of Zn and the adsorption of the hydrolysed species
by the oxide surfaces. Barrown and Whelan (1998) studied the effects of soil pH on
sorption of cadmium, zinc, nickel and cobalt by changing the pH of a soil and
measuring sorption and observed that when the metal ions were incubated with the soil,
an unit increase in pH decreased the concentration of metal ions about 10-fold for zinc,
about 7-fold for nickel, about 6-fold for cobalt, and about 4-fold for cadmium; however
when the soil was mixed with a large volume of solution, the effects were similar for
zinc and cadmium but slightly smaller for cobalt and slightly larger for nickel. Metal
sorption depended more on metal type than soil composition. Sorption characteristics of
two metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) were
investigated by Appel and Ma (2002) who found that all soils sorbed more Pb than Cd.
Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere
complexation at pH above 3.7. However, the amount of Pb sorbed by the Oxisol was
greater than the amount of negative surface charge.

Effect of redox reactions

The redox potential of a soil system is a measure of the electrochemical potential

or availability of electrons within a system. A measure of the redox potential indicates
whether the metals are in oxidised or reduced state (McLean and Bledsoe, 1992).

- 23 -
Metals or elements which gain electrons and lose in valence are undergoing reduction,
while those losing electrons and gaining in valence are becoming oxidized. In soils,
reducing conditions are brought by the absence of oxygen (anaerobie). This is caused by
the oxygen being consumed by the oxidation of organic matter at a greater rate that it
can be transported into the soil system. This can be caused by water-logged soils or
soils containing oxygen consuming compounds. Oxidising conditions are normally
found in well-drained soils as well as soils that have not been subjected to
contamination by spills or leaks (McLean and Bledsoe, 1992).

Soil redox potential can influence the solubility of metals in soils. In reducing
conditions, the solubility of Zn, Cu, Cd, and Pb is higher in alkaline soil as a result of
the formation of stable soluble organomineral complexes. However in oxidised
conditions, the solubility of metals increases with decreasing pH (Silveira et al., 2003).
Chuan et al. (1996) reported that the mobilities of Pb, Cd, and Zn from a contaminated
soil increased when the redox potential decreased. Generally acidic and reducing
conditions were most favorable for metal solubilization and mobility. The dissolution of
Fe-Mn oxyhydroxides under reducing conditions results in the remobilisation of
adsorbed heavy metals from soils (Chuan et al., 1996). In contrast, under soil flooding
conditions, exchangeable Cd decreases and Cd increases in the complexed fraction,
while under in upland conditions, Cd uptake would be more favourable rather than
flooded conditions (Xiong and Lu, 1993). For instance in submerged paddy rice, the
higher solubility of Fe maintained by Fe3(OH)8 may depress Zn2+ solubility through the
formation of ZnFe2O4 or a franklinite-like solid material (Sajwan and Lindsay,1986).
The behaviour of chromium and selenium also illustrates the importance of redox
conditions to metals mobility in soils. Hexavalent Cr (VI) is toxic and a relatively
mobile anion while trivalent Cr(III) is less toxic, relatively insoluble and strongly
adsorbs to surfaces. Selenate Se(VI) is mobile but less toxic than selenite Se(IV) which
is more toxic, but less mobile (McLean and Bledsoe, 1992).

In general, oxidising conditions help to immobilize metals in soils while

reducing conditions contribute to an accelerated migration. Redox reactions can greatly

- 24 -
affect the transport of contaminants; in slightly acidic to alkaline environments, Fe(III)
precipitates as a highly adsorptive solid phase (ferric hydroxide), while Fe(II) is very
soluble and does not retain other metals. The reduction of Fe (III) to Fe (II) will bring
the release of ferrous iron to the pore waters and also any metals that were adsorbed to
the ferric hydroxide surfaces (McLean and Bledsoe, 1992). In addition, redox
conditions may change as a result of fluctuating soil moisture content or decaying
organic matter or due to biological activity, particularly in the rhizosphere. Staunton and
Wang (2005) found that the change in redox conditions induced by soil moisture
conditions did have some effect on the solubility of Cu and Zn and these changes could
be partially related to changing pH and the solubility of soil metal oxides.

Effect of adsorption

A charged solute ion is attracted to a charged soil surface by electrostatic

attraction and/or through the formation of specific bonds. Retention of charged solutes
by charged surfaces can be broadly grouped into specific and nonspecific retention
(Bolan et al., 2003). The nonspecific adsorption is a process in which the charge of the
solute ions balances the charge on the soil particles through electrostatic attraction,
while the specific adsorption involves the formation of a chemical bond between the
ions and the sorption sites on the soil surface (Bolan et al., 2003; Adriano et al., 2004).
Therefore, the amount of metal sorbed exceeds the cation /anion exchange cabacity of
the soils (Bolan et al., 2003). This infers that the nonspecific adsorption and other
processes such as specific adsorption, precipitation and complex formation also
contribute to the retention of metals in soils (Bolan et al., 2003; Adriano et al., 2004).

In general, both soil properties and soil solution composition determine the
equilibrium between metals in the soil solution and the soil solid phases. The
concentration of metals in soil solution is largely influenced by the pH and the nature of
both organic and inorganic anions (Shuman, 1986; Naidu et al., 1994; Adriano, 2001;
Bolan et al., 2003). The effect of pH values higher than 6 in lowering free metal ion
activities in soils can be attributed to the increase in the pH-dependent surface charge on

- 25 -
oxides of Fe, Al and Mn, chelation by organic matter, or precipitation of metal
hydroxides (Adriano, 2001). Naidu et al. (1994) studied the effect of pH and ionic
strength on the surface charge of soil and sorption of cadmium and who observed that
Cd is adsorbed when the potential of adsorption is either positive or negative providing
evidence for both specific and non-specific adsorption of Cd.

Effect of competitive major cations

Metal adsorption reactions, in a competitive system, are important to determine

the metals availability to plants and their mobility throughout the soil. For specific
adsorption sites, trace cationic metals are preferentially adsorbed over the major cations
(Na, Ca, Mg), while trace anionic metals are preferentially adsorbed over the major
anions (SO4, NO3, soluble ionized organic acids). However, when the specific
adsorption sites of the soil solid phase become saturated, exchange reactions dominate
and competition for these sites with soil major ions becomes important (McLean and
Bledsoe, 1992). Cavallaro and McBride, (1978) reported that in the presence of 0.01M
CaCl2, adsorption of Cu and Cd were much reduced, suggesting that Ca2+ compete for
adsorption sites. The adsorption of Pb from Pb(NO3)2 solutions by Ca-montmorillonite
is depends on the Pb/Ca ratio. Thus, the adsorption of Pb from 0.1M Ca (ClO4)2
solutions were considerably lower and were not sensitive to the weight of the clay
(Griffin and Au, 1977).

The complex formation inhibits the sorption of metals on the clay, with an
increasing influence in the order: Mn ≤ Pb ≤ Cd ≤ Zn < Ni < Cu < Cr. The Na-
montmorillonite clay shows that it is a good sorbent towards all these metals (Abollino
et al., 2003). Ma (1996) studied the effects of Ca, K and Na on Pb immobilisation by
hydroxyapatite [Ca10 (PO4)6(OH) 2] and found that neither Na nor K affected Pb
immobilisation. However aqueous Ca slightly inhibited Pb immobilisation. In addition,
Pb(OH) 2 precipitate was present as positively charged Pb polymers (Janssen et al.,
2007). In acid contaminated soils, copper sorption increased with increasing pH and Cu
was preferentially sorbed over Zn and Cd (Kuo and Baker, 1980). In addition, the
influence of Ni and Cu on Zn sorption was significant only when metal concentration in

- 26 -
the soil solution was in excess of the sorbing capacity of the soil. Thus Cu was more
effective than Ni in decreasing Zn sorption (Elrashidi and O,Connor, 1982). The effects
of aqueous Al, Cd, Cu, Fe, Ni and Zn on Pb immobilisation by hydroxyapatite [Ca10
(PO4)6(OH) 2] was reported by Ma et al. (1994b) who found that these metals inhibited
Pb immobilisation by hydroxyapatite in the order of: Al > Cu > Fe > Cd > Zn > Ni and
Cu > Fe > Cd > Zn > Al > Ni at high and low initial Pb concentrations. This inhibition
was probably through the precipitation of amorphous to poorly crystalline metal
phosphates. For the competitive adsorption, Gomes et al. (2001) reported that the soil
properties may have affected the heavy metals adsorption represented by the distribution
coefficients; pH and cation-exchange capacity (CEC) for Cd, Ni, Pb and Cr while
organic carbon, clay, and gibbsite contents for Cu.

Effect of complex formation

The effect of complex formation on the sorption of metals by soils is dependent

on several factors: the type and amount of metal present, the type and amount of ligands
present, soil surface properties, soil solution composition, pH soil and redox conditions.
The decrease in positive charge on the complexed metals ions reduces adsorption to a
negatively charged surface (McLean and Bledsoe, 1992). In general the formation of
metal cations complexes with inorganic and organic ligands can enhance or inhibit on
the adsorption metals.

a. Complexation by inorganic ligands

Hydrolysis and chloride complexation are important factors in the distribution

and solubility of metals ions. Both the hydroxy and chloride complexes may contribute
to the mobilisation of metal ions such as Hg (II), Cd (II), Zn (II), and Pb (II) in the
environment (Hahne and Kroontje, 1973). In addition, chloride increases the mobility of
Cd(II) and, to a lesser extent, Ni(II) and Cu(II) through soil (Doner, 1978). Elrashidi
and O’Connor (1982) reported that the complexation of Zn (ZnSO4) in the SO42- was
higher than in either the NO-3 [Zn (NO3) +] or Cl- [Zn (Cl) +] form. In an acid soil,
Shuman (1986) also observed that the adsorption zinc with SO2-4 complexes produced

- 27 -
higher adsorption than NO-3 or Cl- ions. Moreover increasing ionic strengths decreased
the amount of Cd sorbed on the clay surfaces. Garcia-Miragaya and Page (1976) found
that the sorption of Cd in the chloride form was higher than in the SO4 form. This is due
to the presence of uncharged and negatively charged complexes of Cd with Cl ligands.

The mechanisms of Cu2+ bond on noncrystalline aluminum hydroxide with or

without various levels of pre-sorbed phosphate was reported by McBride (1985) and
found that high levels of sorbed phosphate suppressed Cu2+ adsorption. The decrease
adsorption of Cu2+ was a result of the weaker coordination of Cu2+ to the phosphate-
coated surface than to the alumina surface in the absence of phosphate. In addition, the
sorption of cadmium by phosphate-free and phosphate-enriched hydrous iron oxides
was investigated by Kuo and Neal (1984). They found that the precipitation of these
compounds was not a likely mechanism controlling the concentrations of soluble Cd for
these systems. The adsorption of Zn was increased when the presence of phosphate on
oxide surface (Bolland et al., 1977). Ma et al. (1994a) also studied the effects of
inorganic ligands such as (NO3-, Cl-, F-, SO42-, and CO32-) on Pb2+ immobilisation by
hydroxyapatite. Results indicate that the solution concentrations of Pb2+ were reduced
after reaction with hydroxyapatite, except in the presence of high levels of CO32- and
Pb2+.

b. Complexation by organic ligands

Soil organic matter is important for cation exchange reactions and in the
formation of complexes with metals. Soluble organic molecules can form stable
complexes with metals which are mobile in the soil solution and bioavailable due to the
protection on the metal from adsorption on soil colloid surfaces by the organic ligand
(Alloway and Ayres, 1997). With increasing pH, the carboxyl, phenolic, alcoholic and
carbonyl functional groups of organic matter dissociate, thereby increasing the affinity
of ligand ions for metal cations. The general order of affinity for metal cations
complexed by organic matter is present in the following sequence (Adriano, 2001).

Cu2+>Cd2+>Fe2+>Pb2+>Ni2+>Co2+>Mn2+>Zn2+

- 28 -
 The complex formation between metals and organic ligands influences the
adsorption and mobility of metals. The extent of complexation between a metal and
soluble organic matter depends on the competition between the metal-binding surface
sites and the soluble organic ligand for the metal (McLean and Bledsoe, 1992).
Interaction of Cu with dissolved organic matter (DOM) is an important physico-
chemical process affecting Cu mobility in the soils. The presence of soluble organic and
complexed Cu in the solution is depending on the pH soil and high amount of organic
matter (McBrid et al., 1997). Zhou and Wong (2001) suggested that the sorption of Cu
increased with an increase in the pH for soils without the addition of DOM, while Cu
sorption in the presence of DOM was decreased with an increase in pH at a pH higher
than 6.8. The mobility of some micronutrients such as Mn, Zn, Cu, and Fe was
investigated and found to be affected by soil organic matter and humic acid fraction
(Khan et al., 1997); it was also found that the soil organic matter concentration
increased caused by the decreased of the metal mobility, while the increasing
concentration of the humic acid fraction generated an increase in their mobility in the
order Mn >Zn >Cu >Fe. In addition, the metal mobility through the soil followed the
order: Ni > Mn > Cr > Cu > Pb and the higher mobility were observed in soil with
decomposed organic matter than in soil with organic matter (Khan et al., 1996).

The distribution of trace metals in natural aqueous systems may be controlled by

surface binding on colloidal particles coated with humic compounds rather than
reactions with simple oxide surface sites. In some cases metal uptake is increased by the
presence of adsorbed ligands at the mineral surface. Trace metal adsorption can be
significantly enhanced when a ligand is adsorbed with a strongly complexing such as
thiosulfate, glutamic acid, 2,3-PDCA, ethylenediamine (Davis and Leckie, 1978;
McLean and Bledsoe, 1992). Copper uptake was significantly decreased by the presence
of picolinic acid. Therefore picolinic acid complexed Cu and the resulting complex
were not adsorbed by the oxide surface (Davis and Leckie, 1978). In contrast, Cd(II)
adsorption was not significantly affected by the presence of organic matter at the oxide
surface, due to weak complex formation with the organic ligands (Davis, 1984).

- 29 -
2.3.5. Soil additives for physico-chemical immobilisation of metals

In situ remediation techniques or in situ immobilisation methods generally aim

at decreasing the labile pool of metals and metalloids such as Cr, Cu, As that originate
from chromated copper arsenate (CCA) used as wood impregnation and also reduce
other metals such as Zn, Pb, Cd, Ni by incorporation of amendments into the
contaminated soil. In situ immobilisation by the addition of amendments is less
expensive and non-disruptive for the natural landscape, hydrology, and ecosystems as
compared to the conventional excavation, treatment, and disposal methods. These
techniques are able to enhance one or several sorption processes such as metal
adsorption through increased surface charge, increased formation of organic and
inorganic metal complexes, sorption on Fe, Mn and Al oxides, and precipitation. This
technique can be used in in situ and ex situ applications to reclaim and re-vegetate
industrially devastated areas and mine-spoils, restore the physical, chemical, and
biological soil properties, and reduce the contaminant mobility and bioavailability with
various chemical and mineralogical agents (Mench et al., 2000; Oste et al., 2002; Bolan
and Duraisamy 2003; Adriano et al., 2004; Pérez de Mora et al., 2005; Raicevic et al.,
2005; Kumpiene et al., 2006; Kumpiene et al., 2008).

Several application studies have demonstrated that the in situ immobilisation of

contaminated soils and groundwaters by using inexpensive soil amendments, such as
alkaline materials (calcite, lime, dolomite and slag), phosphate minerals (phosphoric
acid, phosphate rocks, synthesized apatites), aluminosilicates mineral (clay and
zeolites), iron and manganese oxides and hydroxides and zerovalent iron, organic matter
and alkaline biosolids (waste by-products) were found to be suitable for the remediation
of metal-contaminated soils. The amendments significantly reduced the mobility of
metals in soil, metal uptake by plants, and metal phytotoxicity. The following common
soil additives for the in situ immobilisation of metals contaminated soil will be
discussed in detail.

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2.3.5.1. Alkaline materials

Neutralizing agents in the form of alkaline materials are usually added to acidic
soils to ameliorate the chemical and physical properties of these soils (e.g. EC and pH)
and reduce the mobility and bioavailability of metals to plants. Tylar and McBride
(1982) reported that the addition of lime to an acidic soil can reduce the metals
mobility. The amount of liming material required to rectify the soil acidity depends on
the neutralising value of the liming material and pH buffering capacity of the soil
(Brallier et al., 1996; Brown et al. 1997; Bolan and Duraisamy, 2003; Tlustos et al.,
2006). A range of liming materials is available including calcite (CaCO3), burnt lime
(CaO), slaked lime [Ca(OH)2], dolomite [CaMg(CO3)2], and slag [CaSiO3], with
various ability to neutralise the acidity (Bolan and Duraisamy, 2003).

The lime binds H+ ions which are sorbed to binding sites on the surface of soil
particles. According to changes in the soil pH, the lime can induce metal hydrolysis
reactions and/or co-precipitation with carbonates, thus acting as a precipitating agent for
metals in the soil (Mench et al., 1998). In general, a rise in pH decreases the mobility of
metals in the soil. In contrast, under alkaline conditions in the soil the mobility of anions
(e.g., arsenate and chromate) (Singh and Oste, 2001) or organic contaminants can be
increased by increasing the soluble organic matter fractions (Mench et al., 1998). The
addition of lime in acid soil does not only replace hydrogen ions and raises the soil pH,
thereby eliminating most major problems associated with acid soils, but also provides
two nutrients, calcium and magnesium, to the soil. Lime also makes phosphorus that is
added to the soil more available for plant growth and increases the availability of
nitrogen by hastening the decomposition of organic matter (SUNY-ESF, 2009).

Lime is a well known amendment in agriculture and it is used to increase the

availability of essential nutrients and also to decrease the availability of elements
harmful to plants, animals and humans (Singh and Oste, 2001). Liming is one of the
methods commonly in soil to reduce the solubility and plant uptake of Zn and Cd
(Krebs et al., 1998) and decreases the soluble fraction and the concentration of Cd, Ni,
Zn and Cu in plants significantly in metals rich soils (Singh and Oste, 2001).

- 31 -
Applications of lime combined with organic matter were already practiced more than
thirty years ago to remediate the Cu phytotoxicity in French vineyard (Mench et al.,
1998). Derome and Saarsalmi, (1999) found that the addition of lime can decrease the
Cu, Ni and Zn concentration in the soil solution sampled by a lysimeter in a
contaminated soil. The addition of lime at high excess copper in a contaminated soil
improved the growth of plant seedling (Fessenden and Sutherland, 1979). Bes and
Mench (2008) reported that the application of lime to remediate a copper contaminated
soil can increase the pH soil, improve the beans plant growth and decrease the Cu
concentration in the soil solution and primary leaves. On the other hand, Mench et al.
(1998) found that liming of contaminated soils was less effective to reduce the Cd
mobility and plant Cd and Zn uptake. In addition, the application of lime in acid soils
reduced the uptake of Cd, Ni and Zn to crops as well as increasing crop yield, but
generally did not change Cu uptake by crops (Brallier et al., 1996). Similarly, Tlustos et
al. (2006) found that the efficiency of liming for immobilisation of Cd, Pb, and Zn in
acid contaminated soil reduced these metals uptake and increase the crop production.

The addition of alkaline materials may be an effective chemical treatment for the
immobilisation of cationic metals in the acid soil solution (Mench et al., 1998; Singh
and Oste, 2001). Limestone addition to contaminated soils can reduce the labile Zn soil
fractions, increase the soybeans yield and decrease tissue metal concentration (Mench et
al., 1998). In addition to the effects of limestone or manure on the availability of soil
Zn, Cd and Pb to soybeans grown in metal contaminated soil, the soybeans yield was
significantly increased and the Zn concentration was reduced while the root tissue Cd or
Pb concentration were not significantly influenced by the addition rate of limestone or
manure (Pierzynski and Schwab, 1993). Similarly the application of sugar foam and
dolomite residue in a metal contaminated soil reduced the availability and mobility of
Cd, Cu and to a lesser extent, Pb, while the application of red gypsum and
phosphogypsum in this soil proved effective in immobilizing Pb and to a lesser extent
Cu and Cd (Garrido et al., 2005).

- 32 -
2.3.5.2. Phosphate minerals

Phosphate compounds and associated materials such as phosphoric acid,

phosphate rocks, synthesized apatites have been successfully applied to stabilize Pb, Cd,
Zn and Cu in contaminated soils, sediments and solid wastes, reducing their
bioavailability for plant uptake and thus their mobility in soils and subsequent
groundwater contamination (Bolan et al., 2003; Liu and Zhao, 2007). Phosphate
enhance the immobilisation of metals in soils through several processes including direct
metal adsorption by the phosphate, phosphate anion-induced metal adsorption and
precipitation of metals with phosphate as metal phosphates (Adriano et al., 2004).
Surface complexation and coprecipitation are the most important mechanisms with
possibly ion exchange and solid diffusion; the major metal surface species are likely to
be ≡POZn+ and ≡POCd+ (Xu et al., 1994). The effects of phosphate addition on Zn
sorption could be large and could either increase or decrease Zn sorption depending on
the direction of the pH effect (Barrow, 1987).

Phosphates minerals have the potential to sorb and /or coprecipitate trace metals
(Ma et al., 1993; Pierzynski and Schwab, 1993; Xu et al., 1994; Ma, 1996; Mench et al.,
1998). The application of phosphate minerals for the remediation of contaminated soils
with in situ immobilisation of Pb was reported by numerous authors (Ma et al., 1995;
Ma 1996; Basta et al., 2001; Cao et al., 2003; Chen et al., 2003; Geebelen et al., 2003).
Hydroxyapatite [Ca10(PO4)6(OH)2 ; HA] is effective in immobilizing aqueous Pb in the
presence of anions (NO3-, Cl -, F-, SO4 2-, or CO3 2- ) and cations (Al3+, Cd2+, Cu2+, Fe2+,
Ni2+ or Zn2+) (Ma et al., 1994a,b). The sorption of aqueous Pb was primarily through a
process of dissolution of apatite followed by the precipitation of variable pyromorphite-
type minerals (Wright et al., 1995). The addition of hydroxyapatite [Ca10(PO4)6(OH)2 ;
(HA) in the presence of Ca, K, Na, calcite and EDTA in Pb-contaminated soils can
reduce aqueous Pb by 97% in the form of hydroxypyromorphite [Pb10(PO4)6(OH)2 ; HP]
( Ma, 1996). HA was also effective at reducing the solubility of Ni, Al, Ba, U, Cd, Co,
Mn, and Pb in several contaminated soils (Seaman et al., 2001). In addition, the
application 0.5% and 1% hydroxyapatite (HA) as a soil additive for the in situ
remediation of metals (Zn, Pb, Cu, and Cd) in contaminated soils resulted in a decreased

- 33 -
of the exchangeable metal contents in soil and also a decrease of toxic metals in the
plant leaves; however As mobility increased due to the phosphate-arsenate competition
for the sorption complex of the solid soil phase (Boisson et al., 1999a,b).

On the other hand, phosphate rock (PR) was equally or more effective than triple
superphosphate (TSP) or phosphoric acid (PA) in reducing bioavailable Pb in
contaminated soils. Thus, the dissolution of PR and subsequent formation of
pyromorphite can be expressed as follows (Hettiarachchi et al., 2001).

Ca5 (PO4)3X (s) + 6H+ (aq) 5Ca+2(aq) + 3H2PO4- (aq) + X- (aq) [1]

5Pb2+ (aq) + 3H2PO4- +X-(aq) Pb5 (PO4)3X (s) +6H+ (aq) [2]

Where X = F-, OH-, or Cl-.

In Pb contaminated soils, the addition of triple superphosphate (TSP)

significantly reduced bioavailable Pb, Cd, and Zn concentrations in shoot plants and did
not change with the addition of phosphate rock (PR), while the combination of
phosphate rock (PR) and Mn oxide significantly reduced Pb concentrations in plants
(Hettiarachchi and Pierzynski, 2002). In contrast, Cao et al.(2004) found that PR has the
highest affinity for Pb, followed by Cu and Zn in contaminated soil and also reported
that the greatest stability of Pb retention by PR can be attributed to the formation of
insoluble fluoropyromorphite [Pb10 (PO4)6F2]. In addition, PR amendment enhanced
metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it also
significantly reduced metal translocation from root to shoot, especially Pb via the
formation of a pyromorphite-like mineral on the membrane surface of the root (Cao et
al., 2003).

Thomas phosphate basic slag was used as an amendment in several

contaminated soils, which affect KdCd especially in acid soil, decreases Cd and Zn in
shoot uptake by ryegrass, restorate dwarf beans growth and also lowers Pb

- 34 -
bioavailability in contaminated soils and concentration of Pb uptake by plants (Mench
et al., 1994a,b). The combination of Thomas phosphate basic slag and steel shots were
more effective in reducing Zn and Cd mobility than when used separately for
contaminated soils. This combination may also limits possible Mn phytotoxicity in
sensitive plant species (Mench et al., 1998). The incorporation of phosphate compounds
(e.g. Thomas basic slag, ammonium phosphate and triple super phosphates) into a
highly Cu contaminated soil from wood treatments facility was reported by Bes and
Mench (2008). They also found that Thomas basic slag increased the soil pH values and
foliar Ca concentration, decreased the Cu concentration in the soil solution and restored
shoot and root biomass of beans plants. Additionally the effect of ammonium phosphate
and triple super phosphate on plants production was consistent with high Cu
concentration in the soil solution.

Vivianite minerals (iron phosphate) are a group of phosphates that have very
similar structures (Fe3 (PO4)2 .8(H2O) and are used for the in situ immobilisation of
metals in contaminated soils. Liu and Zhao (2007) reported that the use of iron
phosphate as a stabilizer for the in situ immobilisation of Cu in contaminated soils can
effectively reduce the leachability of Cu. The formation of copper phosphate minerals
through precipitation and adsorption was probably responsible for the decrease of the
Cu availability in soils. On the other hand, the combination of Ca (H2PO4)2 and CaCO3
stabilizers in a multi-metal contaminated site containing Cd, Cu, Ni, Pb and Zn reduced
the leaching extractable concentrations of these metals by more than 87% in a
laboratory test, while the reduction ratios were 98% for Cd, 97% for Cu, 99% for Pb,
96% for Zn and 65% Ni for the field treatments (Wang et al., 2001). In addition, the
incorporation of K2HPO4 into a Zn contaminated soil significantly increased soybeans
yields and significantly decreased the Zn concentrations in soybeans tissues (Pierzynski
and Schwab, 1993).

- 35 -
2.3.5.3. Aluminosilicates minerals

Aluminosilicates mineral consists of natural materials like clay and zeolites,

synthetic zeolites and incinerator ashes. Zeolites are naturally crystalline and highly
porous materials. The framework of zeolites consists of [SiO4]4- and [AlO4]5- tetrahedral
linked at all corners and creating fixed negatively charged sites through the structure.
These tetrahedral are the basic building blocks for various zeolite structures, such as
zeolites A and X (the most common commercial adsorbents) (Singh and Oste, 2001).
While the negative charges are balanced by an equivalent number of mobile cations
loosely in the crystal structure and free to exchange with other cations in solution
(Mench et al., 1998). Several studies were focused on the use of zeolites as
immobilisation agents (Gworek, 1992; Chlopecka and Adriano, 1997; Leggo and
Ledésert, 2001; Singh and Oste, 2001; Oste et al., 2002; Mahabadi et al., 2007).
Zeolites can decrease the free metal concentrations in the soil solution, leading to a
decreased metal uptake by plants. A small amount of zeolites may influence soils with a
high acid buffering capacity and a pH above 6, particularly to reduce metal uptake by
plants (Oste et al., 2002). Zeolites were used for a long time in Japan to improve the
soil quality. In general, farmers add zeolites to the soil to control the soil pH and
nitrogen retention. In wastewater treatment plant, natural zeolites were used to remove
ammonium ions and heavy metals (Singh and Oste, 2001). The combination of a
nutrient source with a zeolite amendment is beneficial for plant growth on a heavily
polluted soil as zeolite does not interfere with the action of the fertilizer by binding
nutrient cations (Mench et al., 1998).

Synthetic zeolites have a high capacity to bind heavy metals; moreover the
alkaline character of this material can increase metal sorption to the soil. For instance a
sodium-saturated zeolite can be bound high amounts of Ca and the competition of Ca in
the soil can be decerased (Oste et al., 2002). Oste et al. (2002) reported that the addition
of synthetic zeolite had an effect on the immobilisation of Cd and Zn. They found that
the free ionic concentration of Cd and Zn strongly decreased after the addition of
zeolites which might explain the reduction in metal uptake in plant growth. The addition
of zeolite reduced heavy metal concentration in the leachate, as well as inhibited heavy

- 36 -
metal mobility in the soil. In fact, the higher cation exchange capacity of the zeolite-soil
mixtures and higher pH were responsible for stabilising Cd in soils. Lin et al. (1998)
reported that the effect of synthesized zeolite on a Cd-contaminated acidic loamy soil
reduced Cd leaching. The addition of synthetic zeolites to metal contaminated soils can
reduce the soil phytotoxicity and improve the quality of plant growth (Edwards et al.,
1999).

Beringite, a modified alumino-silicate that originates from the fluidized bed

burning of coal refuse (mine pile material) was investigated for the immobilisation
metals contaminated soil. The high metal immobilisation capacity of beringite is based
on chemical precipitation, ion exchange and crystal growth. The combination of these
sorption mechanisms can explain its high metal sorption capacity (Mench et al., 1998).
Beringite has been used in several studies to reduce the metal concentration in soil
solution and the metal uptake by plants (Mench et al., 1994b; Oste et al., 2001;
Geebelen et al., 2006). Beringite can be used for the fixation Zn and Cd in contaminated
soils and can strongly reduce or eliminate the phytotoxicity of these metals in beans
plants. Therefore the addition of 5% beringite to a Zn-contaminated sandy soil resulted
in an increased shoot length and leaf area of beans plants and also reduced the Zn
concentration in leaves from 350 mg kg−1 to 146 mg kg−1 (Mench et al., 1998).
Similarly, the application of beringite to immobilize Cu in metal contaminated soils of
coffee gardens in Tanzania increased the plant growth of maize and beans plants
(Loland and Singh, 2004). Beringite also increased concentration of Cu extracted by
diethylenetriaminepentaacetic acid (DTPA) (Singh and Oste, 2001).

2.3.5.4. Iron and manganese Oxides and hydroxides

Iron and manganese oxides and hydroxides are known to play an important role
in the retention, mobility and bioavailability of metals in contaminated soil (Mench et
al., 1994a; Silveira et al., 2003). Iron oxides can used to stabilise many trace elements
in soils contaminated from industrial activities such as mining, wood impregnation in
soil (Moore et al., 2000; Mench et al., 2003; Warren et al., 2003; Kumpiene et al.,

- 37 -
2006; Mench et al., 2006). Specific adsorption of copper on goethite was reported by
Padmanabham, (1983) who found that the goethite has a great capacity to immobilise
Cu. Hartley et al. (2004) studied the effect of Fe3+, Fe2+, iron grit, goethite and lime on
immobilising soluble arsenic in contaminated soils and found that Fe-oxides formed in
situ were more effective at immobilising soluble arsenic compared to goethite. In
addition, iron oxide application for the treatment of As-contaminated garden soils
resulted in a 50% reduction of water extractable As and a decrease of As accumulation
in dwarf beans leaves (Mench et al., 1998). On the other hand, the addition of hydrous
manganese oxides (HMO) in Cd and Pb contaminated soil decreased to a maximum
extent Cd in ryegrass and tobacco plants. Therefore the used of HMO reduced Pb
concentrations only in ryegrass shoots and HMO exhibited a most promising potential to
reduce either Cd or Pb transfer from the soil to soil solution or their entry into the food
chain via plant uptake (Mench et al., 1994a). In addition, the soluble and exchangeable
fractions of Cd, Ni and Zn in a contaminated soil were decreased by the addition of 1%
of hydrous iron oxide and to a lesser extent with hydrous manganese oxide. However, in
these studies, hydrous iron oxide did not generally reduce shoot metal uptake by plants
(Mench et al., 1998).

Zerovalent iron (Fe0) was also used for the stabilization of trace metals in a
contaminated soil (Sastre et al., 2004; Kumpiene et al., 2006). The application of 1%
Zerovalent iron (Fe0) to reduce the mobility and bioavailability of Cr, Cu, As and Zn in
a CCA-contaminated soil was investigated by Kumpiene et al. (2006). They found that
both As and Cr concentrations decreased in soil leachates by 98% and 45% respectively,
whereas As and Cr concentrations in soil pore water decreased by 99% and 94%
respectively ; additionally As and Cr concentrations in plant shoots decreased by 84%
and 95% respectively. However zerovalent iron was not effectively to stabilize Cu. Steel
abrasive (SA) or oxygen scarfing granulate (OSG) may be effective amendments for
CCA-contaminated soil. The application of SA or OSG to stabilization of metals from
CCA-contaminated soil decreased the concentrations of As, Cr, Cu, and Zn in leachates
and soil pore waters, while the effect of the mobility As was lower in the soil with
higher organic matter content, probably due to dissolved organic matter competing for
sorption sites on the iron oxides (Lidelöw et al., 2007). The application of red mud as a

- 38 -
soil amendment in metal contaminated soil was reported by Friesl et al. (2003). These
authors found that the red mud decreased the lability of Zn, Cd, and Ni in soils and the
plant uptake of metals.

2.3.5.5. Coal fly ashes

Industrial by-products, like coal and biofuel combustion fly ashes (CFA), are
alkaline materials with a high sorption capacity (Kumpiene et al., 2007). Fly ashes are
frequently composed of a ferro-aluminosilicate mineral in which Al, Si, Fe, K and Na
are the predominant elements. The fine sand-silt particle size of fly ash makes it more
susceptible than natural soils to detachment and transport by erosive processes. In
addition, because the high content of the silt-size particles in a fly ash, the soil is more
susceptible to surface crust formation, resulting in reduced infiltration and increased
surface runoff and erosion (Gorman et al., 2000). Fly ash is a useful ameliorant that
may improve the physical, chemical and biological properties of degraded soils and
mine lands (Gorman et al., 2000; Jala and Goyal, 2006). As many fly ashes are highly
alkaline, they have been used as amendments to neutralize highly acidic soils, decrease
the bulk density, increase the water holding capacity, reduce the soil compaction and
precipitate soluble metals. However the application of fly ash may also result in
excessive soluble salts concentrations, excess boron, and adverse effects on the soil
properties (e.g. cementation) and may even generate increased the concentrations of
potentially toxic trace elements (Mench et al., 1998). However the addition of fly ash
reduced metals content in a contaminated soil (Ciccu et al., 2001). Soil amendment with
coal fly ash and peat reduced the leaching of Cu and Pb from a contaminated soil
(Kumpiene et al., 2007). This is possibly due to an increased amount of sorptive sites.

The most immediate effects of fly ash incorporation into soil are increases in
both alkalinity and salinity (Mench et al., 1998). The application 10 t ha−1 of fly ash in
combination with organic sources and chemical fertilisers increased the grain yield and
nutrient uptake of rice, the pod yield of peanut compared to the application of chemical
fertilisers alone. Additionally the metal contents in the plant and soil system were found

- 39 -
to remain below the permissible level (Mittra et al., 2005). Moreover, in acid lateritic
soil, the low availability of P and high content of Al and Fe generates nutritional
imbalance which is generally corrected by lime materials. Alkaline fly ash can be used
in such problematic soils as an amended material and also acts as a source of readily
available plant macro and micronutrients (Mittra et al., 2005; Jala and Goyal, 2006).
Therefore the integrated use of fly ash, organic wastes and chemical fertilizers was
beneficial in improving crop yield, soil pH, organic carbon and available N, P and K in
sandy loam acid lateritic soil (Rautaray et al., 2003). In addition the application of a
combination of coal fly ash and peat increased the soil pH and decreased the metal
mobility to allow the re-vegetate soil and reduce the metal uptake into plant shoots and
reduced the soil toxicity to microorganisms (Kumpiene et al., 2007).

2.3.5.6. Organic amendments

Organic matter is one the most important soil constituents retaining metals.
Metal-organic associations can occur both in solution and in the solid surfaces of either
native soil constituents or any added material (e.g. biosolids) (Silveira et al., 2003). The
application of sewage sludge or biosolids on soils has been widespread in agricultural
areas; depending on their characteristics, they may cause an increase in metal
concentration of the treated soils. Li et al. (2000) reported that the application of
biosolids compost reduced soluble Zn and Cd in a highly Zn-contaminated soil. The
potential for biosolids products to reduce Pb availability in a high Pb urban soil was
shown by Brown et al.(2003). Kiikkila et al. (2002) studied the effect of biosolids as
organic immobilizing agents in a heavy metal-polluted forest soil. They observed that
the exchangeable Cu concentration decreased in the polluted soil; on the other hand,
copper and lead mobility and bioavailability in soil were effectively reduced by using a
combination of coal fly ash and natural organic matter (peat) as soil amendments
(Kumpiene et al., 2006). In addition, organic amendments such as manures were
successul to immobilise Zn, Cd, and Pb in a metal- contaminated alluvial soil
(Pierzynski and Schwab, 1993). The addition of a paper mill sludge, consisting mainly
of carbonates, silicates and organic matter to a heavy-metal polluted soil decreased the
available metal forms (Calace et al., 2005).

- 40 -
2.3.6. Remediation of trace elements in contaminated soils using slags
as soil amendments
2.3.6.1. Definition

Slag is a final waste material in steel making processes. In blast furnace iron
making, limestone (as fluxes) is added to react with the gangue minerals (iron ore and
coke) to form iron slags. In a basic oxygen furnace, the molten iron is converted into
steel reacting with oxygen (Li, 1999). Kim et al. (2008) reported that slag is an alkaline
by-product of metallurgical processes or a residue of incineration processes. Although
slags are in fact, classified as wastes, they can currently consider as a product (Geiseler,
1996).

2.3.6.2. Production and application of slag in different fields

Slag is produced in metallurgical processes or as residues in incineration

processes. The amounts of steel slag production in different countries are presented in
Table 2.3 (Shen and Forsberg, 2003). Slag have been successfully used in different
applications such as fertiliser (phosphates fertiliser), mainly used as aggregates for road
construction (e.g. asphaltic or unbound layers), as armourstones for hydraulic
engineering constructions (e.g. stabilization of shores), civil engineering work, and
production of metallic iron and iron concentrate (Geiseler, 1996; Motz and Geiseler,
2001; Shen and Forsberg, 2003; Charles and Nemmer, 2006), and also used as landfill
daily cover, soil reclamation and water refinement (Li, 1999; Ortiz et al., 2000). In
Europe, approximately 85% of basic steel slag is re-used, 42% in civil engineering, 17%
for metallurgical use, 16% as fertiliser for agriculture purposes, and 10% as bulk fill
material (Geiseler, 1996). The application of steel slag in the different fields is shown in
Figure 2.1 (Shen and Forsberg, 2003).

- 41 -
 Table 2.3: Production of steel slags in the different countries
Country Steel slag (BOF+EAF) (Million tons/year)
Europe 12
USA 8
China 14.07
Japan 12.60
Source: Shen and Forsberg (2003)

Figure 2.1: Application of steel slag in different fields

2.3.6.3. Chemical composition of various slags

A large percentage of solid wastes are the metallurgical slags containing a

quantity of various metals such as CaO, MgO, SiO2, Al2O3,FeO, MnO and P2O5 which
are usually utilized as a resource material in many areas. In the steel making process,
steel making slag is produced from basic oxygen furnace (BOF steel slag), electric arc
furnace (EAF steel slag) and ladle furnace (LF steel slag). The chemical compositions
of the various slag is presented in Table 2.4 (Motz and Geiseler, 2001; Shi, 2002;
Alanyali et al., 2006). In addition, Kawatra and Ripke (2002) reported that the

- 42 -
steelmaking slags are produced by the steel production techniques such as blast furnace
(BOF), electric arc furnace (EAF), and ladle furnace (LF) and they are typically contain
20–25% iron. The mineral composition of steel slag also varies. The main mineral
composition of slag may include major solid phases such as calcium-silicate
(dicalciumsilicate, tricalciumsilicate and dicalciumferrite), calciowustite,
magnesiowustite, calcium aluminate, free lime and free magnesium (Dimitrova, 1996;
Geiseler, 1996; Dimitrova and Mehanjiev, 1998; Motz and Geiseler, 2001). The content
of free lime and free MgO is the most important component for the utilisation of steel
slags for different remediation applications. The free lime and free MgO in the slag
occur as both precipitate from the melt, which would be associated with a more
complicated mechanism of adsorbing and fixing metal ions due to the participation of
different active phases (Geiseler, 1996; Motz and Geiseler, 2001). Radosavljevic et al.
(1996) reported that the mineralogical composition of the slag is made of iron, calcium
ferrite, larnite, rankinite, wustite, periclase, manganosite, Fe and Mn monticellite, Mn--
cordierite, melilite and glass. Steel slag consists of CaO, Fe2O3, SiO2, MgO, Al2O3 and
MnO (Shen and Forssberg, 2003; Tsakiridis et al., 2008). Olivine, merwinite, C3S, C2S,
C4AF, C2F, RO phase (CaO-FeO-MnO-MgO solid solution) and free-CaO are the
common minerals in the steel slag (Shi and Qiua, 2000; Shi, 2002). In addition, steel
slag is mainly composed of CaO, SiO2, Fe2O3, Al2O3, MgO, MnO and P2O5 (Cha et al.,
2006; Tossavainen et al., 2007). The major mineral in ladle slag fines is γ-C2S, C3S, β-
C2S, 54CaO.MgO.Al2O3.16SiO2, 11CaO.7Al2O3.CaF2, γ-C2S, 3CaO.MgO.3SiO2,
CaMg(CO3)2, CaF2 and Ca(OH)2 ( Shi, 2002).

Table 2.4: Chemical compositions of various slags %

Slag indicates Fe products CaO SiO2 Al2O3 MnO MgO

BF <1 30-40 32-40 7-11 <1 12-18
BOF 5-35 31-55 10-22 1-4.5 0-8 2-15
EAF 10-34 1-60 6-57 2-14 0-15 0.5-15
LF 0-10 40-60 3-27 5-40 0-10 3-15
BF: Blast furnace; BOF: basic oxygen furnace; EAF: electric arc furnace; LF: ladle furnace

- 43 -
 Some steel slags contain higher amount of P2O5 and S than iron concentrate.
This may affect the direct recycling of the steel slags to the iron and steel making
process (Shen and Forsberg, 2003). Phosphorus slag is a by-product of the production of
elemental phosphorus and is composed mainly of SiO2 and CaO, the CaO/SiO2 ratio of
phosphorus slag usually ranges from 0.8 to 1.2. The main minor components in
phosphorus slag are 2.5–5% Al2O3, 0.2–2.5% Fe2O3, 0.5–3% MgO, 1–5% P2O5 and 0-
2.5% F. (Shi and Qiua, 2000). In addition, the main crystalline compounds in air-
cooled phosphorus slag are CaO·SiO2; 3CaO·2SiO2 and 3CaO·2SiO2 (Shi and Qiua,
2000). On the other hand, in acidic soils, the phosphorus availability of Thomas slag is
similar to that of other water soluble phosphorus fertilisers (Sinaj et al., 1994). The
Thomas slag was composed of P, Si and Ca and silicato-calcium phosphates were the
prevailing form of P in the cells and a high Fe, Ca and Mn content was found in the
walls (Sinaj et al., 1994). In addition, Thomas basic slag consists of 37.8% CaO, 2.8%
Al2O3, 14.4% Fe2O3, 10.6%, SiO2, 1.9%, MgO, 1.6% MnO2 and 1.2% P2O5 (Panfili et
al., 2005). Also, Thomas basic slag contains some phases such as larnite, calcium silico
phosphate containing P2O5, calcium ferrite (Ca2Fe2O3), wustite (FeO), lime and
magnetite (Panfili et al., 2005).

2.3.6.4. Slags sorption properties

The adsorption capacity of the slag is dependent on the pH and the hydration of
the slag in aqueous solutions. The sorption of metal ions by slag from ferrous and
nonferrous metallurgy is caused by various processes: ion-exchange and replacement of
calcium ions from the slag by the metal ions in the solutions as chemical bonding of
hydrolysis metal species with the surface. The composition of the slags (oxides, calcium
silicates, aluminosilicates, etc.) is associated with a more complicated mechanism of
adsorbing and fixing metal ions due to the participation of different active phases
(Dimitrova, 1996; Dimitrova and Mehanjiev, 1998). These ions react with the
hydrolysed silicates resulting in the formation of scarcely soluble metal silicates on the
slag surface and the metal ions sorption takes place mainly in the form of 2CaO.SiO2.
Major hydration reactions may occur with calcium oxide, magnesium oxide, calcium
silicates, and calcium aluminates as following (Yan et al., 2000; Cha et al., 2006).

- 44 -
For free-CaO and free-MgO

CaO+H2O→Ca (OH) 2 (1)

MgO+H2O→Mg (OH) 2 (2)

For calcium silicates and calcium aluminate

2Ca2SiO4+4H2O→3CaO.2SiO2.3H2O+Ca (OH) 2 (3)

2Ca3SiO5+6H2O→3CaO.2SiO2.3H2O+3Ca (OH) 2 (4)

CaO.7Al2O3+12H2O→CaO.Al2O3.6H2O+6Al2O3.H2O (5)

In general, slag, which consists of calcium oxide, aluminium oxide, and other
metal oxides, is an abundant by-product in the steel-making process. It has been used as
an adsorbent to remove various metals, the major removal mechanisms being
precipitation and adsorption on the surface of metal oxide. The relative contribution of
adsorption on the removal of copper using slag decreased dramatically and that of
precipitation increased sharply as the initial pH increased. The mechanism of copper
removal using slag is not adsorption on slag surface but rather precipitation with
hydroxide dissolved from slag as most of copper was removed by slag in the form of
copper hydroxide (Kim et al., 2008). In addition, Ortiz et al. (2001) reported that
magnetite which is the main component of converter slag in the steel industry can be
used like an adsorber material for wastewater treatment. In fact the application of 1g of
the converter slag reduced the Ni concentration from 20 to 1.57 mg/l. Moreover blast-
furnace slag is an effective sorbent for Cu, Zn, Ni and Pb ions in a wide range of ion
concentration and pH values (Dimitrova1996; Dimitrova and Mehandjiev, 1998).

2.3.6.5. Effect of slags addition on soil properties

Alkaline materials are usually added to acidic soils to ameliorate soil chemical
and physical properties and also to reduce the mobility and bioavailability of metals in
contaminated soils (Brallier et al., 1996; Brown et al., 1997; Krebs et al., 1998; Singh

- 45 -
and Oste 2001; Bolan and Duraisamy 2003; Gray et al., 2006; Tlustos et al., 2006). Slag
has been used as a soil additive to remove various metals in contaminated soils by
precipitation and adsorption on the surface of the metal oxide (Kim et al., 2008). The
application of Linz-Donawitz (LD) slag in acid soils managed under pastures increased
the soil pH with and without NPK fertilization (Pinto et al., 1995). Ali and Shahram
(2007) found that the increasing rate of soil pH was proportional to the slag amount
added in the soils. The application of slag treatments in the soil increased more the soil
pH than converter sludge treatments (Forghani et al., 2006). Calcium silicate slag can
reduce the soil acidity and increase the available Ca, Mg, Si and P (Besga et al., 1996;
Barbosa Filho et al., 2004), whereas exchangeable Al, Mn, Cu and Zn decreased (Besga
et al., 1996). Thomas phosphate basic slag (TBS) was used as an amendment in several
contaminated soils to decrease the mobility and bioavailability of Cd, Zn and Pb
(Mench et al., 1994a,b). In addition, the incorporation of Thomas basic slag into an
excessively Cu contaminated topsoil from a wood treatment facility increased the soil
pH and decreased Cu concentration in the soil (Bes and Mench, 2008). However the
combination of basic slag and steel shots was more effective in reducing Zn and Cd
mobility than when used separately in contaminated soils (Mench et al., 1998). In
addition, the application of steel abrasive (SA) or oxygen scarfing granulate (OSG) to
stabilise metals from CCA-contaminated soil can decrease the concentrations of As, Cr,
Cu, and Zn in leachates and soil pore water (Lidelöw et al., 2007).

2.3.6.6. Effect of slags addition on plant production

Several alkaline slags have been used in acid soils for the amelioration of plant
growth and increase of the biomass production. The application of Linz-Donawitz (LD)
slag in acid soils in combination with NPK fertilizers resulted in highest crop yields and
nutrient concentrations in plants (Lopez et al., 1995). In greenhouse studies, the
application of respectively 1 % and 2 % (w/w) of slag in tea garden soil and 0.5, 1 and 2
% slag in rice field soil increased the plant shoot dry yield and also increased P and Mn
uptake (Ali and Shahram, 2007). In addition Fe and K uptake increased in rice field,
but K uptake decreased in tea garden soil and Fe uptake was not changed (Ali and

- 46 -
Shahram, 2007). In addition, the application of blast furnace slag to correct the soil
acidity promotes maximum root growth and higher shoots dry matter of upland rice
under sprinkler irrigation (Carvalho-Pupatto et al., 2004). Both calcitic limestone and
basic slag (BS) applied in Brazil sugarcane fields increased the yield of sugarcane
rattoon (Prado et al., 2003). A combination of converter slag and fungicide did not
decrease the density of dormant spores of Plasmodiophora brassicae in the soil but
suppressed the clubroot disease (Murakami and Goto, 2005). The combination of slag
and converter sludge treatments enhanced the plant Ca and Mg concentrations
(Forghani et al., 2006). The application of TBS in a copper contaminated soil from a
wood treatment facility increased the shoot and root biomass, and increased the foliar
Ca concentration whereas foliar Cu concentration in plant decreased (Bes and Mench,
2008). In contrast, the incorporation of TBS in contaminated soil did not increase the
plant biomass production but reduced shoot Pb concentrations (Mench et al., 1994a).

- 47 -
 CHAPTER 3: Research Objectives

The objectives of this study were to evaluate the physical and chemical
characteristics of a contaminated soil together with the characteristics of two different
slags, basic slag (BS) and basic slag phosphate (BSP) used as soil additives into a
highly copper and others trace elements contaminated soil originated mainly from Cu
sulphate and in a lesser extent from standard CCA type C (copper oxide 11.1 % w/w,
chromium trioxide 30 % w/w, arsenic pentoxide 19.9 % w/w) (Bes and Mench, 2008;
Mench and Bes, 2009). The effects of addition BS and BSP on physical, chemical and
mineralogy soil properties were also investigated. Therefore the concentration and
accumulation of these metals in beans plants were evaluated to change the availability
and mobility of these metals in contaminated soil and metal uptake by plants. Several
objectives were carried out under laboratory and pot experiments as followed.

-Soil physico-chemical properties and distribution metals in contaminated soil

The objective of this research was (1) to study the physical and chemical soil
properties of a CCA-contaminated soil (2) to identify the distribution of trace elements
in the contaminated soil (3) to determine the relationships between the metal
concentration in the contaminated soil and the soil parameters such as particle size
distribution, organic matter, soil pH and cation exchange capacity.

-Characteristics of slags used as remediation technology for contaminated soils

Two types of slag samples, a basic slag (BS) and a basic slag phosphate (BSP),
were used as soil amendments to remediate trace elements contaminated soils. This
study aims at evaluating the chemical and mineralogical properties of both slags by
several analytical techniques. The chemical composition was analysed by an atomic
adsorption spectrophotometer after acid digestion, the mineralogical analysis performed
by X-ray diffraction (XRD), the microstructure was observed by optical microscope,

- 48 -
scanning electron microscope (SEM) coupled with energy dispersive (EDX) and
electron microprobe analysis (EMPA).

-Effect of the addition basic slag on soil properties and trace elements mobility in
contaminated soils

This study aimed at investigating a basic slag (BS) addition into a soil mainly
Cu-contaminated from a wood treatment facility to improve the soil characteristics such
as the soil pH and soil electrical conductivity (EC) and also may reduce the labile pool
of trace elements in soil for root-to-shoot transfer in beans. Pot experiments were
carried out on a 2-week period with (Phaseolus vulgaris L.) beans plants. An
uncontaminated sandy soil was used as a control (CTRL). BS was added into the soil (1
kg soil/pot) to constitute four treatments in triplicates: 0 % (T1), 1 % (T2), 2 % (T3) and
4 % (T4) BS/kg air-dried soil. Changes in soil EC and pH, plant growth, biomass
production and the foliar elemental concentrations of both nutrients and trace elements
of primary leaves were determined.

-Effect of the addition basic slag phosphate used as in situ remediation of trace
elements contaminated soils

In this study, basic slag phosphate (BSP) was used as a soil remediation
technique to improve the physical and chemical soil properties and also the in situ
immobilisation of copper and other trace elements in a CCA contaminated soil by
increasing the precipitation and adsorption on the surface metal oxide of the slag thus
changing the availability and mobility of metals. The objectives of this study were :(1)
to determine the influence of BSP addition into a strongly Cu-contaminated soil from a
wood treatment facility by solutions of Cu sulphates and chromated copper arsenate to
improve soil properties such as soil pH and EC soil, (2) to evaluate the effect of BSP
addition on the plant yield production and the foliar elemental concentrations of primary
leaves, (3) to determine the potential of BSP to reduce copper and other trace elements
in a CCA contaminated soil as well as to reduce the metal toxicity uptake by beans
plants. Pot experiments were carried out with dwarf beans (Phaseolus vulgaris L.)
grown on the contaminated soil. BSP was added into the pots (1 kg/ soil) with four

- 49 -
different treatments in triplicates: 0 % (T1), 1 % (T2), 2 % (T3) and 4 % (T4) BSP/kg
air-dried soil. An uncontaminated sandy soil was used as a control (CTRL). After a two
weeks period, soil and plant samples were collected to determine the soil pH and EC,
growth and mineral analysis of plants. In addition, clay and silt fractions of soil mixed
with BSP were separated by pipette methods and they were determined by X-ray
powder diffraction analysis (XRD), performed on a PANanalytical X pert MPD
diffractmeter using Cu Kα radiation of 40Kv and 40 mA with the range 2θ secondary
monochromator and counting time of one hour.

- 50 -
 CHAPTER 4: Material and Methods

4.1. Location

The case study is a large post-industrial site (former wood treatment facility)
located in south Bordeaux (France, X 1973.15; Y 376.8), France. The industrial facility
goes back to 1846, with the building of a railway. Since 1913 a wood saturation factory
has treated crosspieces with creosote and vineyard and telegraph posts with Cu sulphate.
An autoclave to inject copper sulphate solution under vacuum and pressure was
installed in 1950. After 1980, another autoclave was installed to treat wood timbers with
an aqueous solution of Cu, Cr and As salts (standard CCA type C, Copper oxide 11.1%
w/w, Chromium trioxide 30% w/w, Arsenic pentoxide 19.9% w/w) (Bes and Mench,
2008; Mench and Bes, 2009). About 10 ha were derelict areas and waste repositories
(Figure 4.1).

The study area has been previously studied by (Mench and Bes, 2009), regarding
the apperent concentrations of trace pollutants on the ground. They selected 10 plots
that we conserved for the work thesis. Plots P1 to P4 were located at a former area for
stacking freshly treated timbers. Plots P1, P2 and P3 formed an isoscele right-angled
triangle (10 m) in a homogeneous barren area, with a similar soil type. Plot P5
corresponded to a fallow and plot P6 to a section for staking phone posts. Plot P7 was
located near the former crosspiece treatment plant, and was also a barren area. At Plot
P8 freshly treated vineyard posts were stacked. Plot P9 was on the side of a former
railway. Plot P10 was a garden adjacent to the treatment facility with a similar sandy
soil texture (Bes and Mench, 2008; Mench and Bes, 2009).

- 51 -
4.2. Field study and soil sampling

Four soil profiles (P1-3, P5, P7 and P9) were selected from the location under
study (Figure 4.1). They are the most contaminated by Cu and other trace metals. For
the remediation test, only the plot P7 has been selected. The reason of this selection is
mainly due to the weak mass of slags available for this study. Soil profiles were dug to a
suitable depth according to the type and nature of the soil material. In our study, soil
samples (15 samples) were collected from studied soil profiles to represent various soil
pedons of the location under study. Soil samples were taken from each layer of the soil
profile. They were air dried, then sieved with 2- mm and finally stored in plastic
containers for physical and chemical analysis.

Figure 4.1: Location of the studied soil profiles

4.3. Methods of analysis

4.3.1. Soil physical and chemical analysis

The soil physical and chemical analysis of the studied soil are presented in the
Tables 4.1

- 52 -
 Table 4. 1: Physical and chemical methods in soil analysis
Soil parameters Methods References

Particle size Gravel percentage was measured by (Richards, 1954).

distribution weight for each soil layer and soil
material (50g) was used for the particle
size distribution analysis. Total
carbonates were removed by
hydrochloric acid. Hydrogen peroxide
was used to oxidise organic matter.
Sodium hexameta phosphate solution
(10%) was used as a dispersing agent.
Sand fraction was separated from silt
and clay by sieving. Clay fraction was
determined in the suspension by the
pipette methods. Silt content was
calculated by difference.
Organic matter The organic matter content was (Jackson, 1967).
content determined by a modified Walkely-
Blake method; 0.5 g soil was placed in a
500-ml conical flask and mixed with
10ml of 0.17M K2Cr2O7, followed by
the addition of 20 ml of H2SO4, 200 ml
of water, 10 ml of H3PO4 FeSO4 and
one ml of diphenylamine indicator.
Finally the contents were titrated with
0.5 M.7H20. The estimation of organic
matter assumes that 77% of the organic
carbon is oxidized by the method and
that soil organic matter contains 58% C.
Calcium carbonate Calcium carbonate content was (Jackson, 1967).
content measured gasometrically using a
calibrated Collin’s calcimeter method.
Soil pH The soil pH was measured in 1:1 soil: (Jackson, 1967).
water suspension using a glass electrode
pH meter.
Soil electrical The soil electrical conductivity (EC) (Jackson, 1967).
conductivity (EC) was measured in 1:1 soil: water
suspension by using the glass electrode.
Cation exchange The cation exchange capacity (CEC) (Ciesielski and
capacity (CEC) was determined using cobaltihexamine Sterckeman, 1997).
chloride.
Total metal contents Total metal content in soil were Ciesielski et al.,
determined by ICP-AES after wet 1997).
digestion in HF and HCIO4 (AFNOR
NF X 31-147).

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4.3.2. Slag analysis

From the year 60s’, slag has been used as fertilizer like the Scories Thomas
(Sinaj et al., 1994). These slag are mainly issued from the by products of the steel and
coal industry in France. New generation of slags from electric furnace are produced and
contains more trace metals (CTPL, 2008). The CTPL kindly furnished 10 kg
kilogrammes of these slag called basic slag (BS). Half of the BS has modified by liquid
chemical reaction to enhance the amount of phosphorus, in order to synthetize
micrometric phosphates minerals (Amin, 1992). The aim of this reaserch was to
evaluate the chemistry and mineralogy of the slag samples. The analysis was carried out
using the following analytical techniques: chemical composition was determined by an
atomic adsorption spectrophotometer after acid digestion. The mineralogy was
performed by X-ray diffraction (XRD). The petrography and microstructure was
observed by optical microscope for the microlitic phases and by scanning electron
microscope (SEM, JEOL 2000FX) coupled with energy dispersive (EDX, TRACOR
Detector) for submicrolitic and amorphous phases of the slags. Electron microprobe
analysis (EMPA) is also performed to correlate the chemical composition obtained by
X-EDS analysis.

-Chemical composition

The chemical compositions of slag samples were carried out with an atomic
absorption spectrophotometer. Slag is digested in dilute HNO3 after flux-fusion at 1100
°C in the presence of lithium metaborate.

-Polarized Optical Microscope (PLM)

The BS and BSP were examined by using polarized optical microscope (PLM)
to identify the different mineralogical phases and their association (petrology). Polished
petrography thin sections (normative thickness of 25 µm) have been prepared after
impregnation of the slag samples with an epoxid resin. The analyses were performed
using a Zeiss Axioskop 40A polarization microscope and a leica DM 6000 B digital
microscope equipped with a digital camera. The magnification used varied from X10 up

- 54 -
to X100 allowing a resolution of 2 µm. The analysis has been performed at the (UMR
EPOC- University of Bordeaux1).

-X – Ray Diffraction analysis (XRD)

Characterisation of the crystallized phases of both slags was carried out by X –

ray powder diffraction analysis (XRD), performed on a PANanalytical X` Pert MPD
diffractometer using Cu Kα radiation of 40Kv and 40 mA with the range 2θ secondary
monochromator and counting time of one hour. The analysis of the spectrogram allows
the identification of the crystalline phases present and thus with the determination of the
crystallographic composition of the main diffracted minerals. All diffraction analysis of
both slag samples was performed at the (ICMCB-CNRS- University of Bordeaux1).

-Scanning Electron Microscope (SEM)

Scanning electron microscope investigations were conducted with a JEOL- JSM-

840A operated at 25 kv and linked with an energy dispersive (EDS from Tracor). Image
analyses have been performed on thin section made from slag samples with a 100
to1000 nm resolution. The interest of SEM/X-EDS analysis compared to Optical
microscope is to identify the submicrolitic mineral and amorphous phases but also their
elemental composition. The X-EDS analysis covered a range from C up to U with a
sensibility of 1% coupling with an electron probe of few micrometers (1 square µm).
The analysis has been performed at the CREMEM (Microscopy facility center of
University of Bordeaux1).

-Electron Microprobe Analysis

Chemical microanalysis of slag samples were carried out by using electron

microprobe analysis (EMPA), CAM.ECA model SX100 which combines scanning
electron microscopy (SEM) and compositional analysis using x-ray spectrometry. Both
slags samples were carried out by service CECAMA (located at ICMCB- University of
Bordeaux1).

- 55 -
4.4. Remediation techniques
4.4.1. Soil properties

The topsoil of P7 (0 - 0.25 m) of a mainly Cu-contaminated soil was sampled

from a soil French wood treatment facility (Mench and Bes, 2009). This anthropogenic
soil developed on an alluvial soil in terrace (Fluviosol) containing alluvial materials
from the Garonne River combined with wind deposits (BRGM, 1978). Copper
contamination originated mainly from Cu sulphate and to a lesser extent from standard
CCA type C (copper oxide 11.1 % w/w, chromium trioxide 30 % w/w, arsenic
pentoxide 19.9 % w/w) used as wood preservatives (Bes and Mench, 2008; Mench and
Bes, 2009). The soil was air-dried and sieved at 2 mm. A sandy control soil from the
same soil type was sampled (0-0.25 m) in an uncontaminated kitchen garden,
Gradignan, France. A soil aliquot (50g) was used for particle size distribution analysis
by sieving and pipette methods (Richards, 1954). The soil pH was measured in 1:1 soil:
water suspension using a glass electrode pH meter (Jackson, 1967). The soil electrical
conductivity (EC) was measured in 1:1 soil: water suspension by using the glass
electrode (Jackson, 1967). Total nitrogen was determined at the INRA laboratoroire
d’Analyses des sols (LAS), Arras, France using standard methods (Inra Las, 2007). The
organic matter content was determined by a modified Walkely-Blake method: 0.5 g soil
was placed in a 500-ml conical flask and mixed with 10ml of 0.17M K2Cr2O7, followed
by addition of 20 ml of H2SO4, 200 ml of water, 10 ml of H3PO4 and one ml of
diphenylamine indicator. Finally the contents were titrated with 0.5 M FeSO4.7H20.
The estimation of organic matter assumes that 77% of the organic carbon is oxidized by
the method and that soil organic matter contains 58% C (Jackson, 1967). The cation
exchange capacity (CEC) was determined using cobaltihexamine chloride (Ciesielski
and Sterckeman, 1997). Total metal content in the soil was determined by ICP-AES
after wet digestion with HF and HCIO4 (AFNOR NF X 31-147, Ciesielski et al., 1997).
The physico-chemical properties of the contaminated and control soils are presented in
Table 4.2.

- 56 -
 Table 4. 2: Physico-chemical properties of contaminated and control soils
Parameters Contaminated soil Control soil
P7 CTRL
Particle size distribution
Sand % 88.8 66.5
Silt % 4.8 15.5
Clay % 6.4 18.0
pH 5.64 7.01
EC mS cm-1 0.11 0.62
Total nitrogen (N) g kg-1 0.693 2.94
Organic carbon g kg-1 14.8 40.4
C/N % 21.3 13.8
Organic matter g kg-1 25.6 69.9
CEC cmol+ kg-1 1.94 16.1
As mg kg-1 27.4 3.6
Co mg kg-1 3.37 2.62
Cr mg kg-1 41.9 17.9
Cu mg kg-1 630 21.5
Mn mg kg-1 147 189
Ni mg kg-1 8.31 7.46
Zn mg kg-1 42.3 50.9

4.4.2. Pot experiments

4.4.2.1. Effect of basic slag addition on soil properties, growth and leaf mineral
composition of beans in a Cu-contaminated soil

This study aimed at investigating a BS addition into a mainly Cu-contaminated

soil from a wood treatment facility. The addition of BS may improve the soil
characteristics such as pH and EC and reduce the labile pool of trace metals in soil for
root-to-shoot transfer in beans plant.

-Treatments and preparation of pot experiment

Four soil treatments were prepared by mixing soil P7 (1 kg air-dried weight)

with 0 %, 1 %, 2 % and 4 % of BS. Amended soils (made in triplicates) were
homogenised by rotation in 2-L plastic flasks, transferred into 1.3-L plastic pots, then
watered daily and maintained at 70 % of water holding capacity (WHC, 10% of soil air-
dried weight) by manual irrigation with distilled water and allowed to react for four
weeks at 20°C. The control soil was treated in the same way. Four dwarf beans

- 57 -
(Phaseolus vulgaris L. cv vroege Limburgs) were sown in all pots and cultivated (15
days) in controlled conditions: illumination 12 h light/12 h darkness regime, intensity
150 µmol m-2 s-1, temperature 25°C/22°C, and 50% relative humidity. Pots were
arranged in a fully randomised block design on a bench and watered daily with
deionised water (at 50% WHC) without loss from drainage. The plant growth was
monitored on a daily basis using an index based on plant development steps for two
weeks and then plants were harvested.

-Plant analysis

Biometrical parameters, i.e. the fresh weight (FW) of roots, shoots and primary
leaves were determined after the plants were harvested. Plant materials were washed
with deionised water (2 times) and distilled water, oven dried at 70 °C and weighted to
determine the DW biomass production. Plant samples (0.5 g) were wet digested in 5 mL
14M HNO3, 2 mL H2O2 and 1 mL distilled water at 180°C in PFA (perfluoroalkoxy
copolymer resin) tubes under microwaves (MarXpress, CEM). Mineral composition in
the plant digests (Al, Ca, Mg, K, P, Cr, Cd, Cu and Zn) was determined by ICP-AES
(Ultima, Jobin Yvon Horiba, Longjumeau, France).

-Soil-BS analysis

Soil treatments were taken from all pots experiment to measure the soil pH and
the EC in the suspension soil: distilled water in the ratio 1:1 using a glass electrode pH
meter and electrical conductivity respectively (Jackson, 1967).

4.4.2.2. In situ remediation of CCA - contaminated soil by basic slag phosphate

(BSP)

The effect of BSP on soil pH, soil conductivity, growth and biomass of beans
plants were investigated using acid, sandy topsoil (0-25cm) of P7. The soil was strongly
Cu-contaminated (630 mg Cu /kg) from a wood treatment facility using solutions of Cu
sulphates and chromated copper arsenate. Clay and silt fractions of the soil treatments
were determined by X – ray powder diffraction analysis (XRD) to identify the
mineralogical form of copper in the soil.

- 58 -
-Characteristics of the soil amendment

BSP is an alkaline by-product of the French steel industry using electric furnace.
It has been used as a soil amendment to improve the physical and chemical soil
properties and to improve the in situ immobilisation of copper and trace elements in a
chromated copper arsenate (CCA) contaminated soil in order to change the availability
and mobility of trace elements in soil and their uptake by plants. In this study the BSP
consists of phosphorus slag incorporating several oxides (calcium, silicon, iron oxide
and other metal oxides). They are supposed to meliorate the phytoremediation by a
double effect. First one is related to the fertilizing capacity of the amendment which can
help the plant growth. The second one is supposed to adsorbate and trap some trace
metals from the soils on the surface of the oxides and phosphates plases of the BSP slag.
This hypothesis will be discussed .in the chapter 8.

-Treatments and preparation of pot experiments

The top layer (0-25 cm) of a Cu contaminated soil (630 mg/kg) originating
mainly from Cu sulphate and in a lesser extent from standard CCA type C was sampled.
BSP treatments were applied to improve soil properties and stabilize copper and other
trace elements in the contaminated soil. Four soil treatments (1 kg air-dried weight)
were prepared and mixed with 0 %, 1 %, 2 % and 4 % of BSP. Three replicates of each
treatment were homogenised by rotation in 2-L plastic flasks, transferred into 1.3-L
plastic pots. The control soil (CTRL) was treated in the same way. After incorporation
of the BSP into the soil, the moisture content was raised to 70 % of water holding
capacity (WHC, 10% of soil air-dried weight) by manual irrigation with distilled water
and the soil was allowed to react for four weeks at 20°C before seeds were sown. Four
dwarf beans (Phaseolus vulgaris L. cv vroege Limburgs) were sown in all pots just
below the soil surface. Plants were cultivated in the laboratory under controlled
environmental conditions: illumination 12 h light/12 h darkness regime, intensity 150
µmol m-2 s-1, temperature 25°C/22°C, and 50% relative humidity.. Pots were arranged in
a fully randomised block design on a bench and watered daily with deionised water (at
50% WHC) without loss from drainage. The plant growth was monitored on a daily
basis using an index based on plant development steps for two weeks and then plants
were harvested.

- 59 -
-Plant analysis

Several biometrical parameters, i.e. the fresh weight (FW) of roots, shoots and
primary leaves were measured after plant harvested. Plant parts were washed with
deionised water (2 times) and distilled water, oven dried at 70 °C, and weighted to
determine the DW biomass production. Plant samples (0.5 g) were wet digested in 5 mL
14M HNO3, 2 mL H2O2 and 1 mL distilled water at 180°C in PFA (perfluoroalkoxy
copolymer resin) tubes under microwaves (MarXpress, CEM). Minerals composition in
the plants digests were determined by ICP-AES (Ultima, Jobin Yvon Horiba,
Longjumeau, France).

-Chemical and mineralogical analysis of the soil-BSP

BSP was applied into a copper contaminated soil (P7) to change its chemical and
mineralogical properties. After soil incorporation with BSP, the soil pH and electrical
conductivity (EC) were measured in suspension soil: distilled water in the ration 1:1
using a glass electrode pH meter and electrical conductivity respectively (Jackson,
1967). The clay and silt fractions of the soil mixed with BSP were separated by pipette
methods (Richards, 1954; Jackson, 1969). The mineralogical of soil fractions was
investigated to identify the form of copper in the soil treatments using X – ray powder
diffraction analysis (XRD). In fact, it is important to verify that slag addition do not
increase the concentration in trace elements in the soils which significated that BSP
desorbebd or release trace metal inducing additional contamination.

-Statistical analysis

The soil and plant samples data collected from the pots experiments were tested
by statistical analysis (ANOVA, Kruskall-Wallis and Tukey test) with SAS software
version 9.1 to evaluate the soil properties (soil pH and EC soil), plant yield (root and
shoot yield), elemental concentrations in primary leaves and the total element
concentrations in primary leaves [µg plant-1, so-called here element accumulation which
calculated based on the foliar element concentration (µg kg-1 DW) and leaf biomass
production (µg DW plant-1) of plants. All analytical determinations were performed in

- 60 -
triplicate. Statistical analysis is supposed to quantify relation between different
parameter and reveal potential or supposed correlation (linear, exponential, etc.).

- 61 -
 CHAPTER 5: Soil Physico-Chemical Properties and Trace
Elements Distribution in Soil

5.1. Soil physical properties

Soil physical properties such as particle size distribution, calcium carbonate

content and organic matter of the soil under study are presented in Table 5.1. The results
indicates that the soils of the study are mostly coarse in texture (mainly sand and loamy
sand), the sandy texture dominating in most soil samples followed by loamy sand.
Additionally, all soil samples have a very low content in fine materials (silt + clay). The
gravel contents of the soil study ranged between 12 to 87 % by weight. The shape and
size of gravels are different from one site to another and among various layers of each
profile. Very gravely soil texture (gravel content > 50%) occurs in the surface and
subsurface layer of profile P7 and the deepest layer of profiles P1-3, P5 and P9. It is
noticed that the high amount of gravels in soil samples could be the result of its
concentration on the account of transport action and loss of fine earth materials (<
2mm) by wind, rainfall and running water from soil surface during earlier stages of soil
formation.

Organic matter content in soil samples is ranges between 0.67 to 3.01%. The
highest level of OM was found in the surface layer of profile P9 and the lowest level of
the OM was found in the subsurface layer of profile P5. All soil samples contained OM
more than 1% with the exception of the subsurface layer of profile P5 which content
0.67 % of OM. Most soil profiles show a clear decrease of OM with depth indicating
that little amount of OM accumulation in the soil surface. The low amounts of OM in
most soil samples are the result of poor vegetation cover and indicate a poor soil
fertility. On the other hand, the relatively high values of OM in some surface and
subsurface soil samples could be due to the growth of some vegetation cover and also to
the addition of relatively OM rich alluvium to the soil surface in some cases.

- 62 -
 Table 5.1: Some physical properties of the soil samples profiles in the study area
Transect Depth of Gravel
Sample Sand Sand Silt Clay CaCO3 OM
/ layer % by
No. >100 µ 50-100 µ % % % %
profile cm weight
1 0-15 35.83 84.73 2.67 6.4 6.2 2.14 2.68
2 15-30 30.39 84.64 2.16 6.4 6.8 1.77 2.01
P1-3
3 30-60 47.12 88.12 2.08 6.2 3.6 1.98 1.34
4 60-100 76.79 93.46 1.34 3.6 1.6 1.98 1.34
Aver. 47.53 87.73 2.06 5.65 4.55 1.96 1.84
5 0-10 31.17 82.86 3.54 8.4 5.2 2.14 1.67
6 10-55 36.94 80.52 4.48 10.2 4.8 1.75 0.67
P5
7 55-75 86.9 88.66 4.14 3.6 3.6 1.34 1.20
8 75-100 56.8 96.06 0.34 2.8 0.8 1.75 1.34
Aver. 52.95 87.02 3.12 6.25 3.6 1.74 1.22
9 0-10 56.34 86.28 2.52 4.8 6.4 1.75 1.20
10 10-35 73.76 82.52 2.08 10.2 5.2 2.3 1.34
P7
11 35-55 33.51 85.66 2.74 8.8 2.8 1.82 1.54
12 55-100 12.38 81.16 4.84 8.8 5.2 2.14 1.34
Aver. 43.99 83.90 3.04 8.15 4.9 2.00 1.35
13 0-15 36.23 84.66 4.34 7.8 3.2 2.23 3.01
14 P9 15-65 31.14 85.56 4.44 7.2 2.8 2.02 2.01
15 65-100 69.78 93.2 0.8 4.8 1.2 2.14 1.87
Aver. 45.71 87.80 3.19 6.6 2.4 2.13 2.29

The results of calcium carbonate distribution in soil samples showed that the
concentration of calcium carbonate is range between 1.34 and 2.3%. The highest
content of calcium carbonate was found in the subsurface layer of profile P7 and the
lowest content of the calcium carbonate was occur in the deepest layer of profile P5.
Generally, the decrease of calcium carbonate in soil profiles may be due to the absence
of the basic cations such as (Ca, Mg, and K). In addition, in some soil profiles, calcium
carbonate content slightly increases with depth probably due to the leaching soil.

5.2. Soil chemical properties

The results of the soil chemical properties such as soil pH, soil EC and cation
exchange capacity (CEC) of the study area are shown in Table 5.2.

- 63 -
 Table 5.2: Some chemical properties of the soil samples profiles in the study area
Sample Transect Depth of pH EC CEC
No. / layer 1:1 (dS/m) (cmol (+) /kg)
profile Cm
1 0-15 7.05 0.13 3.36
2 15-30 4.69 0.44 1.39
P1-3
3 30-60 4.04 0.39 1.17
4 60-100 4.09 0.29 1.09
Aver. 4.96 0.31 1.75
5 0-10 6.95 0.15 6.87
6 10-55 7.03 0.11 3.07
P5
7 55-75 7.05 0.11 2.49
8 75-100 7.07 0.10 1
Aver. 7.02 0.11 3.35
9 0-10 6.34 0.11 1.94
10 10-35 5.73 0.12 2.37
P7
11 35-55 5.49 0.17 1.07
12 55-100 5.78 0.10 2.01
Aver. 5.83 0.12 1.84
13 0-15 7.11 0.05 10.6
14 P9 15-65 6.44 0.05 2
15 65-100 5.96 0.02 1
Aver. 6.50 0.04 4.53

Soil pH is an indication of the acidity or alkalinity of the soils. The pH soil

varied from 4.04 to 7.11 with the lowest level in the deepest layer of profile P1-3 and
the highest level in the surface layer of profile P9. Few soil samples are extremely acid
such as the subsurface and the deepest layer of profile P1-3, slightly acid for the
subsurface layer of profile P7 and deepest layer of profiles P7 and P9. All surface layers
of soil samples are slightly alkaline and the soil pH decreases with depth. Generally, pH
range of approximately 6 to 7 promotes the most ready availability of plant nutrients. In
fact, extremely and strongly acid soils (pH 4.0-5.0) can have high concentrations of
soluble aluminum, iron and manganese which may be toxic towards the growth of some
plants (McLean and Bledsoe, 1992). Moreover when the soil pH is lower than 6.0; there
is a decrease of the availability of the nutrients such as phosphorus, potassium, calcium,
sodium and magnesium. In addition, the availability of some metals such as zinc,
manganese, aluminium, copper, zinc and iron increases as the pH decreases. Most
minerals and nutrients are more soluble or available in acid soils than in neutral or

- 64 -
slightly alkaline soils (McLean and Bledsoe, 1992). The rainfall also influences the soil
pH by leaching basic cations such as (e.g. Ca, Mg and K) into the drainage water. These
cations are replaced by acidic cations such as (e.g., Al3+, H+ and Fe). For this reason,
soils formed under high rainfall conditions are more acid than those formed under arid
conditions. The dissolution of lead, copper, nickel, and zinc precipitates are strongly
dependent on the soil pH and their retention dramatically increasing above pH 7.0 to 7.5
(Harter, 1983). The EC values of the soil samples study ranged from 0.02 to 0.44 dS/m.
All soil samples are non saline (0-4 dS/m). The much lower salinity level in the studied
soil is possibly due to the effect of rainfall and leaching of the soil profiles. In most soil
profiles, the EC value increases more in the subsurface layers than in the surface layer
probably due to the leaching of basic cations such as (e.g. Ca, Mg, K) into the drainage
water. The result of the CEC indicates that the soil study ranged between 1 and 10.6
cmol (+)/kg CEC. The highest value of CEC was found in the surface layer of profile P9
whereas the lowest value of CEC was found in the deepest layers of profiles P5 and P9.
In general, CEC decreases with depth along the soil profiles. The low value of CEC is
probably due to the coarse texture of most soil profiles. The surface layers of the soil
profiles have higher values of CEC than the subsurface and deepest layers of the soil
profiles. This is possibly due to the effect of organic matter contents and soil fine
particle in some soil surface.

5.3. Trace elements content and distribution in soil profiles

The concentrations and distribution of different trace elements with depth in the
soil profiles are shown in Table 5.3 and Figure 5.1. The result indicate that, from all soil
samples studied, Cu is the dominant followed by Cr, Zn, As, Ni then Co and they
ranged from 4.2 to 1970, 10.9 to 114, 15.4 to 95.7, 1.93 to 51.1, 5.22 to 14 and 1.66 to
4.81 mg/kg respectively. The accumulation of toxic metals in soil is mainly inherited
from parent materials or inputs through anthropogenic (He et al., 2005). The main
source of metals in agricultural contaminated soils has included the impurities in
fertilisers, swage sludge, manures from intensive animal production, pesticides and
wood preservatives (Alloway, 1995). The concentrations of many contaminants tend to
accumulate in the soil surface (Alloway and Ayres, 1997). Our study indicate that the

- 65 -
distribution of Cu, Cr, As and Zn increases in the surface layer of soil profiles and then
decreases with depth in all soil profiles. In general, Ag, As, Cd, Cu, Hg, Pb, Sb and Zn
are found concentrated in the surface layers as a result of cycling through vegetation,
atmospheric deposition and adsorption by the soil organic matter (Alloway, 1995). In
addition, Kumpiene et al. (2008) reported that As, Cu, Cr, and Zn can be found in
excess in contaminated soils at wood treatment facilities, especially when Cu sulphates
and chromated copper arsenate (CCA) were used as a preservative against insects and
fungi, which may result in soil phytotoxicity. In contrast, Co and Ni were decreased in
the surface layer of soil profiles and then increased with depth in all soil profiles.
Similar results obtained by Hernandez et al. (2003) who found that in some French acid
soil, Ni and Co increases with depth while copper and zinc decreases with depth.

Table 5.3: Trace elements contents and distribution in the soil samples profiles
Sample Transect Depth of Cu Cr Zn As Ni Co
No. / layer
profile Cm mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg

1 0-15 1970 34.1 54.9 15.5 5.22 1.66

2 15-30 772 16.3 30.5 3.53 5.35 1.87
P1-3
3 30-60 411 18.4 28.7 4.71 7.97 2.28
4 60-100 111 22.5 29.3 6.11 10.6 2.67
Aver. 816 22.82 35.85 2.12 7.28 2.12
5 0-10 152 49.8 36.8 49.4 6.1 1.83
6 10-55 11.2 18 32.1 4.48 7.45 2.4
P5
7 55_75 8.1 21.7 29.7 6.63 11.9 2.6
8 75-100 4.25 10.9 15.4 4.36 8.42 2.03
Aver. 43.88 25.1 28.5 2.21 8.46 2.21
9 0-10 630 41.9 42.3 27.4 8.31 3.37
10 10-35 120 23.8 42.9 7.38 11.5 4.12
P7
11 35-55 752 26.7 95.7 7.85 14 4.81
12 55-100 11.3 19.4 32.1 3.04 8.35 2.53
Aver. 378 27.95 53.25 3.70 10.54 3.70
13 0-15 207 114 52.3 51.1 7.15 2.18
14 P9 15-65 9.77 19.2 27.6 3.77 7.95 2.32
15 65-100 4.97 14.5 23.4 1.93 9.1 2.86
Aver. 73.91 49.23 34.43 2.45 8.06 2.45

- 66 -
 Cu (mg/kg) Cr (mg/kg)
0 10 20 30 40 50 60 70 80 90 100 110 120
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0
0 10
10 20
20 30
30 P1-3
D e p th (c m )

40

D e p th (c m )
40 P1-3
50 P5
50 P5
60 P7
60 P7
70 70 P9
P9 80
80
90 90
100 100
110 110

Zn (mg/kg) As (mg/kg)
0 10 20 30 40 50 60 70 80 90 100 0 5 10 15 20 25 30 35 40 45 50 55 60
0 0
10 10
20 20
30 30
P1-3 P1-3
D e p th (c m )

D e p th (c m )

40 40
50 P5 50 P5
60 P7 60 P7
70 P9 70 P9
80 80
90 90
100 100
110 110

Ni (mg/kg) Co (mg/kg)
0 2 4 6 8 10 12 14 16 18 20 0 1 2 3 4 5
0 0
10 10
20 20
30 30
P1-3 P1-3
D e p th (c m )

D e p th (c m )

40 40
50 P5 50 P5
60 P7 60 P7
70 P9 70 P9
80 80
90 90
100 100
110 110

Figure 5.1: Vertical distribution of trace elements in the soil profiles

- 67 -
5.3.1. Copper content in the soil profiles

According to the results in Table 5.3 and Figure 5.1, the concentration of Cu in
soil samples profiles ranges between 4.25 to 1970 mg/kg. Copper is highly phytotoxic at
higher concentrations above 30 mg/kg (Alloway, 1995; Song et al., 2004). Therefore,
this is probably causing a problem of toxicity to plants then animals and humans.
Copper contamination of soils is widespread as a result of mining, smelting, land
applications of sewage sludge, use of Cu as fungicides, algicides, chromated copper
arsenate (CCA) pressure treated lumber, copper pipes and other industrial activities
(Evanko and Dzombak, 1997; Song et al., 2004).

In our study, the deepest layer of profile P5 has the lowest level Cu, and the
surface layer of profile P1-3 has the highest level of Cu. Higher concentration of Cu
found in all surface layers of soil profiles and then decreases with depth. In some cases,
copper concentration increases with depth in soil. In fact, higher concentrations of Cu
occur in the subsurface and deepest layer of profiles P1-3 and P7. This is possibly due
to copper mobilised under extreme acid conditions (Baize, 1997). In most cases, the
retention of copper in the deepest layers of the soil is probably due by the leaching soil
(Besnard et al., 2001). On the other hand, it can be noticed that, in all surface soil
profiles, the Cu concentration was exceeding 100 mg/kg. The exceeded levels were
observed also in subsurface and deepest layers of profiles P1-3 and P7 indicating that all
soil profiles were copper contaminated. This is possibly resulted from the anthropogenic
contamination influence probably related to the input of CCA-C in the soil study. The
top layer (0-25 cm) has been mainly contaminated by Cu originated mainly from Cu
sulphate and in a lesser extent from standard CCA type C (copper oxide 11.1 % w/w,
chromium trioxide 30 % w/w, arsenic pentoxide 19.9 % w/w) used as wood
impregnation from an industrial site (Bes and Mench, 2008; Mench and Bes, 2009).

5.3.2. Relationships between trace elements contents and soil parameters

The aim of this study was to identify which soil parameters were the best related
with copper and other trace metals content in soil profiles. The results of the principal

- 68 -
component analysis (PCA) which was used for all soil samples to identify the
relationships between trace elements concentration in soil and physico-chemical soil
parameters are presented in Figure 5.2 and Table 5.4. From the Figure 5.2 it is possible
to consider two axis F1 and F2 axis which explained respectively 31% and 21% of the
variance. This indicates that soil properties can explain 52% of the trace metals
distribution into this kind of soils. F1 split the distribution of the metals in two domains.
First one incorporates Fe, Co, Ni and Zn; while the other one integrate Cr and As. It is
possible that group 1 (Fe-Co-Ni and Zn) exhibit the same fingerprint in this context
while group2 (Cr and As) an another behaviour. F1 can be named soil metal chemical
affinity. From this hypothesis Cu which close to the barycentre of the projection exhibit
an another behaviour. The axis F2 splits the projection sphere in two distributions based
on the granulometry of the soil fraction. On the right, large particles (Gravel and coarse
sand), and on the left, thin one (fine sand, silt and clay). F2 can be named granulometry
axis. The soil parameters EC is linked to the large granulometry indicated that this
fraction assume the water tranfer by open porosity; while pH, CEC and OM could
control partially the local chemistry of the Cr and As. These metals can be supposed to
have a strong affinity with the OM, clay and CEC. The other metals exhibits an another
behaviour more mechanistic and based on the diffusion through a media with a complex
porosity. Regarding the figure 5.1 As and Cr have the same trend while the other metal
show a global decrease the metal content from the surface to the bottom of the profile
but with cumulation front depth around 60 cm. At this level the content of clay tends to
decrease roughly compared to the surface and the depth of 100 cm. Thus trace metal
accumulation of Zn, Co and Ni can be governed by a mechanism of diffusion control by
the porosity of the soil. The Cr and As can be governed by a mechanism of adsorption
on the surface of the fine fraction (OM or/and silt-clay fraction). Cu has a behaviour
more complex in the studied soil. This is possibly due to the anthropogenic
contamination by the input of CCA-C in the soil study. Thus, we will discuss in detail
the relationships between copper concentration in studied soil and physico-chemical soil
parameters.

- 69 -
 1
F2 Fe Plan F1F2 Var

0.8
Co
Zn
Silt
0.6
Ni

0.4

Sand_2
Clay
0.2

Cu
EC F1
0
CaCO3
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
Cr
CECAs -0.2 Gravel
pH
O.M
-0.4

Sand_1
-0.6

-0.8

-1

Figure 5.2: The principal plan component analysis performed for trace elements
concentrations and physico-chemical soil properties of the soil samples

- 70 -
 Table 5.4: Linear correlations coefficients between physico-chemical properties
and trace elements contents in soil study
Gravel Sand 1 Sand 2 Silt Clay CaCO3 OM pH EC CEC
Parameters (cmol (+)
% (>100 µ) (50-100 µ) % % % % 1:1 dS/m /kg)
Gravel %
1 0.60 -0.49 -0.55 -0.39 -0.29 -0.29 -0.09 -0.05 -0.26
Sand 1 (>100 µ)
0.60 1 -0.75 -0.87 -0.76 -0.24 -0.04 -0.18 0.04 -0.38
Sand 2 (50-100 µ)
-0.49 -0.75 1 0.55 0.38 -0.02 0.06 0.38 -0.28 0.48
Silt %
-0.55 -0.87 0.55 1 0.44 0.46 0.00 0.08 -0.11 0.32
Clay %
-0.39 -0.76 0.38 0.44 1 0.03 0.04 0.05 0.25 0.160
CaCO3 %
-0.29 -0.24 -0.02 0.46 0.03 1 0.48 -0.09 -0.17 0.36
O.M %
-0.29 -0.04 0.06 0.00 0.04 0.48 1 0.19 -0.11 0.56
pH 1:1
-0.09 -0.18 0.38 0.08 0.05 -0.09 0.19 1 -0.77 0.50
EC dS/m
-0.05 0.04 -0.28 -0.11 0.25 -0.17 -0.11 -0.77 1 -0.30
CEC (cmol (+) /kg)
-0.26 -0.38 0.48 0.32 0.16 0.36 0.56 0.50 -0.30 1
Cu mg/kg
-0.25 -0.17 -0.11 0.01 0.49 0.08 0.46 -0.01 0.25 -0.01
Co mg/kg
0.26 -0.06 -0.12 0.27 -0.11 -0.02 -0.33 -0.22 -0.14 -0.30
Cr mg/kg
-0.19 -0.25 0.35 0.19 0.11 0.35 0.62 0.35 -0.25 0.92
Ni mg/kg
0.51 0.24 -0.12 -0.03 -0.44 -0.26 -0.42 -0.20 -0.15 -0.35
Zn mg/kg
-0.26 -0.35 0.18 0.43 0.18 0.11 0.25 0.02 -0.05 0.18
As mg/kg
-0.20 -0.27 0.28 0.16 0.22 0.31 0.46 0.42 -0.22 0.88
Fe µg/kg
0.01 -0.30 0.20 0.39 0.09 -0.18 -0.32 -0.35 0.17 -0.27

5.3.3. Relationship between copper concentration and physico-chemical soil

parameters

The mobility of copper in soil is controlled by different physico-chemical soil

properties such as, the soil particle size distribution, organic matter content, CEC, soil
salinity, pH soil and iron and aluminum oxide content (Qian et al., 1996; Brun et al.,
1998; Chaignon et al., 2003; Hernandez et al., 2003). In addition, copper is complexed
with organic matter and adsorbed onto the surface of clay fractions that will strongly
influence on the mobility and bioavailability of copper in the soil (Adamo et al., 1996;
Chaignon et al., 2003; Sterckeman et al., 2006).

- 71 -
5.3.3. 1.Relationship between copper concentration and particle size distribution
soil

According to data obtained from the principal component analysis (PCA), the
results indicate that there is no relationship between copper contents and gravel content
and sand fractions in soil samples. A weak positive correlation can be observed between
copper content and clay proportion for the soil samples but it is weak due to the low
clay content in soil profiles (r2 = 0.24) (Figure 5.3). Particle size distribution soil can be
used to assess the distribution of copper in soil contaminated. In general, from the
particle size fractions (sand, silt and clay) the metals tend to accumulate in fine particles
especially on the clay fractions of the soil due to increased the surface area, higher clay
content and organic matter content (Qian et al., 1996; Acosta et al., 2009). Besnard et
al. (2001) found that copper contents in soil increased with a decreasing size fraction
and the soil having highest amounts of clay fractions showed the highest values for
metal adsorption (Singh and Oste, 2001). In fact, the soil clay mineralogy influences the
chemical adsorption and co-precipitation, thereby affecting the solubility and mobility
of trace elements contaminated soil (Hesterberg, 1998). Thus, it can be noticed that the
high concentrations of copper related with increased clay size fraction in all soil profiles
but not enough to explain the Cu distribution into the different soil profils. The level of
Cu on the surface is so high that remobilization of the Cu allow its precipitation under
mineralogical phases (Cuprite, Malachite, Copper oxide). The period is too short to
allow mineral precipitation of copper phases and only a biological process is able to
generate such mineralization. This point should be discussed after another
experimentation and analysis.

- 72 -
 2200

2000 1

1800

1600

1400

1200

1000
y = 137.54x - 199.68
800
11 R2 = 0.2466 2

600 9

400 3

200 13
4 5
10
0 8 15 14 7 6 12
0 1 2 3 4 5 6 7 8

Figure 5.3: Relationship between copper and clay contents in soil samples

5.3.3. 2.Relationship between copper concentration and soil organic matter

The relationship between copper concentration and organic matter content in the
soil profiles study is given in Figure 5.4. Organic matter has a direct effect on the
retention copper in the soil. In fact, the high OM content can retain copper fraction by
96% of the total copper in the soil (Balasoiu et al., 2001). In our study, organic matter
was much higher in the surface soil than in the subsurface and deepest layers of all soil
profiles. The high concentrations of copper in the surface layer of some soil profiles
were related with the increasing organic matter content. Copper content in the surface
layer was high increased as the OM content increases (Besnard et al., 2001). The results
indicate the correlation analysis shows that copper was low strongly associated with
OM of soil samples (r2 =0.22). McBride et al. (1997) found that the absence of
correlation between trace metals adsorption and soil organic matter is probably caused
by the reactive fraction of the OM could be assessed in the relationship.

- 73 -
 2000 1

1800 y = 409.34x - 325.26

R2 = 0.2171
1600

1400

1200

1000

800 2
11
600 9

400 3

200 13
10
4 5
0 6 7 12
8 15 14
0 0.5 1 1.5 2 2.5 3 3.5

Figure 5.4: Relationship between copper and OM contents in soil samples

5.3.3. 3.Relationship between copper concentration and pH soil

The relationship between copper concentration and soil pH in the soil samples
study is presented in Figure 5.5. The results indicate that the correlation analysis shows
that there is no relationship between copper content and pH soil which related to the
anthropogenic contamination influence probably related to the input of CCA-C in the
soil study. All surface soil has been mainly contaminated by Cu originated mainly from
Cu sulphate and in a lesser extent from standard CCA type C (copper oxide 11.1 %
w/w, chromium trioxide 30 % w/w, arsenic pentoxide 19.9 % w/w) used as wood
impregnation from an industrial site (Bes and Mench, 2008; Mench and Bes, 2009). The
pH of the soil system is a very important parameter, directly influencing the sorption
/desorption, precipitation / dissolution, complex formation, and oxidation-reduction
reactions (McLean and Bledsoe, 1992). In general, the stability of copper in the soil is
strongly pH dependent and the mobility of copper increases with decreasing pH. The
high concentrations of copper in the surface layer of soil profile P7, subsurface and
deepest layers of profiles P1-3 and P7 was occur with an decreased soil pH indicated
that copper concentration is a high mobility with pH decreased in the soil.

- 74 -
 2200

2000

1800

1600

1400

1200

1000 y = -115.9x + 922.4

R2 = 0.1896
800 1 10
600 8

400 2

200 12
3 9 4
0 11 14 13 567
3 3.5 4 4.5 5 5.5 6 6.5 7 7.5

Figure 5.5: Relationship between copper contents and pH in soil samples

Copper is distinctly soluble under oxidised condition than under reduced in the
pH rang 5.4-6.5 (Bhattacharya et al., 2002). In addition, the cupric ion Cu2+ is the most
common mobile in the surface environment below pH 6.9 (Alloway, 1995; Kabata-
Pendias, 2001). In general the mobility of copper in the soil is usually lowest at slightly
alkaline pH (Kumpiene et al., 2008). In most cases, our study indicates that copper
content in the surface layer of profiles, P1-3, P5 and P9 was increased as above pH 7.
This is possibly causing by the accumulation of copper concentration from the use of
CCA-C in treatements wood in the soil. Therefore, increasing pH soil causing Cu was
strongly adsorbed at the colloidal surfaces by decreasing the exchangeable form. It has
also been suggested that in the pH =7, copper tend to precipitate in the form carbonate
and hydroxide (Alloway, 1995; Gagnon, 1998).

5.4. Conclusion

The soil studied was strongly Cu-contaminated originated mainly from Cu

sulphate and in a lesser extent from standard CCA type C (copper oxide 11.1 % w/w,
chromium trioxide 30 % w/w, arsenic pentoxide 19.9 % w/w). Physico-chemical soil

- 75 -
properties and distribution of trace metals in the contaminated soil were investigated.
The relationships between copper concentration in the contaminated soil and soil
properties were measured using PCA. Results indicate that the sandy texture dominates
in most soil samples followed by loamy sand and all soil samples were very low
contents in fine materials (silt + clay). Organic matter content in soil samples ranges
between 0.67 to 3.01% and decreases with depth. Calcium carbonate distribution in soil
samples showed that the range is between 1.34 and 2.3%. The pH soil varied from 4.04
to 7.11 and decreases with depth. The EC values of the soil study ranged from 0.02 to
0.44 dS/m. Cation exchange capacity (CEC) indicates that the soil study ranged
between 1 and 10.6 cmol (+)/kg and decreased with depth. The distribution of trace
metals indicates that Cu is the dominant followed by Cr, Zn, As, Ni then Co and they
ranged from 4.2 to 1970, 10.9 to 114, 15.4 to 95.7, 1.93 to 51.1, 5.22 to 14 and 1.66 to
4.81 mg/kg for Cu, Cr, Zn, As, Ni and Co respectively. The distribution of Cu, Cr, As
and Zn increases in the surface layer of soil profiles and then decreases with depth in all
soil profiles. Co and Ni decreased in the surface layer of soil profiles and then increased
with depth. In most cases, Cu concentration exceeded 100 mg/kg in all surface soil
profiles and some subsurface and deepest layers of soil profiles indicating that all soil
profiles were Cu contaminated. PCA indicates that there was a relationship between
copper contents and clay proportion for the soil samples but it is weak due to the low
clay content in soil profiles (r2= 0.24). While copper was low strongly associated with
OM of soil samples (r2= 0.22). There was no relationship between copper content and
pH soil. This is possibly resulted from the anthropogenic contamination influence
probably related to the input of CCA-C in the soil.

- 76 -
 CHAPTER 6: Slag Characterisation

6.1. Chemical composition of the slag samples

The elemental composition of both slag samples (BS and BSP) expressed as
oxides in mass percentage are presented in Table 6.1. The results indicate that the major
compound of BS is mainly consists of Ca (60.69 wt % CaO), Fe (14.61 wt % Fe2O3), Si
(12.54 wt % SiO2), Al (5.91 wt % Al2O3) and Mg (2.51 wt % MgO). Other compounds
such as TiO2, MnO, P2O5 and K2O are low contents; they represent respectively 1.47,
1.06, 1.05 and 0.15 wt%. In general, steel slag is mainly consists of CaO, Fe2O3, SiO2,
MgO, Al2O3 and MnO (Shen and Forssberg, 2003; Tsakiridis et al., 2008). In addition,
the composition of steel slag is mainly composed of CaO, SiO2, Fe2O3, Al2O3, MgO,
MnO and P2O5 (Cha et al., 2006; Tossavainen et al., 2007). Other studies reported that
the chemical composition of steel slag is mainly contains CaO (45-60 wt %), Fe2O3 (3-9
wt %), FeO (7-20 wt %), SiO2 (10-15 wt %), MgO (3-13 wt %) and Al2O3 (1-5 wt %)
(Shi and Qians, 2000).

The major compound of BSP is mainly composed of Ca (30.71 wt % CaO), Fe

(21.4 wt % Fe2O3), Si (14.63 wt % SiO2), P (14 wt % P2O5), Mg (9.55 wt % MgO), Al
(5.56 wt % Al2O3) and Mn (2.53 wt % MnO2). Other compounds such as, TiO2 and K2O
are observed in few amounts; they represent respectively 1.09 and 0.53 wt %. Thomas
basic slag is used as a phosphorus fertilizer in acidic soils and it is consists of 37.8%
CaO, 2.8% Al2O3, 14.4% Fe2O3, 10.6%, SiO2, 1.9%, MgO, 1.6 MnO2 and 1.2% P2O5
(Sinaj et al., 1994; Panfili et al., 2005). Other studies showed that the main components
of basic slag phosphate are composed of CaO, Fe2O3, SiO2, P2O5, MnO and MgO
(Forghani et al., 2006; Ali and Shahram, 2007). The comparison between chemical
composition of BS and BSP revealed that the levels of the elements in BSP are higher
than in the BS contents with the excepted Ca, Al and Ti which increased in the BS
composition. In addition it can be noticed that the amounts of phosphorus oxide in the
BSP is very much higher than in the BS indicating that BSP is rich in phosphorus oxide.

- 77 -
Some steel slag contain higher amount of P2O5 than iron content (Shen and Forssberg,
2003). Both slag samples (BS and BSP) are basic resulting by index Mb= (CaO + MgO /
Al2O3 + SiO2) > 1 (Tossavainen et al., 2007). The values of Mb in BS and BSP are > 1
and they represent respectively 3.42 and 2.

Table 6.1: Chemical composition of both slag samples

Oxide BS BSP
wt % wt %
Al2O3 5.91 5.56
CaO 60.69 30.71
Fe2O3 14.61 21.4
K2O 0.15 0.53
MgO 2.51 9.55
MnO 1.06 2.53
P2O5 1.05 14
SiO2 12.54 14.63
TiO2 1.47 1.09
Mb= ( CaO + MgO / Al2O3 + SiO2) 3.42 2
From this table BS can be described as a calco iron silicate while BSP is a calco
phospho silicate.

6.2. Polarizing microscope

The examination of both slag (BS and BSP) by polarizing microscope were
shown in Figures 6.1 and 6.2. The results indicate that both slag samples mainly consist
of opaque minerals and they mostly composed of iron materials (illmenite, magnetite,
hematite and limonite) and sulfied (pyrite). They show subangular to subrounded shapes
and represent more than 80% of the total minerals. Zircons and epidotes are the
predominant of non-opaque minerals in BSP and they represent 16% of the total
minerals. Other minerals such as feldspars (plagioclases and orthoclases), quartz, garnet,
calcite, rutile, and tourmaline were observed in low amounts in BS and BSP. The POM
reveal that the two samples are amorphous with microlitic minerals randomly
distributed into the aphanitic phase. The range size of the mineral is between 100 and
500 micrometers and porosity is also present in the two samples.

- 78 -
Figure 6.1: Thin section image of BS under polarised light

- 79 -
Figure 6.2: Thin section image of BSP under polarised light

- 80 -
6.3. X – ray diffraction analysis

According to XRD analysis, the diffraction patterns and the principal crystalline
phases of both slag samples (BS and BSP) are given in Table 6.2 and Figure 6.3. The
examination of XRD analysis gives a high several phases identified by the search-match
program. Comparison between the results of XRD analysis for both slag samples
revealed that many phases compounds such as larnite, wustite, brownmillerite, calcite
and merwinite are generally similar in BS and BSP composition. In general, the main
mineral composition of the slag may include major solid phases such as calcium-silicate
(dicalciumsilicate, tricalciumsilicate and dicalciumferrite), calciowustite,
magnesiowustite, calcium aluminate and free lime and magnesium (Dimitrova, 1996;
Geiseler, 1996; Dimitrova and Mehanjiev, 1998; Motz and Geiseler, 2001).

Some phases were observed in BS such as mayenite, portlandite, melilite,

grossular, imandrite and calcium silicate oxide. In addition, some crystallized
compounds were detected in BSP than BS phases such as rodolicoite, calcium silicon,
calcium aluminum iron oxide, calcium phosphate, titanium hydrogen phosphate,
amonium hydrogen phosphate oxide and whitlockite. Thomas basic slag contains some
phases such as larnite, calcium silico phosphate containing P2O5, calcium ferrite
(Ca2Fe2O3), wustite (FeO), lime and magnetite (Panfili et al., 2005). On the other hand,
in acidic soils, the phosphorus availability of Thomas slag is similar to that of other
water soluble phosphorus fertilizer (Sinaj et al., 1994). Thomas slag was composed of
silicato-calcium phosphates which were the prevailing form of P in the cells and a high
Fe, Ca and Mn content in the walls (Sinaj et al., 1994). Our results are in line with
Setien et al. (2009) who observed that the major compounds of basic slag are calcium
silicates such as (merwinite and larnite), portlandite, iron oxides and mayenite or
tricalcium aluminate. Similar result obtained by XRD analysis for basic slag that
compounds some phases such as tricalcium silicate (3CaO.SiO2), dicalcium silicate
(2CaO.SiO2), merwinite, mayenite, wustite, larnite and portlandite (Shi, 2002;
Tossavainan et al., 2007; Taskiridis et al., 2008).

- 81 -
 Table 6.2: The principal crystalline phases of BS and BSP analysis

Mineral compound Formula BS BSP

Larnite Ca2SiO4 + +

Wustite Fe0.942O + +

Brownmillerite Ca2 (Fe1.44 Al 0.559) O5 + +

Calcite CaCO3 + +

Merwinite Ca3Mg (SiO4)2 + +

Mayenite Ca12Al14O33 + -

Portlandite Ca OH2 + -

Melilite Ca8Al2Mg3Si7O28 + -

Grossular Ca3Al2 (SiO4)3 + -

Imandrite Na12Ca3Fe+3 2Si12O36 + -

Calcium silicate oxide Ca3 (SiO4) O + -

Rodolicoite Fe+3 PO4 - +

Calcium silicon CaSi2 - +

Calcium aluminum iron oxide Ca2Fe1.40 Al 0.60O5 - +

Calcium phosphate Ca3PO4 - +

Titanium hydrogen phosphate Ti(PO4)(H2PO4) - +

Amonium hydrogen phosphate oxide (NH4)2H2P2O7 - +

Whitlockite Ca18Mg2H2(PO4)14 - +

- 82 -
 12000

11000

10000

9000

BSP
8000
Lin (Counts)

7000

6000

5000

4000

3000
BS

2000

1000

10 20 30 40 50 60 70 80

2-Theta - Scale

Figure 6.3: XRD spectrogram of BS and BSP analysis

From XRD analysis, it is possible to conclude that BS is depleted in phosphate phase

while BSP is enriched in phosphate phases.

6.4. Scanning electron microscope (SEM/EDS)

According to the combination of SEM/X-EDS analysis to identify the elements

in both slag samples, the chemical analysis is given in Table 6.3 and Figures 6.4, 6.5,
6.6, 6.7 and 6.8. From the EDS analysis the results indicate that the major elements of
BS is mainly consists of Ca, Fe and Si. They are represented more than 90% of the total
mass. Other elements such as Mn, P, Mg, K and Al are observed low amounts in BS.
Setien et al. (2009) reported that the major compounds of basic slag are mainly silicates
and aluminates of calcium and magnesium due to Ca, Si, Mg and Al oxides contains

- 83 -
more than 95% of the total mass. While Ca, P, Fe and Si are the major elements in BSP
and they are represented more than 95% of the total mass. In addition, few amounts of
the elements such as Mn, K, Mg and Al were also observed in the BSP. Tomas basic
slag is used as phosphorus fertilizer and composed of slicato-calcium phosphate (Sinaj
et al., 1994). A comparison SEM analysis between BS and BSP revealed that the
amounts of Ca, Fe and Si are higher in both slag. In addition the level of P in BS is very
low compared with the P content in BSP indicating that the BSP is rich in this element.

Table 6.3: SEM analysis of both slag (BS and BSP)

Element BS (wt. %) BSP (wt. %)
Al 0.65 0.62
Ca 69.06 68.16
Fe 17.71 10.0
K 0.93 1.26
Mg 1.20 0.69
Mn 2.64 1.43
P 1.46 10.60
Si 5.81 7.23

75
70
65
60
55
50
45
wt %

40 BS
35 BSP
30
25
20
15
10
5
0
Al Ca Fe K Mg Mn P Si

Figure 6.4: Comparison SEM analysis between BS and BSP

- 84 -
 Figure 6.5: X-EDS of BS

Figure 6.6: X-EDS of BSP

From X-EDS data, it is clear that the enrichment of BSP by P compared to BS is

evident. In addition X-EDS is performed on local region of few micrometer (here about
10X10 µm) and confirmed that P is not distributed ramdomly but in phases identified
previously by the XRD.

- 85 -
 Grain bonded by
amorphous phase

Figure 6.7: SEM images of BS

The texture of BS is a random distribution of the microlit of several micrometers. The

microlit exhibit a granular microtexture bonded by an amorphous phase. Large open
porosity is menaged by this texture

Elongated
mineral
Grain bonded by
amorphous phase

Figure 6.8: SEM images of BSP

The texture of BSP is quite similar to BS one with granular texture and large open
porosity. But in detail (Fig.6.8) it is possible to distinguish different shape of the
microlit with spheric one and tabular or rectangular ones. Phosphate mineral are
knowned to exhibit different forms and especially elongated ones.

- 86 -
6.5. Electron microprobe analysis (EPMA)

The results of both slags analysis by electron microprobe analysis (EPMA) are
presented in Figure 6.9 and Appendixes 1and 2. The EPMA reveal that the major
compounds of BS are Ca, Fe, Si and Mg; they are represented more than 90% of the
total mass. Mn, Al, P, Ti and Cr are observed in few amounts. On the other hand, the
major compounds of BSP are Ca, Fe, Si and P; they contain more than 95% of the total
mass. Lesser amounts of the elements Al, Ti, Mn, and Cr were also observed.

BS BSP

2
4
4

2
3
1 3

Figure 6.9: EPMA image of BS and BSP

According to data obtained from EPMA (Appendices 1 and 2), it can be seen that higher
levels of Ca, Fe and Si are observed in both slag. While higher concentration of P is
found in BSP compared with P content in BS indicated that the BSP is rich in
phosphorus. Similar results were obtained by chemical composition analysis and
scanning electron microscope.

- 87 -
 CHAPTER 7: Effect of Basic Slag Addition on Soil
Properties, Growth and Leaf Mineral Composition of Beans
in a Cu-Contaminated Soil

7.1. Introduction

In contaminated soils, stabilization techniques aim at decreasing the labile pool

of metals and metalloids such as As, Cr, Cu, Pb, Cd and Zn by the incorporation of
amendments. These techniques are able to enhance one or several processes such as the
metal adsorption through increased surface charge, the formation of organic and
inorganic metal complexes, sorption on Fe, Mn, and Al oxides, and precipitation. It can
be used in in situ and ex situ applications to reclaim and re-vegetate industrially
devastated areas and mine-spoils, restore the physical, chemical, and biological soil
properties, and reduce the contaminant mobility and bioavailability with various
chemical and mineralogical agents such as industrial by-products (Bolan and
Duraisamy, 2003; Pérez de Mora et al., 2005; Raicevic et al., 2005; Kumpiene et al.,
2008). Elements such as As, Cu, Cr, and Zn can be found in excess in contaminated
soils at wood treatment facilities, especially when Cu sulphates and chromated copper
arsenate (CCA) were used as a preservative against insects and fungi, which may result
in soil phytotoxicity (Kumpiene et al., 2008). The As stabilization can occur through
sorption on Fe oxides by replacing the surface hydroxyl groups with the As ions and
also by the formation of amorphous Fe (III) arsenates and/or insoluble secondary
oxidation minerals. The Cr immobilisation mostly deals with Cr reduction from toxic
and mobile hexavalent form Cr (VI) to stable Cr (III) in natural environments. Copper
immobilisation by clays, organic matter, carbonates, phosphates, and Fe oxides
amendments was reported with precipitation of Cu carbonates and oxy-hydroxides, ion
exchange and the formation of ternary cation–anion complexes on the surface of Fe and
Al oxy-hydroxides (Kumpiene et al., 2008). Phosphorus amendments, clays, birnessite
and coal fly ash such as beringite can successfully immobilise Zn in soil (Mench et al.,

- 88 -
2000; Bolan et al., 2003; Kumpiene et al., 2008). Several amendments such as coal or
bio-fuel fly ashes have been used for the in situ immobilisation of metals in
contaminated soils (Clark et al., 2001; Dermatas and Meng, 2003; Kumpiene et al.,
2007). Copper and Pb mobility and bioavailability in contaminated soil can be
effectively reduced using a combination of coal fly ash and peat by 96 % and 97 % in
the field respectively (Kumpiene et al., 2007) but also by sewage and paper mill sludge
(Merrington et al., 2003; Sajwan et al., 2003; Battaglia et al., 2006). Soil amended with
composted sewage sludge (Herwijen et al., 2006), organic matter (Brown et al., 2003;
Brown et al., 2004; Farfel et al., 2005; Stuczynski et al., 2007), lime (Hooda and
Alloway1996; Dutré et al., 1998; McKinley et al., 2001; Moon et al., 2004 ; Chen and
Wong, 2006), gypsum and lime-rich industrial by-products (Illera et al., 2004; Garrido
et al., 2005), hydroxyapatite (Boisson et al., 1999a), zeolites (Lin et al., 1998; Edwards
et al., 1999; Oste et al., 2002; Friesl et al., 2003 ; Mahabadi et al., 2007), birnessite
(Mench et al., 2000), iron grit (Mench et al., 1994b) and beringite (Vangronsveld et al.,
1996; Boisson et al., 1999b; Lombi et al., 2002 ; Mench et al., 2006) were used for the
in situ stabilization of metals in contaminated soils. The application of both lime and red
mud at 3 or 5% increased the soil pH and decreased the metal availability; thus it can be
used to remediate a heavily contaminated acid soil to allow re-vegetation (Gray et al.,
2006). Out of amendments including various alkaline materials, organic matter,
phosphates, alumino-silicates and iron grit, basic slag (3.9%) and compost of sewage
sludge (5%) combined with iron grit were the most efficient to promote shoot
production and limit the foliar Cu accumulation in dwarf beans cultivated in a highly
Cu-contaminated soil (Bes and Mench, 2008).

Several alkaline slags have been used for amending acid soils. Phosphogypsum
can improve soil properties such as pH, soil EC, CEC, exchangeable Ca, Mg, and metal
availability to plant, and also increase the crop yield (Alva and Sumner, 1990). Slag
treatments increased more soil pH than converter sludge treatments (Forghani et al.,
2006). Combination of slag and converter sludge treatments enhanced the plant Ca and
Mg concentrations. The application of calcium silicate slag reduced the soil acidity and
increased the available P, Si and exchangeable Ca in soil (Barbosa Filho et al., 2004).
Blast furnace slag are used to correct soil acidity and can promote root growth and

- 89 -
distribution in the soil profile, which results in higher shoot dry matter and grain yield
of upland rice under sprinkler irrigation (Carvalho-Pupatto et al., 2004). A combination
of converter slag and fungicide did not decrease the density of dormant spores of
Plasmodiophora brassicae in the soil but suppressed the clubroot disease (Murakami
and Goto, 2004). The application of Linz-Donawitz (LD) slag in acid soils managed
under pastures increased the soil pH with and without NPK fertilization (Pinto et al.,
1995), increased exchangeable soil Ca and Mg whereas exchangeable soil Al, Mn, Cu
and Zn decreased (Besga et al., 1996), and its combination with NPK fertilizers resulted
in highest crop yields and nutrient concentrations in plants (Lopez et al., 1995). Both
calcitic limestone and BS applied in Brazil sugarcane fields generated a beneficial
residual effect in the correction of soil acidity, the increase of base saturation and the
yield of sugar cane rattoon (Prado et al., 2003). For Ali and Shahram (2007), the
increasing rate of soil pH was proportional to the slag amount used. The slag decreased
the Fe availability at a pH range of 7.4 - 8.5 but increased at higher pH, while the use of
slag also proportionately increased the P and Mn availability. In greenhouse studies the
application of respectively 1 % and 2 % (w/w) of slag in tea garden soil and 0.5, 1 and 2
% slag in rice field soil increased the plant shoot dry yield and P and Mn uptake. Fe and
K uptake increased in rice field, K uptake decreased in tea garden soil and Fe uptake
was not changed. The addition of Thomas basic slag (TBS), hydrous manganese oxide
(HMO), iron grit (ST) and beringite to a contaminated soil did not increase the plant
biomass production but decreased the mobility and bioavailability of Cd, Zn and Pb
(Mench et al., 1994a,b). These agents effectively mitigated the Cd uptake by plants. In
ryegrass, HMO and ST decreased either shoot Pb or Zn concentrations, and TBS
reduced shoot Pb concentrations.

The Ca and P contents in BS make it a potential liming agent to increase the

precipitation and sorption of metals such as Cu and a potential fertiliser promoting plant
growth and improving the physico-chemical properties of the soil. Therefore this study
aimed at investigating a BS addition into a soil mainly Cu-contaminated from a wood
treatment facility to improve soil characteristics such as pH and EC and reduce the
labile pool of trace elements in soil for root-to-shoot transfer in beans. Hypotheses were
that BS compounds may influence the composition of soil solution through acid-base,

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precipitation and sorption reactions, and foliar concentrations through changes in soil
solution, competitions for root uptake and root-to-shoot transfer. Beans plants were
cultivated in potted soils with increasing BS addition rates, from 0% to 4%, placed in
controlled conditions. Changes in soil EC and pH, plant growth, biomass production
and the foliar elemental concentrations of primary leaves were determined.

7.2. Material and Methods

7.2.1. Basic slag characterisation

BS is a by-product of the steel industry, containing mainly calcium oxide, silicon

oxide, iron oxide, and other metal oxides. They were determined by using an atomic
absorption spectrophotometer. Arsenic (As) was analysed by GF-AAS according to
norm NF EN ISO 15586 (T90-119) after digestion with regal water (NF EN 13346),
other trace elements were analysis by ICP-AES according to norm NF EN ISO 11885
after mineralisation (total digestion NFX31-147). The pH and electrical conductivity
(EC) for BS were measured in 1:1 BS: water suspension by using pH meter and glass
electrode EC respectively. The characterisation of BS is shown in Table 7.1.

Table 7.1: Characterisation of the BS

pH 1:1 12.72
EC mS/cm 12.2
Al2O3 % 5.91
CaO % 60.69
Fe2O3 % 14.61
K 2O % 0.15
MgO % 2.51
MnO % 1.06
P2O5 % 1.05
SiO2 % 12.54
TiO2 % 1.47
As mg/kg <5
Cr mg/kg 615
Co mg/kg <5
Ni mg/kg <10
Cu mg/kg 5
Zn mg/kg 42
Pb mg/kg <20
Mn % 0.01

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7.2.2. Pot experiment

The topsoil of P7 (0-0.25 m) of a soil mainly contaminated by Cu was sampled

from a soil French wood treatment facility (Mench and Bes, 2009). Pot experiments
were carried out on a 2-week period with Phaseolus vulgaris L. An uncontaminated,
sandy soil was used as a control (CTRL). BS was added into the soil (1 kg soil/pot) to
constitute four treatments in triplicates: 0 % (T1), 1 % (T2), 2 % (T3) and 4 % (T4)
BS/kg air-dried soil. Four dwarf beans (Phaseolus vulgaris L. cv vroege Limburgs)
were sown in all pots and cultivated (15 days) in controlled conditions: illumination 12
h light/12 h darkness regime, intensity 150 µmol m-2 s-1, temperature 25°C/22°C, and
50% relative humidity. Pots were arranged in a fully randomised block design on a
bench and watered daily with deionised water (at 50% WHC) without loss from
drainage. The plant growth was monitored on a daily basis using an index based on
plant development steps for two weeks and then plants were harvested. Biometrical
parameters, i.e. fresh weight (FW) of roots, shoots, and primary leaves were measured.
Plant materials were washed with deionised water (2 times) and distilled water, oven
dried at 70°C, and weighted to determine the DW biomass production. Plant samples
(0.5 g) were wet digested in 5 mL 14M HNO3, 2 mL H2O2 and 1 mL distilled water at
180°C in PFA (perfluoroalkoxy copolymer resin) tubes under microwaves (MarXpress,
CEM). The mineral composition in the plant digests were measured by ICP-AES
(Ultima, Jobin Yvon Horiba, Longjumeau, France). The soil samples were taken from
all pots experiment to measure the soil pH and the EC in suspension soil: water in the
ratio 1:1 using a glass electrode pH meter and electrical conductivity respectively
(Jackson, 1967).

7.2.3. Statistics

The soil properties and plant yield, element concentrations and total element
amount in primary leaves [µg plant-1, so-called here element accumulation and
calculated based on foliar element concentration (µg kg-1 DW) and leaf biomass
production (µg DW plant-1)] of plants from the pot experiment were tested by statistical
analysis (ANOVA, Kruskall-Wallis and Tukey test) with SAS software version 9.1.

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7.3. Results and Discussion
7.3.1. Soil parameters

The BS incorporation in soil P7 increased the soil pH in relation with the

addition rate, from 5.6 for the T1 treatment to 7.9, 8.3 and 9.8 for the T2, T3, and T4
treatments respectively. This resulted in soil pH values higher in the T2, T3, and T4
treatments than in the control soil (7.0) (Figure 7.1). Increase in soil pH was predicted
by a polynomial equation (y = -0.223x2 + 1.883x + 5.774, R2 = 0.96). Ali and Shahram
(2007) found that the increasing rate of soil pH was proportional to the slag amount
used in the soils. Basic slag affected also the soil EC which increased from (in mS cm-1)
0.14 (T1) to 0.39, 0.46 and 0.82 for the T2, T3, and T4 treatments respectively.
Consequently, the soil EC was lower in the T1, T2 and T3 treatments and higher in T4
than in the control soil (0.62 mS cm-1) (Figure 7.2). A linear equation predicted the
increase in soil EC in relation with the BS addition rate (y = 0.161x + 0.176, R2 = 0.97).
The enhanced soil pH and EC in amended soils were likely due to the alkaline property
and composition of BS. Su and Evans (1996) reported that EC increased in soil treated
with lime. Amelioration of acid soils with amendments such as alkaline by-products can
improve soil properties such as pH and EC (Alva and Sumner, 1990). Our results are in
line with Pinto et al. (1995) who reported that BS application in acid soils increased the
soil pH with and without NPK fertilization. In addition, the incorporation of Thomas
basic slag into an excessively Cu contaminated topsoil from a wood treatment facility
increased the soil pH (Bes and Mench, 2008). Our results confirmed BS as a potential
liming agent able to improve the soil acidity. A 1% addition rate would correspond to
25000-30000 kg BS/ha depending of the soil depth considered, i.e. 0.25 or 0.3 m.
Rodriguez et al. (1994) suggested that Linz-Donawitz (LD) slag application increased
the soil pH linearly, especially where fertiliser was not applied. In fact the addition of
7500 kg, without NPK fertilisation, increased the soil pH from 5.3 to 6.5. When 3000 kg
ha–1 of slag was added, the increase in soil pH was accompanied by a decrease of Al
saturation percentage in the cation exchange complex to <10%.

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 12
A
11
B ***
10
C ***
9
*** D
8
***
E
Soil pH

7
6 ***
5
4
3
2
1
0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Bar graphs with different letters
were significantly difference; P (0.001<***<0.0001).

Figure7.1: Effects of BS addition on the soil pH

1 A
0.9 ***
0.8
B
0.7
***
EC (mS/cm)

0.6 C
D ***
0.5
***
0.4
0.3
E
0.2 ***
0.1
0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs
indicate a significant difference; P (0.001<***<0.0001).

Figure7.2: Effects of BS addition on the soil EC

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7.3.2. Plant analysis

7.3.2.1. Plant yield

Some basic slags previously used in acid soils have ameliorated plant growth
and their biomass production (Lopez et al., 1995). Shoot yield DW are presented in
Figure 7.3. The biomass of beans primary leaves is affected by the BS incorporation
into soil P7 and its effect varied across the treatments. The shoot yield was the highest
for the control soil and the lowest for the T1 treatment. This confirmed that soil P7
negatively impacted beans (Bes and Mench, 2008). Shoot yield numerically increased
for all amended soils. Compared to the untreated soil P7 (T1), T2 and T3 treatments
delivered the highest increases for the shoot yield, i.e. 1.89 and 1.75 times for T2 and
T3, while the T4 treatments gave an intermediate value. These values for shoot yields in
the T2 and T3 treatment corresponded to 89 % and 83 % based on the control soil value.
Only the difference between T1 and T2 treatments however was statistically significant.
The application of respectively 1 % and 2 % (w/w) of the slag in tea garden soil and 0.5,
1 and 2 % slag in rice field soil increased the plant shoot dry yield (Ali and Shahram,
2007). In addition, the application of Linz-Donawitz (LD) slag in acid soils combination
with NPK fertilizers resulted in highest crop yields (Lopez et al., 1995). The decrease in
shoot yield for the T4 treatment compared to the T2 and T3 treatments likely indicated
an excessive BS addition rate. The ideal soil pH for beans is in the 6.0-7.5 range
(Gardener’s Network, 2009) and soil pH for the T4 treatment largely exceeded these
values. In addition the soil conductivity in the 0-0.45 mS cm-1 range is suitable for most
plants if recommended fertilisers are used, but a high conductivity (0.46-0.7 mS cm-1)
may reduce the emergence and cause a slight to severe damage to salt sensitive plants
(Omafra, 2008). Indeed the soil EC in the T4 treatment which reached 0.8 mS cm-1
would be excessive and may contribute to limit beans shoot yields.

The BS effect on the root DW yield varied with the BS addition rate in soil.
Results are given in Figure 7.4. The highest value of the root DW yield occurred in the
T2 treatment and the lowest value in the T1 treatment. Root yield was significantly
higher in T2 and T3 BS-amended soils than in the untreated soil (T1) and control soil
(CTRL). The differences however remained relatively low.

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 0.09 A
A *
0.08
* AB
0.07 *
AB
Shoot dry weight(g)

0.06
*
0.05
B
0.04 *
0.03

0.02

0.01

0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs indicate
a significant difference; P (0.05<*<0.01).

Figure7.3: Effect of BS on the shoot yield of beans (g DW plant-1) for

each treatment

1.9
A AB
** ** C C
1.8 C
** **
**
1.7
Root dry weight(g)

1.6

1.5

1.4
1.3
1.2
1.1

1
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs indicate a
significant difference; P (0.01<**<0.001).

Figure 7.4: Effect of BS on the root yield of beans (g DW plant-1) for

each treatment

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 For the T2 and T3 treatments, the root yield increased 1.06 and 1.05 times
respectively compared to the untreated soil (T1). Higher increases in root biomass were
previously obtained with the addition of Thomas basic slag (TBS) in a Cu-contaminated
soil from a wood treatment facility (Bes and Mench, 2008) and of blast furnace slag to
upland rice (Carvalho-Pupatto et al., 2004). At 4% addition rate, the beneficial BS effect
on root yield disappeared again likely due to excessive increases in soil pH and EC.

7.3.2.2. Foliar elemental concentrations and accumulations

The effect of BS addition in soil on the foliar element concentrations and foliar
element accumulations are presented in Tables 7.2 and 7.3 respectively.

7.3.2.2.1. Foliar nutrients concentrations and accumulations

Foliar Al concentrations significantly decreased in plants from all BS-amended

soils, especially for the T3 plants, and were similar compared to the control level. The
decrease in foliar Al concentration is likely due to the liming effect, i.e. the increase in
the soil pH and competition with Ca for root uptake, and increase in primary leaf
biomass. The foliar Al accumulation varied in the 1.2-3.3 µg plant-1 range with lowest
and highest values for T3 and T2 plants but differences were not significant. Foliar Mg
concentration was higher in T1 plants than in control plants likely due to a lower leaf
biomass. The increase in the leaf biomass for the T2 and T3 beans reduced foliar Mg
concentration. In addition the increase in foliar Ca concentration may have also
decreased foliar Mg concentration in plant. Changes in foliar Mg accumulation were not
significant. The calcium concentration was 3 times lower in the primary leaves of beans
grown in soil compared to that in control beans. It was also below frequent values for
primary leaf Ca concentrations in dwarf beans. In the literature, 1% slag and 1%
converter sludge treatments increased Ca and Mg concentration in the plant (Forghani et
al., 2006). Bes and Mench (2008) suggested that the low foliar Ca concentration vs.
foliar Cu concentration can limit beans growth. The foliar Ca concentration was
increased 8.9 times for both T2 and T3 plants compared to T1 plants and 2.7 times
compared to the control plants. This reflected the Ca inputs in soil P7 due to the BS
incorporation. It decreased in T4 plants probably because roots were negatively

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impacted by the high soil EC value. The foliar Ca accumulation classed as: T1 < CTRL,
T4 < T2, T3. The foliar P concentrations ranked in the following order: T2, T3 < T4 <
CTRL, T1. The control soil contained a high organic matter content which could supply
organic P and was regularly fertilised. Both low leaf yield for the T1 plant and acid soil
pH in T1 treatment could likely enhance the foliar P concentration. Despite P inputs in
soil due to the BS incorporation, the foliar P concentration was not increased in beans
from BS-amended soils. We assumed that several soil and plant factors can explain this
result. Firstly, the BS contained a high Ca content and relatively high Fe and Al
contents. Therefore phosphates could be sorbed with these 3 cations and not easily
available in the soil solution for root uptake. Increase in the leaf yield could contribute
to reduce foliar P concentration in T2 and T3 beans. Regarding foliar P accumulation,
plants from untreated and BS-treated P7 soils have a lower value than the CTRL soil.

Table 7.2: Elemental concentrations in the primary leaves of beans

Frequent
Treatments T1 T2 T3 T4 CTRL values (#)
0.07 a 0.04 ab 0.02 b 0.04 ab 0.03 b
Al mg/kg ± 0.01* ± 0.02* ± 0.01* ± 0.01* ± 0.01*
3.14 a 1.93 c 1.93 c 2.18 c 2.51 b
Mg g/kg ± 0.10*** ± 0.20*** ± 0.15*** ± 0.03*** ± 0.21*** 1.9 - 3.7
3.37 d 29.41 a 29.45 a 21.54 b 10.97 c
6.4 - 29
Ca g/kg ± 1.03*** ± 3.21*** ± 1.37*** ± 1.77*** ± 1.95***
5.24 a 3.16 b 3.30 b 4.23 ab 4.82 a
1-6
P g/kg ± 0.52** ± 0.55** ± 0.41** ± 0.42** ± 0.14**
16.01 b 18.62 b 21.17 b 29.77 a 19.31 b
13 - 22
K g/kg ± 1.23** ± 2.78** ± 2.16** ± 3.95** ± 0.13**
0.11 a
<dl <dl <dl <dl 0.03 - 0.07
Cd mg/kg ± 0.10 NS
0.41 a 0.33 a 0.61 a 0.65 a 1.70 a
0.13 - 1.7
Cr mg/kg ± 0.09 NS ± 0.11 NS ± 0.27 NS ± 0.07 NS ± 1.02 NS
53.13 a 22.59 b 27.54 b 27.64 b 5.65 c
4.9 - 7.9
Cu mg/kg ± 14.04** ± 1.59** ± 1.51** ± 0.71** ± 0.67**
25 a 31.5 a 16.5 a 24 a 12 a
13 - 20
Zn mg/kg ± 14 NS ± 20.5 NS ± 3.5 NS ± 12 NS ± 2.5 NS

- In a column mean values (± standard deviations) followed by the same letter do not differ significantly P
(0.05<*<0.01), P (0.01<**<0.001), P (0.001<***<0.0001) and non significant NS (p>0.05).
- (#) ranges of frequent values for element concentrations in the primary leaves of dwarf beans grown on
uncontaminated control soils (Mench et al., 1996).
- dl: (detection limit).

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 Table 7. 3: Elemental accumulation in the primary leaves of beans (µg plant-1)

Treatments T1 T2 T3 T4 CTRL
2.87 a 3.31 a 1.18 a 2.16 a 2.28 a
Al ± 1 .28 NS ± 2.26 NS ± 0.25 NS ± 0.97 NS ± 0.40 NS
119 a 138 a 128 a 117 a 195 a
Mg ± 34 NS ± 16 NS ± 30 NS ± 25 NS ± 34 NS
127 c 2140 a 1950 a 1170 b 843 b
Ca ± 49*** ± 531*** ± 430*** ± 337*** ± 71***
198 b 225 b 214 b 224 b 377 a
P ± 57* ± 27* ± 22* ± 29* ± 87*
602 b 1354 a 1405 a 1583 a 1521 a
K ± 151* ± 343* ± 361* ± 260* ± 406*
0.01 a
<dl <dl <dl <dl
Cd ± 0.01 NS
0.02 a 0.02 a 0.04 a 0.03 a 0.15 a
Cr ± 0.01 NS ± 0.01 NS ± 0.02 NS ± 0.00 NS ± 0.10 NS
2.04 a 1.63 a 1.81 a 1.48 a 0.43 b
Cu ± 0.80 NS ± 0.32 NS ± 0.34 NS ± 0.27 NS ± 0.06 NS
0.92 a 2.26 a 1,07 a 1.27 a 0.94 a
Zn ± 0.04NS ± 1.08 NS ± 0.06 NS ± 0.8 NS ± 0.03 NS

- In a column (mean values ± standard deviations) followed by the same letter do not differ
significantly P (0.05<*<0.01), P (0.001<***<0.0001) and non significant NS (P>0.05).
- dl: (detection limit).

The foliar K concentration increased in relation with the BS addition rate but
differences were only significant between T4 plants and the other plants. The foliar K
concentration was 1.8 times and 1.5 times higher in T4 plants than in T1 plants and
control plants, respectively. This slightly exceeded frequent values for foliar K
concentration in beans primary leaves. However in plants the critical K concentration is
in the range of 20-50 g kg-1 DW (Marschner, 1995). The foliar K accumulation was
similar in T2, T3, T4 and CTRL. Only the T1 plants showed a decrease in foliar K
accumulation compared to all other plants.

7.3.2.2.2. Foliar trace element concentrations and accumulations

The foliar Cu concentration varied from 5.6 mg kg-1 to 53.1 mg kg-1 in the
following order: CTRL < T2, T3, T4 < T1. The foliar Cu concentration in T1 plants
exceeded its frequent values and the critical Cu concentration for beans leaves i.e. 15-30
mg Cukg-1 DW (MacNicol and Beckett, 1985). We assumed that this mainly caused the

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phytotoxic effect in plants grown in the untreated, Cu-contaminated soil 630 mg Cu/ kg.
The highest decrease in the foliar Cu concentration, i.e. 2.3 times compared to the T1
plants, was obtained for the T2 plants. This suggested that the Cu labile pool for root
uptake in the soil is low at the T2 soil pH and that further increase in the soil pH for the
T3 and T4 treatments could enhance Cu complexation with dissolved organic matter in
the soil solution (Sauvé et al., 1997). The mobility of copper in soil depended on several
factors, including the Cu-complexing ability of the solid phase, the Cu-complexing
ability of the DOM, and the molecular weight of the DOM fractions (Han and
Thompson, 2003). Cu–DOM complexation increases approximately 10-fold per pH unit
(Lu and Allen, 2000). However the availability of such Cu-DOM complexes for root
uptake in T3 and T4 soils is questionable. The BS addition at 1% into studied soil
promoted beans growth with the lowest foliar Cu concentration and highest Ca
concentrations. Foliar Cu accumulation varied from 0.4 mg to 2.0 mg plant-1 in the
following order: CTRL < T4, T2, T3, T1. Indeed the Cu amount accumulated in
primary leaves was not significantly changed in plants from BS-treated soils, but their
improved shoot yield resulted in reducing foliar Cu concentrations through a biomass
dilution effect. The rise in foliar Ca accumulation in BS-treated plants may contribute to
a better pectin methylesterase functioning (Micheli, 2001), resulting in the restoration of
cell elongation and a higher Cu sorption on the cell walls. Restoration of Ca
homeostasis may also promote plant metabolism and the Cu sorption by various ligands
(Pilon et al., 2006). Changes in foliar Zn concentration were not significant across the
treatments. Foliar Zn concentration exceeded its frequent values in some dwarf beans
from BS-treated soils but remained below the critical leaf concentration for dwarf beans
i.e. 100 mg kg-1 DW (Mench et al., 2000). Usually an increase in soil pH reduces Zn
availability in the soil solution and changes in the leaf yield affect the foliar Zn
concentration causing a decrease in foliar Zn concentration (Mench et al., 2000). For
instance the addition of Thomas BS decreased the mobility and bioavailability of Cd,
Zn and Pb in a highly contaminated soil, near smelters at Evin (Pas de Calais, France)
(Mench et al., 1994a). But here our results did not confirm such previous studies. The
foliar Cr concentration was not significantly changed in BS-treated soils compared with
the control soil, and all values fell in the range of Cr frequent values. The foliar Cr
accumulations were also similar for all treatments. Foliar Cd concentration and

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accumulation decreased below the analytical detection limits with the BS application
compared with untreated soil.

7.4. Conclusion

A BS was incorporated at increasing addition rates (1, 2 and 4%) in an acid

sandy Cu-contaminated soil. The soil pH was increased from 5.6 in the untreated soil up
to 9.8 for the 4 % BS-amended soil. The soil conductivity rose from 0.14 mS cm-1 in the
untreated soil to 0.38 mS cm-1, 0.46 mS cm-1, and 0.82 mS cm-1 in the 1%, 2%, and 4%
BS-amended soils respectively. These increases in soil pH and EC in all BS-amended
soils likely resulted from the BS composition and in particular its high Ca content. The
pot experiment carried out with dwarf beans demonstrated that (i) the foliar Cu
concentration likely caused a phytotoxic effect in plants grown in the untreated, Cu-
contaminated soil, (ii) the BS incorporation at 1% addition rate into the contaminated
soil promoted beans growth with the lowest foliar Cu concentration and highest Ca
concentrations, and (iii) foliar P concentration however was not enhanced by the BS
incorporation into the Cu-contaminated soil. Instead, foliar K accumulation in primary
leaves was restored up to the control level. Therefore this by-product was effective at
1% addition rate as a liming material but not as a P fertilizer in this short-term
experiment. The BS incorporation in the contaminated soil did not increase the foliar
concentrations and accumulations for Cd, Cr, and Zn.

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 CHAPTER 8: In Situ Remediation of Trace Elements in
Chromated Copper Arsenate (CCA)-Contaminated Soil Using
Basic Slag Phosphate (BSP)

8.1. Introduction

Soil contamination by trace elements is a widespread problem in many parts of

the world. The accumulation of toxic metals in soil is mainly inherited from parent
materials or inputs through human activities (He et al., 2005). One of the sources of soil
contaminations is very important resulting from chemical widely used wood
preservative industries in aquatic environments and storing the wood after treatment by
chromated copper arsenate (CCA). Elements such as As, Cu, Cr, and Zn can be found in
excess in contaminated soils at wood treatment facilities, especially when Cu sulphates
and chromated copper arsenate (CCA) were used as a preservative against insects and
fungi, which may result in soil phytotoxicity (Kumpiene et al., 2008). After
impregnation of the wood with a CCA solution the metal compounds are fixed to the
cell walls of the wood matrix (Helsen et al., 1998). The rain is playing a key-role in
leaching these metals from the recently treated timber and lumber stored at the
treatment facility. Under conditions storage the soils contain high concentrations of
CCA (Buchireddy et al., 2008). Therefore it is very important to reduce or immobilise
these metals in contaminated soil. Currently there are several technologies can be used
to clean up or remove the soils and the mining wastes contaminated by toxic metals,
such as thermal treatments, biological and physical/chemical procedures. These removal
technologies are generally costly to practice and destructive to the application sites, and
only partially effective for the total removal (efficient clean up) of toxic metals, or for
the sufficient reduction of their mobility and bioavailability (Raicevic et al., 2005). In
the past few decades, the stabilization technique or in situ immobilisation of trace
elements in contaminated soil by adding amendments is one of the common practices
reducing negative effects of contaminants such as As, Cr, Cu, Pb, Cd and Zn to improve
the quality of contaminated soil. It is considered as a simple and cost-effective approach
for the treatment of metals in contaminated soils, particularly when these soils are

- 102 -
difficult or costly to be removed or treated ex situ. In situ immobilisation aims at
enhancing natural attenuation mechanisms such as (ad)sorption through increased
surface charge, precipitation, complexation and redox reactions that occur naturally in
the soils to reclaim and re-vegetate industrially devastated areas and mine-spoils,
restore the physical, chemical, and biological soil properties, and reduce the
contaminant mobility and bioavailability with various chemical and mineralogical
agents ( Mench et al., 2000; Oste et al., 2002; Bolan and Duraisamy, 2003; Adriano et
al., 2004; Pérez de Mora et al., 2005; Raicevic et al., 2005; Kumpiene et al., 2006;
Kumpiene et al., 2008 ).

Several application studies have demonstrated that in situ immobilisation of

contaminated soils and groundwaters by using inexpensive soil amendments. The
amendments can significantly reduce the mobility of metals in soils, metal uptake by
plants and metal phytotoxicity. Neutralizing agents in form of alkaline materials are
usually added to acidic soils to ameliorate soil chemical and physical properties and
reduce the bioavailability of contaminant to plants. (Brallier et al., 1996; Brown et al.,
1997; Bolan and Duraisamy, 2003; Gray et al., 2006; Tlustos et al., 2006). A range of
liming materials available, such as calcite (CaCO3), burnt lime (CaO), slaked lime
(Ca(OH)2), dolomite (CaMg(CO3)2), and slag (CaSiO3), varying in their ability to
neutralise the acidity (Bolan and Duraisamy, 2003). According to changes in the soil
pH, alkaline materials may be effective treatment chemicals to induce metal hydrolysis
reactions and/or co-precipitation with carbonates, acting as a precipitating agent for
metals in the soil solution acid (Tylar and McBride, 1982; Mench et al., 1998; Singh
and Oste, 2001; Bes and Mench, 2008). The application of lime in acid soil decreased
the soluble fraction and plant uptake of Ni, Cd, Zn and Cu to crops as well as increasing
crop yield (Brallier et al., 1996; Krebs et al., 1998; Singh and Oste, 2001). The addition
of alkaline materials in a highly Cu-contaminated soil can improved the plant growth
and decreased the Cu concentration in both soil and plants (Fessenden and Sutherland,
1979; Bes and Mench, 2008). The combination of Ca (H2PO4)2 and CaCO3 in a multi-
metal contaminated site reduced the toxicity and leaching extractable concentrations of
Cd, Cu, Pb, Ni and Zn by more than 96% for Cd, Cu, Pb, Zn and Ni (Wang et al.,
2001). Phosphogypsum can improve soil properties such as pH, EC, CEC, exchangeable

- 103 -
Ca, Mg, and metal availability to plant, and increase the crop yield (Alva and Sumner,
1990).

Phosphate compounds and associated materials such as phosphoric acid,

phosphate rocks, synthesized apatites have been successfully applied to stabilise the
mobility of Pb, Cd, Zn and Cu in contaminated soils, sediments and solid wastes,
reducing their bioavailability for plant uptake and thus their transport in soils and
subsequent groundwater contamination (Bolan et al., 2003; Liu and Zhao, 2007).
Phosphate minerals have the potential to sorb and /or coprecepite trace metals (Barrow,
1987; Ma et al., 1993; Pierzynski and Schwab, 1993; Xu et al., 1994; Ma, 1996; Mench
et al., 1998). The use of hydroxyapatite (HA) as a soil additive for the in situ
remediation of metals (Zn, Pb, Cu, and Cd) in contaminated soils resulted in a decreased
of the exchangeable metal contents in soil, increased plant growth and decreased the
concentrations of toxic metals in the plant leaves (Boisson et al., 1999a,b). When iron
phosphate (vivianite) was used as in situ immobilisation of copper contaminated soils to
reduce the Cu availability in soils, precipitation and adsorption processes were probably
responsible for the decrease of Cu availability in soils (Liu and Zhao 2007).

Slag, which consists of calcium oxide, aluminium oxide, and other metal oxides,
is an alkaline by-product of metallurgical processes or a residue of incineration
processes. It has been used as a soil additive to remove various metals contaminated soil
by precipitation and adsorption on the surface of metal oxide. The mechanism of copper
removal using slag is precipitation with hydroxide dissolved from slag rather than
adsorption on slag surface (Kim et al., 2008). Blast-furnace slag is an effective sorbent
for Cu, Zn Ni and Pb ions in a wide range of ion concentrations and pH values
(Dimitrova, 1996; Dimitrova and Mehandjiev, 1998). The application of blast furnace
slag to correct soil acidity promotes maximum root growth in depth, higher shoot dry
matter and grain yield (Carvalho-Pupatto et al., 2004). Calcium silicate slag can reduce
the soil acidity and increased the available Ca, Mg, Si and P content (Besga et al., 1996;
Barbosa Filho et al., 2004), whereas exchangeable Al, Mn, Cu and Zn decreased (Besga
et al., 1996). The application of slag addition rate in tea garden and rice field soils

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increased soil pH, plant shoot dry yield and P and Mn uptake, while the Fe and K
uptake increased in the rice field and K uptake decreased in the tea garden soil whereas
Fe uptake was not changed (Ali and Shahram, 2007). Thomas phosphate basic slag
(TBS) was used as an amendment in several contaminated soils and did not increase the
plant biomass production but decreased the mobility and bioavailability of Cd, Zn and
Pb (Mench et al., 1994a,b). While the combination of BS and steel shots were more
effective in reducing Zn and Cd mobility than when used separately in contaminated
soils (Mench et al., 1998). The incorporation of Thomas basic slag into an excessively
Cu contaminated topsoil from a wood treatment facility increased the soil pH, shoot and
root biomass, and foliar Ca concentration whereas foliar Cu concentration in plant
decreased (Bes and Mench, 2008). The application of steel abrasive (SA) or oxygen
scarfing granulate (OSG) to stabilise metals from CCA-contaminated soil can decrease
the concentrations of As, Cr, Cu, and Zn in leachates and soil pore water (Lidelöw et
al., 2007).

In this study, BSP was used as a soil remediation technique to improve physical
and chemical soil properties and also for the in situ immobilisation of copper and other
trace elements in chromated copper arsenate (CCA) contaminated soil by increased the
precipitation and adsorption on the surface metal oxide thus changing the availability
and mobility of metals. The objectives of this study were :(1) to determine the influence
of BSP addition into a strongly Cu-contaminated soil 630 mg/kg from a wood treatment
facility by solutions of Cu sulphates and chromated copper arsenate to improve soil
properties such as soil pH and EC, (2) to evaluate the effect of different BSP addition
rates on the plant yield production and the foliar elemental concentrations of primary
leaves, (3) to determine the potential of BSP to reduce copper and trace metals in CCA
contaminated soil as well as to reduce the metal toxicity uptake by beans plants. Pot
experiments were carried out on a 2-weeks period with dwarf beans (Phaseolus vulgaris
L.). BSP was added into the pots (1 kg soil) with four different treatments in triplicates:
0 % (T1), 1 % (T2), 2 % (T3) and 4 % (T4) BSP/kg air-dried soil. An uncontaminated,
sandy soil was used as a control (CTRL). After the two weeks period, soil and plant
samples were collected to determine soil pH, EC soil, yield production and mineral
analysis of plants. The mineralogy of the clay and silt fractions of soil treated with BSP

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addition rate were determined by X – ray powder diffraction analysis (XRD) to identify
the copper crystalline phases.

8.2. Material and Methods

8.2.1. Characteristics of the soil amendment

BSP has been used as a soil amendment to improve the physical and chemical
soil properties and for in situ immobilisation of copper and trace elements in chromated
copper arsenate (CCA) contaminated soil. In this study BSP containing mainly of
calcium oxide, phosphorus oxide, silicon oxide, iron oxide, and other metal oxides.
They were determined by using an atomic absorption spectrophotometer. Arsenic (As)
was analysed by GF-AAS according to norm NF EN ISO 15586 (T90-119) after
digestion with regal water (NF EN 13346), other trace elements were analysis by ICP-
AES according to norm NF EN ISO 11885 after mineralisation (total digestion NFX31-
147). The pH and electrical conductivity (EC) for BSP were measured in 1:1 BSP:
water suspension by using pH meter and glass electrode EC respectively. The chemical
characteristics of BSP are shown in Table 8.1.

Table 8. 1: Chemical characteristics of BSP

pH 1:1 11.65
EC mS/cm 2.15
Al2O3 % 5.56
CaO % 30.71
Fe2O3 % 21.4
K 2O % 0.53
MgO % 9.55
MnO % 2.53
P2O5 % 14
SiO2 % 14.63
TiO2 % 1.09
As mg/kg <5
Cr mg/kg 511
Co mg/kg <5
Ni mg/kg <10
Cu mg/kg <5
Zn mg/kg 24
Pb mg/kg <20
Mn % 1.13

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8.2.2. Pot experiment

The top layer of P7 (0-25 cm) of a Cu contaminated soil (630 mg/kg) originating
mainly from Cu sulphate and in a lesser extent from standard CCA type C was sampled.
BSP treatments were applied to improve soil properties and stabilize copper and trace
elements in the contaminated soil. Four soil treatments (1 kg air-dried weight) were
prepared and mixing with 0 %, 1 %, 2 % and 4 % of BSP addition rate (Table 8.2).
Three replicates of each treatment were homogenised by rotation in 2-L plastic flasks,
transferred into 1.3-L plastic pots. The control soil (CTRL) was treated in the same way.
After incorporation of the BSP into the soil, the moisture content was raised to 70 % of
water holding capacity (WHC, 10% of soil air-dried weight) by manual irrigation with
distilled water and the soil was allowed to react for four weeks at 20°C before seeds
were sown. Four dwarf beans (Phaseolus vulgaris L. cv vroege Limburgs) were sown in
all pots just below the soil surface. Plants were cultivated in the laboratory under
controlled environmental conditions: illumination 12 h light/12 h darkness regime,
intensity 150 µmol m-2 s-1, temperature 25°C/22°C, and 50% relative humidity. Pots
were arranged in a fully randomised block design on a bench and watered daily with
deionised water (at 50% WHC) without loss from drainage. The plant growth was
monitored on a daily basis using an index based on plant development steps for two
weeks and then plants were harvested.

Several biometrical parameters, i.e. fresh weight (FW) of roots, shoots, and
primary leaves were measured. Plant parts were washed with deionised water (2 times)
and distilled water, oven dried at 70 °C, and weighted to determine the DW biomass
production. Plant samples (0.5 g) were wet digested in 5 mL 14M HNO3, 2 mL H2O2
and 1 mL distilled water at 180°C in PFA (perfluoroalkoxy copolymer resin) tubes
under microwaves (MarXpress, CEM). The acid digested plants; then the solution was
filtered through ash free paper. Mineral composition in digests plants was determined
by ICP-AES (Ultima, Jobin Yvon Horiba, Longjumeau, France). The soil samples were
taken from all pots experiment to measure the soil pH and the EC in suspension soil:
water in the ratio 1:1 using a glass electrode pH meter and electrical conductivity
respectively (Jackson, 1967). Clay and silt fractions of soil mixed with BSP were

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separated by pipette methods (Richards, 1954; Jackson, 1969). They were determined
by X – ray powder diffraction analysis (XRD), performed on a PANanalytical X pert
MPD diffractmeter using Cu Kα radiation of 40Kv and 40 mA with the range 2θ
secondary monochromator and counting time of one hour.

Table 8. 2: Basic slag phosphate (BSP) added to the soil treatments

Treatments Addition
T1 (0%) Untreated soil
T2 (1%) 10 g BSP kg-1 soil
T3 (2%) 20 g BSP kg-1 soil
T4 (4%) 40 g BSP kg-1 soil
CTRL Control soil

8.2.3 Statistical analysis

The soil and plant samples data collected from the pots experiment were tested
by statistical analysis (ANOVA, Kruskall-Wallis and Tukey test) with SAS software
version 9.1 to evaluate soil properties (soil pH and EC soil), plant yield (root and shoot
yield), elemental concentrations in primary leaves and the total element amount in
primary leaves [µg plant-1, so-called here elemental accumulation which calculated
based on the foliar element concentration (µg kg-1 DW) and leaf biomass production
(µg DW plant-1) of plants. All analytical determinations were performed in triplicate.

8.3. Results and Discussion

8.3.1. Effect of BSP on soil properties

The applications of the addition rate of BSP in copper and trace elements
contaminated soil from CCA significantly increased the soil pH and EC soil. In fact the
soil pH increased from 5.68 in the untreated contaminated soil (T1) to 7.04, 7.44 and
7.95 in the T2 (1%), T3 (2%), and T4 (4%) treated soils respectively. This results
indicated that an increase in the soil pH in all treatments of BSP and the highest values
of soil pH occurs for the T3, and T4 treatments compared with the control soil (7.41)
(Figure 8.1). BSP also influences the EC soil which increased from 0.15 mS cm-1 (T1)

- 108 -
to 0.47 mS cm-1, 0.51 mS cm-1 and 1.17 mS cm-1 for the T2, T3, and T4 treatments
respectively. Consequently, EC soil was increased in the T2, T3 and T4 treatments
compared to the control soil (0.41 mS cm-1) (Figure 8.2).

These increases in soil pH and EC soil in all amended soils were caused by the
application of BSP. This is possibly due to the compounds of BSP and in particular the
Ca content in this alkaline product. Other studies showed that the addition of lime to
acid soil increased the soil pH and EC soil. Su and Evans (1996) reported that the EC
soil increased when the mixing of acid soil with lime. The application of lime in heavy
metals contaminated soil increased the soil pH with a corresponding increase in the net
negative charge of variably charged soil colloids such as clays and organic matter (Gray
et al., 2006). Moreover the amelioration of acid soils with the application of soil
amendments such as alkaline by-products can improve the soil pH and EC (Alva and
Sumner, 1990). The application of basic slag in acid soils increased the soil pH with and
without NPK fertilization (Pinto et al., 1995; Besga et al., 1996; Forghani et al., 2006).
The incorporation of Thomas basic slag into acid soil contaminated by copper from a
wood treatment facility can increase the soil pH (Bes and Mench, 2008). Our results
confirmed that the application of BSP addition rates in acid soil is able to ameliorate the
soil properties.

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 12
11
10
9 B A C
8 D *** *** ***
7 E ***
Soil pH

6 ***
5
4
3
2
1
0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs
indicate a significant difference; p (0.001<***<0.0001).

Figure 8.1: Effects of BSP on the soil pH

1.5
1.4
1.3 A
1.2 ***
1.1
1
EC(mS/cm)

0.9
0.8
0.7
C B
0.6
0.5 *** *** D
0.4 ***
0.3 E
0.2 ***
0.1
0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs
indicate a significant difference; p (0.001<***<0.0001).

Figure 8.2: Effects of BSP on the soil EC

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8.3.2. Plant analysis

8.3.2.1. Effect of BSP on shoot biomass

Data of shoot yields DW are given in Figure 8.3. All addition rates of BSP to
copper contaminated soil resulted in increasing the shoot yield of beans primary leaves.
The highest value of the shoot yield occurs in the control soil (CTRL) and the lowest
value of the shoot yield has in the untreated contaminated soil (T1). The results of
variance plant analysis indicated that the beans plants were not able to grow on the
excessive copper contaminated soil 630 Cu mg/Kg. This confirmed that this soil
negatively impacted beans plants (Bes and Mench, 2008). Shoot yield numerically
positive for all amended soils. The best growth responses were obtained after the
application of BSP at 2% and 4% addition rates. Therefore treatments T3 and T4 gave
the highest shoot yields, i.e. 3.4 and 4.2 times respectively compared with the untreated
contaminated soil (T1), while the T2 treatment gave an intermediary value. These
values for the T3 and T4 treatment corresponded to 61 % and 67 % compared with
CTRL treatment. The increases in shoot yields in T3 and T4 treatments compared with
the T2 treatment were related to the increase of the BSP addition rate. This possible is
caused by the application of BSP addition rate which had a positive effect on the
chemical soil properties such as soil pH and EC.

These results agree well with those obtained by (Alva and Sumner, 1990;
Barbosa Filho et al., 2004; Carvalho-Pupatto et al., 2004; Bes and Mench, 2008). They
found that the addition of slag to correct soil acidity promotes higher shoot dry matter
and grain yield. The best soil pH for growth beans plants ranges from 6.0 to 7.5
(Gardener’s Network, 2009). Omafra, (2008) reported that most plants are suitable
growth when the soil conductivity ranges from 0 to 0.45 mS cm-1 ; however when the
soil conductivity ranges from 0.46 to 0.7 mS cm-1 , the plant growth may decrease and
cause a slight to severe damage to salt sensitive plants. Our results indicate that when
the soil pH was 7.95 and EC soil was 1.17 mS cm-1, the addition of 4% BSP increased
more the shoot yield than a 2% BSP addition rate.

- 111 -
 0.35
A
***
0.3

0.25 B
Shoot dry weight(g)

B ***
0.2 ***
B
0.15 ***

0.1
C
0.05 ***

0
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs
indicate a significant difference, p (0.001<***<0.0001).

Figure 8.3: Effect of BSP on the shoot yield of beans (g DW plant-1) for
each treatment

8.3.2.2. Effect of BSP on root biomass

For the root yield DW, the results indicate that the application of BSP increased
the root yield DW in all amended soils compared with the untreated contaminated soil
(T1) and CTRL soils. Results of the root yields DW are given in Figure 8.4. The
treatment T4 has the highest value of the root yield DW whereas the lowest value of the
root yield DW occurs in the T1 treatment. The T2 treatment gave an intermediary value.
Root yield was significantly higher for the T3 and T4 treatments than for the untreated
(T1) and control soils (CTRL). The root yield increased 3 and 3.5 times in the T3 and
T4 treatments respectively compared with the untreated soil (T1), and they increased 1.3
and 1.5 times respectively compared with the CTRL treatment. These results are in
good agreement with (Carvalho-Pupatto et al., 2004; Bes and Mench, 2008). They
reported that the application of slag to correct soil acidity increased the root biomass. In
contrast, Thomas phosphate basic slag (TBS) was used as an amendment in several

- 112 -
contaminated soils and did not increase the plant biomass production but decreased the
mobility and bioavailability of Cd, Zn and Pb (Mench et al., 1994a,b).

0.24 A
0.22 ***
0.2 AB
0.18
***
Root dry weight(g)

0.16 BC
***
0.14 C
0.12 ***
0.1
0.08 D
0.06
***
0.04
0.02
T1 T2 T3 T4 CTRL

Values are mean ± standard errors (n=3). Different letters on bar graphs
indicate a significant difference, p (0.001<***<0.0001).

Figure 8.4: Effect of BSP on the root yield of beans (g DW plant-1) for
each treatment

8.3.2.3. Effect of BSP on concentrations and accumulations of elements in plants

The effects of BSP addition rate in the CCA contaminated soil on the foliar
element concentrations and foliar element accumulations of beans plant are shown in
Tables 8.3 and 8.4 respectively.

Aluminium

The application of BSP significantly decreased the foliar Al concentration in all

treatments compared with the untreated contaminated soil (T1). Foliar Al concentration

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 Table 8. 3: Elemental concentrations in the primary leaves of beans
Treatments T1 T2 T3 T4 CTRL

0.05 a 0.03 b 0.03 b 0.02 b 0.02 b

Al mg/kg
± 0.01** ± 0.01** ± 0.01** ± 0.00** ± 0.00**
3.02 a 1.77 c 1.72 c 1.49 c 2.47 b
Mg g/kg
± 0.20*** ± 0.02*** ± 0.11*** ± 0.10*** ± 0.39***
2.54 b 16.31 a 20.12 a 19.25 a 21.27 a
Ca g/kg
± 1.15*** ± 0.92*** ± 1.58*** ± 3.23*** ± 3.33***
5.21 a 3.55 b 2.71 c 2.33 c 5.23 a
P g/kg
± 0.19*** ± 0.04*** ± 0.59*** ± 0.50*** ± 0.12***
21.91 a 13.03 d 15.63 cd 17.36 b 19.02 b
K g/kg
± 1.27*** ± 1.05*** ± 1.5*** ± 1.59*** ± 1.74***
6.02 a 0.72 b 0.79 b 0.86 b 0.42 b
Cr mg/kg
± 2.01*** ± 0.41*** ± 0.19*** ± 0.71*** ± 0.18***
35.73 a 19.47 b 17.41 c 13.96 d 6.23 e
Cu mg/kg
± 1.31*** ± 1.15*** ± 1.01*** ± 0.74*** ± 0.67***
10.18 a 6.84 ab 4.71 ab 2.9 b 10.91 a
Zn mg/kg
± 6.77* ± 0.31* ± 1.31* ± 1.47* ± 0.65*

In a column mean values (± standard deviations) followed by the same letter do not differ
significantly P (0.05<*<0.01), (0.01<**<0.001), P(0.001<***<0.0001) and non significant
NS (p>0.05).

Table 8. 4: Elemental accumulation in the primary leaves of beans (µg plant-1)

Treatments T1 T2 T3 T4 CTRL

2.61 a 3.79 a 5.26 a 4.09 a 5.94 a

Al
±0 .10 NS ±1.27 NS ±2.70 NS ±0.71 NS ±0.40 NS
166 b 262 b 336 b 311 b 774 a
Mg
±34*** ±16*** ±30*** ±25*** ±34 ***
150 c 2403 b 3934 b 4065 b 6662 a
Ca
±103*** ±142*** ±622*** ±1060*** ±1615***
289 b 524 b 529 b 480 b 1632 a
P
±77*** ±44*** ±48*** ±62*** ±281***
1219 c 1925 c 3055 b 3629 b 5874 a
K
±351*** ±245*** ±474*** ±509.83*** ±703.66***
0.32 a 0.11 a 0.15 a 0.19 a 0.13 a
Cr
±0.07 NS ±0.05 NS ±0.04 NS ±0.17 NS ±0.05 NS
1.96 b 2.86 a 3.41 a 2.91 a 1.92 b
Cu
±0.38*** ±0.07*** ±0.44*** ±0.34*** ±0.22***
0.65 b 1.01 b 0.91 b 0.58 b 3.39 a
Zn
±0.55*** ±0.11*** ±0.18*** ±0.25*** ±0.54***

In a column (mean values ± standard deviations) followed by the same letter do not differ
significantly P (0.001<***<0.0001) and non significant NS (p>0.05).

- 114 -
significantly decreased in plants from all BSP-amended soils, especially in level BSP
4% which was similar compared with the control (CTRL). It can be noticed that the
decrease in foliar Al concentration is possibly due to the influence of the liming agent in
BSP, increasing pH and EC soil and competiting with Ca for root uptake, and increase
in primary leaf biomass. Other studies showed that the addition of lime on the soil
surface significantly increased the soil pH and decreased Al toxicity (Brown et al.,
2008). In most cases the addition of phosphorus to acid soils results in the precipitation
of Al (Wright, 1937). Calcium silicate slag can be reduced the soil acidity and decreased
exchangeable soil Al (Besga et al., 1996). The foliar Al accumulation ranges from 2.61
to 5.94 µg plant-1. The lowest value occurs for the T1 treatment and the highest value
has in CTRL plants. BSP addition rates significantly increased the foliar Al
accumulation in all amended soil compared to the untreated contaminated soil (T1).

Magnesium

The foliar Mg concentration decreased in all amended soil compared with the
untreated contaminated soil (T1) and control soil (CTRL). The foliar Mg concentration
varied between 1.49 to 3.02 g/kg DW. The lowest value was for the T4 treatment and
the highest value occurred for the CTRL plants. In general, Mg concentrations in plants
range between 1.5 and 3.5 g kg-1 DW (Marschner, 1995). It can be noticed the
increases in the leaf biomass for the T3 and T4 treatments reduced the foliar Mg
concentration. This is possibly due to the increases in foliar Ca concentrations. The
foliar Mg accumulation was higher in the CTRL plant than in the untreated
contaminated soil (T1) and all treatments BSP-amended soil. In addition, all BSP
addition rates significantly increased the foliar Mg accumulation compared with the
untreated contaminated soil (T1).

Calcium

The foliar Ca concentration significantly increased in all amended soil compared

with the untreated contaminated soil (T1). The low foliar Ca concentration vs. foliar Cu
concentration can limit beans growth. Similarly the incorporation of a Thomas basic
slag into an excessively Cu-contaminated topsoil from a wood treatment facility can
increase the foliar Ca concentration and decrease the foliar Cu concentration in plant

- 115 -
(Bes and Mench, 2008). The foliar Ca concentration ranges between 2.54 to 21.27 g/kg
DW with the lowest and highest values for T1 and CTRL plants respectively. Generally
the Ca concentration in plants normally ranges between 1 to 50 g/kg DW (Marschner,
1995) and the Ca concentration in the primary leaves of dwarf beans grown on
uncontaminated soils varies between 6.4 to 29 g/kg DW (Mench et al., 1996). The
highest concentrations of Ca in the primary leaves of beans plants occurs for the
addition of BSP 2 % (T3) and 4% (T4) with an increase of 7.92 and 7.57 times
respectively compared with the untreated contaminated soil (T1), while the addition of
BSP 1% (T2) gave an intermediary value. A slightly decrease occurs for the T4
treatment compared with the T3 treatment, probably due to the fact that the roots plants
were negatively impacted by the high value of EC soil. The foliar Ca accumulation also
significantly increased in all amended soil compared with the untreated contaminated
soil (T1). The highest Ca accumulation in the primary leaves of beans plants has in the
CTRL plant and the lowest Ca accumulation occurs in T1 treatment. Generally, the
foliar Ca accumulation was classed as: T1 < T2 < T3, T4 < CTRL.

Phosphorus

In acidic soils the phosphorus availability of Thomas slag is similar to that of

other water soluble phosphorus fertilizer (Sinaj et al., 1994). Thomas slag was
composed of a P, Si and Ca ; silicato-calcium phosphate was the prevailing form of P in
the cells and a high Fe, Ca and Mn content in the walls (Sinaj et al., 1994). The foliar P
concentration decreased with the application of BSP in all treated soils compared to the
untreated contaminated soil (T1) and control soil (CTRL). The foliar P concentration
varies from 2.33 to 5.33 g/kg DW. The lowest value was for the T4 treatment and the
highest values occur for the CTRL plants. The foliar P concentrations ranked in the
following order: CTRL, T1 < T2 < T3, T4. It can be noticed that the reduced in P
concentrations after applied the BSP in all treatments soil are probably directly related
to increasing soil pH and foliar Ca concentrations. The P concentration in the primary
leaves of dwarf beans grown on uncontaminated soils ranged between 1 to 6 g/kg DW
(Mench et al., 1996). The highest P concentration in CTRL plants was probably due to
the increased decomposition of organic matter in soil control. On the other hand, the
increased P concentration in the untreated contaminated soil (T1) may be related to the

- 116 -
low soil pH and low biomass production. It can be assumed because the BSP
composition, particularly its high liming agent, the phosphates are not available in the
soil solution for the root uptake due to the adsorption or precipitation with cations such
as Ca, Fe and Al. Pinto et al. (1995) reported that the addition of slag in acid soil
increases exchangeable soil Ca and Ca concentration in soil solution, therefore,
available soil phosphate contents exhibit a general decrease due to the adsorption and
displacement of phosphate by hydroxyl ions. The foliar P accumulation was higher in
the CTRL than in T1 and all treatments BSP addition rate. In general, all BSP addition
rates significantly increase the foliar P accumulation compared to the untreated
contaminated soil (T1).

Potassium

The foliar K concentration decreased with the application of BSP in all amended
soils compared to the untreated contaminated (T1) and control soils (CTRL). The foliar
K concentration varies between 13.03 to 21.91 g/kg DW with lowest and highest
concentration for T2 and untreated contaminated soil (T1) treatments respectively. The
foliar K concentrations ranked in the following order: T1, CTRL < T4 < T3< T2. It can
noticed that the foliar K concentrations were 1.3 and 1.1 times lower in T4 plants than
in T1 and CTRL plants, respectively. However, the foliar K accumulation increased
with the application of BSP in all treated soils compared with the untreated
contaminated soil (T1), but a decrease foliar K accumulation occurs after the application
of BSP in all treated soils compared with the control plants (CTRL). Pinto et al. (1995)
suggested that the application of slag in acid soil decreased soil K content as a result of
the lime-induced increase in CEC resulted in the decrease in K content related to yield
increase when slag was applied. K uptake decreased in a tea garden soil when the
application slag addition rate (Ali and Shahram, 2007). Generally, the critical K
concentration in some plants range between 20 to 50 g kg-1 DW (Marschner, 1995),
while in the primary leaves of dwarf beans grown on uncontaminated soils, the K
concentration is range between 13 to 22 g/kg DW (Mench et al., 1996).

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Copper

The foliar Cu concentration decreased with the application of BSP for all treated
soils compared with the untreated contaminated soil (T1). The foliar Cu concentration
varied from 6.23 to 35.73 mg kg-1 DW with lowest and highest values for CTRL and T1
treatments respectively. Generally, the foliar Cu concentrations ranked in the following
order: T1 < T2 < T3< T4< CTRL. The lowest concentrations of Cu in the primary
leaves of beans plants occurred in the (T3) and (T4) treatments with a decrease of 2 and
2.5 times respectively compared with the untreated contaminated soil (T1). The critical
Cu concentration for beans leaves i.e. 15-30 mg Cu kg-1 DW (MacNicol and Beckett,
1985). This indicated that the beans plants were not able to grow on the excessive
copper contaminated soil (630 Cu mg/Kg) caused by the phytotoxic effect in this soil.
Kim et al. (2008) suggested that the mechanism of copper removal using slag is
precipitation with hydroxide dissolved from slag rather than adsorption on slag surface.
However Liu and Zhao, (2007) reported that the application of iron phosphate decreased
the Cu availability in copper contaminated soils by precipitation and adsorption
processes. It can be noticed that the levels 2% and 4% BSP incorporation into copper
contaminated soil promoted best beans growth with the highest Ca concentrations and
lowest foliar Cu concentration. The foliar Cu accumulation increased with the
application of BSP in all treated soils compared to the untreated contaminated soil (T1)
and the control plants (CTRL). The foliar Cu accumulation varied from 1.92 to 3.41 µg
plant-1 with lowest and highest values for CTRL and T3 treatments respectively. The
increase in foliar Ca accumulation in all treatments BSP addition rate may contribute to
a better pectin methylesterase functioning (Micheli, 2001), and also promote the Cu
sorption by various ligands (Pilon et al., 2006). These results agree well with those
obtained by (Brallier et al., 1996; Krebs et al., 1998; Singh and Oste, 2001; Bes and
Mench 2008). They found that the addition of alkaline materials in acid soil can
decrease Cu concentration in soil and plant and increased crop yield.

Chromium

The foliar Cr concentration decreased with the application of BSP in all treated
soils compared to the untreated contaminated soil (T1). The foliar Cr concentration
varied from 0.42 to 6.02 mg kg-1 DW with the lowest and highest values for CTRL and

- 118 -
T1 treatments respectively. Generally, the foliar Cr concentrations ranked in the
following order: T1 < T4 < T3< T2< CTRL. The Cr concentration in the primary leaves
of dwarf beans grown on uncontaminated soils was reported to range between 0.13 - 1.7
mg/kg DW (Mench et al., 1996). The reduction of Cr in soils is accelerated by the
presence of organic matter and divalent iron (Kumpiene et al., 2008). The lowest value
of Cr concentration in CTRL plants may be due to the presence of organic matter in the
control soil. Kumpiene et al. (2006) reported that the application of zerovalent iron in a
chromated copper arsenate (CCA) contaminated soil reduced Cr concentration in plant
shoots by 95%. The decreased of Cr contaminated soil may be causing by presence iron
oxide which reduced Cr (VI) to Cr,Fe(OH) precipitation (Fendorf, 1995). However, the
foliar Cr accumulation was higher in the T1 treatment compared with all amended soils.
Thus, it can be noticed that all BSP addition rates significantly decreased the foliar Cr
accumulation compared to the untreated contaminated soil (T1).

Zinc

The foliar Zn concentration significantly decreased with the application of BSP

in all treated soils compared to the untreated contaminated soil (T1) and control soil
(CTRL). The foliar Zn concentration ranges between 2.9 to 10.91 g/kg DW. The lowest
value was for the T4 treatment and the highest value occur for the CTRL plants. Mench
et al. (2000) reported that an increase in soil pH decreases Zn availability in the soil
solution while changes in the leaf yield affect the foliar Zn concentration causing a
decreased foliar Zn concentration. The best lowest concentrations of Zn in the primary
leaves of beans plants occurs when the addition of BSP 4% (T4) with an decreases
were 3.5 and 3.8 times compared with the untreated contaminated soil (T1) and control
soil (CTRL) respectively. The application of Thomas phosphate basic slag (TBS) in
contaminated soils can decrease the mobility and bioavailability of Zn (Mench et al.,
1994a,b). While the combination of basic slag and steel shots were more effective in
reducing Zn mobility than when used separately in contaminated soils (Mench et al.,
1998). The foliar Zn accumulation increased with the application of BSP in all
treatments with an exception decreased when the addition 4% BSP compared with the
untreated contaminated soil (T1). However a decrease of the foliar Zn accumulation
occurred in all amended soil compared with the control plants (CTRL).

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8.4. Mineralogical form of copper in the particle-size fractions of the
soil

Soil stabilization with the addition of BSP to reduce the metal mobility and
bioavailability of copper contaminated soil was investigated by XRD. Analysis was
performed for the silt and clay fractions BSP-soil. The diffraction patterns and the
principal crystalline metal-containing phases from silt and clay fractions of soil
treatments are presented in Figures 8.5 and 8.6 and Tables 8.5 and 8.6.

8.4.1. Copper in the particle-size fractions of the contaminated soil

In our study, the results of the XRD analysis of the silt fraction of the
contaminated soil (T1) indicate that the copper was detected in the form of cuprite
(Cu2O), arsenic copper (AsCu9), and plancheite (Cu2(CO3)(OH)2). While in the clay
fraction in the contaminated soil (T1) shows that copper and other trace elements such
as As and Cr were observed in the form of cuprite (Cu2O), arsenic copper (AsCu9),
malachite (Cu2(CO3)(OH)2), magnesium chromium oxide (MgCr2O4 ) and chromium
arsenate (CrAsO4). In general copper is distinctly more soluble under oxidised
condition than under reduced in the pH rang 5.4-6.5 (Bhattacharya et al., 2002). Thus,
an increase in the pH soil caused Cu to be strongly adsorbed at the colloidal surfaces by
decreasing the exchangeable form, which is the highly mobile form (Lindsay, 1979).
According to changes the soil pH, alkaline materials may be effective treatment
chemicals to induce metal hydrolysis reactions and/or co-precipitation with carbonates,
acting as a precipitating agent for metals in the soil solution acid (Tylar and McBride
1982; Mench et al., 1998; Singh and Oste, 2001; Bes and Mench, 2008). Our results
confirm that BSP increased the soil pH in relation with the addition rate, from 5.7 in the
untreated contaminated soil (T1) to 7.0, 7.4 and 7.9 in the amended soils at 1%, 2% and
4 % BSP addition rate respectively. The increase in soil pH in all amended soils is
possibly due to the composition of BSP in particular the Ca content in this alkaline
product. Liming increases the pH (increase of surface charge) and enhances sorption of
heavy metals by reducing the solubility by adsorption or precipitation in the soil (Singh
and Oste, 2001).

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 15000

14000

13000

12000

11000
T4
10000

9000

T3
Lin (Counts)

8000

7000

6000 T2
5000

4000

T1
3000

2000

1000

10 20 30 40 50 60 70 80

2-Theta - Scale

Figure 8.5: XRD diffraction patterns of the silt fractions for each treatment

12000

11000

10000

T4
9000

8000

T3
Lin (Counts)

7000

6000

5000
T2
4000

3000 T1
2000

1000

10 20 30 40 50 60 70 80

2-Theta - Scale

Figure 8.6: XRD diffraction patterns of the clay fractions for each treatment

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 Table 8. 5: Forms of metals in the silt fractions for each treatment
Treatments
BSP
Mineral compound Formula
Cuprite Cu2O
Arsenic copper AsCu9
T1 (0%)
Plancheite 3CuSiO3.H2O
Silicon oxide SiO2

Cuprite Cu2O
Azurite Cu3(CO3)2(OH) 2
Arsenic copper AsCu9
Plancheite 3CuSiO3.H2O
Silicon oxide SiO2
T2 (1%) Arsenic oxide As2O3
Copper hydrogen nitrogen phosphate chloride Cu4.72H3.2(P12N18O6) Cl2
Hentschelite CuFe3+2(PO4)2(OH) 2
Copper oxide phosphate Cu4O(PO4)
Barium calcium copper thallium oxide TlBa2Ca3Cu4O
Aluminum phosphate silicate Al2O3.0.90P2O5.0.22 SiO2

Cuprite Cu2O
Arsenic copper AsCu9
Plancheite 3CuSiO3.H2O
Silicon oxide SiO2
Copper hydrogen nitrogen phosphate chloride Cu 4.72 H 3.2 (P12N18O6) Cl2
T3 (2%) Hentschelite CuFe3+2(PO4)2(OH)2
Copper oxide phosphate Cu4O(PO4)
Dachiardite (Ca,Na2,K2)5Al10Si38O96·25(H2O)
Aluminum phosphate silicate Al2O3.0.90P2O5.0.22 SiO2
Calcium phosphate Ca2P2O5
Sodium copper oxide hydroxide Na5(CuO2)(OH)2

Cuprite Cu2O
Arsenic copper AsCu9
plancheite 3CuSiO3.H2O
Silicon oxide SiO2
Copper hydrogen nitrogen phosphate chloride Cu 4.72 H 3.2 (P12N18O6) Cl2
Hentschelite CuFe3+2(PO4)2(OH)2
T4 (4%)
Copper oxide phosphate Cu4O(PO4)
Dachiardite (Ca,Na2,K2)5Al10Si38O96·25(H2O)
Aluminum phosphate silicate Al2O3.90P2O5.0.22 SiO2
Calcium phosphate Ca2P2O5
Portalandite Ca(OH)2
Arsenic oxide As2O3

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 Table 8. 6: Forms of metals in the clay fractions for each treatment
Treatments
BSP
Mineral compound Formula
Cuprite Cu2O
Malachite Cu2(CO3)(OH)2
Arsenic copper AsCu9
T1 (0%)
Silicon oxide SiO2
Magnesium chromium oxide MgCr2O4
Chromium arsenate CrAsO4

Cuprite Cu2O
Azurite Cu3(CO3)2(OH)2
Plancheite 3CuSiO3.H2O
Malachite Cu2(CO3)(OH)2
Silicon oxide SiO2
T2 (1%) Hentschelite CuFe3+2(PO4)2(OH)2
Copper oxide phosphate Cu4O(PO4)
Copper nikle phosphate Cu Ni2(PO4)2
Calcium copper hydrogen phosphate Ca Cu HPO4
Calcium copper titanium oxide CaCu3Ti4O12
Calcium copper germanium oxide CaCu3(Ge4)O12

Cuprite Cu2O
Azurite Cu3(CO3)2(OH)2
Plancheite 3CuSiO3.H2O
Malachite Cu2(CO3)(OH)2
Silicon oxide SiO2
T3 (2%) Hentschelite CuFe3+2(PO4)2(OH)2
Pseudomalachite Cu5(PO4)2(OH)4
Copper oxide phosphate Cu4O(PO4)
Calcium copper germanium oxide CaCu3(Ge4)O12
Copper hydrogen nitrogen phosphate chloride Cu4.72 H3.2 (P12N18O6) Cl2
Sodium copper oxide hydroxide Na5(CuO2)(OH)2

Cuprite Cu2O
Azurite Cu3(CO3)2(OH)2
Plancheite 3CuSiO3.H2O
Malachite Cu2(CO3)(OH)2
Silicon oxide SiO2
T4 (4%)
Hentschelite CuFe3+2(PO4)2(OH)2
Pseudomalachite Cu5(PO4)2(OH)4
Copper oxide phosphate Cu4O(PO4)
Copper hydrogen nitrogen phosphate chloride Cu4.72 H3.2 (P12N18O6) Cl2
Sodium copper oxide hydroxide Na5(CuO2)(OH)2

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8.4.2. Copper in the particle-size fractions of the BSP- soil

Stabilization of copper in the soil by clays, organic matter, carbonates,

phosphates and Fe oxides amendments was reported with precipitation of Cu carbonates
and oxy-hydroxides, ion exchange and the formation of ternary cation–anion complexes
on the surface of Fe and Al oxy-hydroxides (Kumpiene et al., 2008). Copper was
strongly associated with organic matter and was homogeneously distributed on the clay
fraction surface (Adamo et al., 1996). Our study indicates that the application of BSP in
the contaminated soil (T1) can reduce the copper mobility by adsorption or precipitation
on the BSP surface. The addition of alkaline materials in a highly Cu-contaminated soil
can be decreased Cu concentration in the soil (Bes and Mench, 2008). In addition the
mechanism of copper removal using slag may be is precipitation with hydroxide
dissolved from slag rather than adsorption on slag surface (Kim et al., 2008).

Silt fractions

In the silt fraction, it seems that in all amended soils, copper was observed in the
forms of cuprite (Cu2O), arsenic copper (AsCu9), in associated with silicate such as
plancheite (3CuSiO3.H2O) and in associated in the form of complex precipitation with
iron and phosphate such as copper hydrogen nitrogen phosphate chloride
(Cu4.72H3.2(P12N18O6)Cl2), hentschelite (CuFe3+2(PO4)2(OH)2) and copper oxide
phosphate (Cu4O(PO4). Only in addition of 1% BSP copper was detected in associated
with carbonate and oxy-hydroxides in the form of azurite (Cu3 (CO3)2(OH)2), and also
in associated with calcium in the form of barium calcium copper thallium oxide
TlBa2Ca3Cu4O. The stabilization of trace elements contaminated soil by amended soil
does not reduce the total content of contaminants but lower the amounts of mobile and
bioavailability of the fractions (Kumpiene et al., 2006).

Clay fractions

Soil clay mineralogy is influences chemical adsorption and coprecipitation,

thereby affecting contaminant solubility and mobility (Hesterberg, 1998). In general, the
soils having highest amounts of clay content showed the highest values for metal
adsorption (Singh and Oste, 2001). Our study indicates that several phases were
observed in the clay fractions compared with the silt fractions. Generally, it seems that

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from all soil treatments BSP addition rate, copper was observed in the form of cuprite
(Cu2O), associated with silicate including plancheite (3CuSiO3.H2O), associated with
carbonate and oxy-hydroxides in the form of azurite (Cu3 (CO3)2(OH)2) and malachite
(Cu2(CO3)(OH)2) and associated in the form complex with calcium, iron and phosphate
including hentschelite (CuFe3+2(PO4)2(OH)2) and copper oxide phosphate(Cu4O(PO4).
The presence of inorganic anions (carbonate, phosphate, sulphate) in the soil water can
influence the soils ability to fix metals chemically. These anions can form relatively
insoluble complexes with metal ions and cause metals to desorb and/or precipitate in
their presence (Evanko and Dzombak, 1997).

Sorption of metal cations onto hydrous oxides generally increases sharply with
pH (Evanko and Dzombak, 1997). For pH above 7, copper tend to precipitate in the
form of carbonate and hydroxide (Gagnon, 1998). The mechanism of copper retention
were precipitation of Cu carbonates and oxy-hydroxide, ion exchange and formation of
ternary cation-anion(SO4, PO4) complexes on the surface of Fe and Al oxy-hydroxides
(Kumpiene et al., 2008). Therefore, in the level of 1% BSP addition rate, copper was
observed in association with calcium and phosphate in the form of copper nickel
phosphate (Cu Ni2(PO4)2), calcium copper hydrogen phosphate(Ca Cu HPO4), calcium
copper titanium oxide (CaCu3Ti4O12). Calcium copper germanium oxide
(CaCu3(Ge4)O12) was only observed in the level of 1% and 2% BSP addition rate. In
the level of 2% and 4% BSP addition rate copper was detected in the form complex in
association with phosphate and sodium hydroxide such as copper hydrogen nitrogen
phosphate chloride (Cu4.72H3.2(P12N18O6)Cl2), sodium copper oxide hydroxide
(Na5(CuO2)(OH)2) and pseudomalachite (Cu5(PO4)2(OH)4). Our results are in line with
Kim et al. (2008). They found that the precipitation amount of copper was highly
depending on pH and slag compounds. These results indicate that most of copper
mobile was precipitated on the surface slag causing by the compound of BSP in
particularly the high Ca and P contents which able to make of it a potential liming agent
to sorb and precipitated metals in soil.

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8.5. Conclusion

Remediation with BSP improved soil properties and reduce the trace elements
mobility and bioavailability in soil and metal uptake by plants. BSP is an alkaline by-
product in steel making process with potential properties to ameliorate physical and
chemical soil properties and metal stabilization from chromated copper arsenate (CCA)
contaminated soil. BSP was mixed at increasing addition rates (1%, 2% and 4%) in an
acid sandy Cu-contaminated soil 630 mg/kg from a wood treatment facility with
solutions of Cu sulphates and chromated copper arsenate. Analysed soil samples
showed that the soil pH was increased from 5.68 in the untreated contaminated soil to
7.04, 7.42 and 7.95 in the 1%, 2% and 4 % BSP addition rate respectively. At the same
time, BSP also influenced the soil EC which increased from 0.15 mS cm-1 in the
untreated soil to 0.47 mS cm-1, 0.51 mS cm-1 and 1.17 mS cm-1 in the 1%, 2% and 4%
BSP addition rate respectively. The pot experiment showed that the addition of BSP
resulted in an increased in the root and shoot DW yield for all treatments compared with
the untreated contaminated soil (T1). Foliar Al concentration decreased with an
increased Al accumulation in plants from all BSP-amended soils compared with the
untreated contaminated soil (T1). Foliar Ca concentration was enhanced for all treated
soils with increased in Ca accumulation compared to the untreated contaminated soil
(T1). The foliar Mg, K and P concentrations were not enhanced by the BSP addition
into the Cu-contaminated soil. All addition rates of BSP-amended soil decreased foliar
Cu concentration compared with the untreated contaminated soil (T1). The foliar Cr and
Zn concentrations and accumulation was not increased with the application BSP into the
soil. We conclude that the incorporation of 2% to 4% BSP into the copper contaminated
soil can promoted highest root and shoot DW yields with the highest Ca concentrations
and lowest foliar Cu concentration. The mineralogical form of copper and other trace
elements in silt and clay fractions of contaminated soil (T1) were observed in the form
of cuprite (Cu2O), arsenic copper (AsCu9), plancheite (Cu2(CO3)(OH)2), malachite
(Cu2(CO3)(OH)2), magnesium chromium oxide (MgCr2O4 ) and chromium arsenate
(CrAsO4). The application of BSP addition rate in contaminated soil (T1) can reduce
copper mobility by adsorption or precipitation on the BSP surface. Therefore, it seems
that in all amended soil BSP, copper observed in association with silicate, carbonate and
oxy-hydroxides and complex precipitation with calcium, sodium, iron and phosphate.

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 SUMMARY

New Technique for Soil Reclamation and Conservation: In Situ Stabilization of

Trace Elements in Contaminated Soils

Soil contamination by trace elements is a widespread problem in many parts of

the world. The accumulation of toxic metals in soil is mainly inherited from parent
materials or inputs through human activities. In fact, one of the sources of soil
contaminations is very important resulting from chemical widely used wood
preservative industries in aquatic environments and storing the wood after treatment by
chromated copper arsenate (CCA). Elements such as As, Cu, Cr, and Zn can be found
in excess in contaminated soils at wood treatment facilities, especially when Cu
sulphates and chromated copper arsenate (CCA) were used as a preservative against
insects and fungi, which may result in soil phytotoxicity as well as toxic to plants,
animals and humans. The mobility and exchangeable fractions of trace elements in soils
are the most important associated to toxicity and bioavailability in contaminated soils.
Therefore, it is very important to removal /uptake or reduces metals contaminated soils
by the application of assisted natural remediation processes. Currently there are several
technologies that can be used to clean up or remove these metals from the contaminated
soils and the mining wastes, such as thermal treatments, biological and
physical/chemical procedures. These removal technologies are generally require the
uptake of contaminated soil, its subsequent treatment and either replacing it on-site, or
disposed in specific landfills and it is costly to practice and destructive to the
application sites, and only partially effective for the total removal of toxic metals, or for
the sufficient reduction of their mobility and bioavailability.

In the past few decades, new techniques are being developed to remediate trace
elements in contaminated soils such as phytoremediation and in situ stabilization. In situ

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stabilization technique or in situ immobilisation is one of the common practices for
reducing negative effects of metals and metalloids such as As, Cr, Cu, Pb, Cd and Zn in
contaminated soils by adding amendments. In situ immobilisation is generally non-
disruptive for the natural landscape, hydrology, and ecosystems than conventional are
excavation, treatment, and disposal methods. It is considered as a simple and cost-
effective approach for the treatment of metals in contaminated soils, when these soils
are difficult or costly to be removed and treated ex situ. This technique can be used in
situ and ex situ to reclaim and re-vegetate industrially devastated areas and mine-spoils,
restore the physical, chemical, and biological soil properties, and reduce the
contaminant mobility and bioavailability with various chemical and mineralogical
agents. It is able to enhance one or several processes such as metal adsorption through
increased surface charge, formation of organic and inorganic metal complexes, sorption
on Fe, Mn, and Al oxides, and precipitation. In addition the main goal of this technique
is not to reduce the total content of contaminants but help to lowers the fraction of toxic
elements or compounds, which are potentially mobile or bioavailable.

Several application studies have demonstrated that in situ immobilisation of

contaminated soils by using inexpensive soil amendments, such as alkaline materials
(calcite, lime, dolomite and slag), phosphate minerals (phosphoric acid, phosphate
rocks, synthesized apatites), aluminosilicates mineral (clay and zeolites), Iron and
manganese oxides and hydroxides (zerovalent iron), organic matter and alkaline
biosolids (waste by-products) were found to be suitable for the remediation metal-
contaminated soil. The amendments significantly reduced the mobility of metals in soil,
metal uptake by plants, and metal phytotoxicity. Therefore, alkaline materials are
usually added to acidic soils to improve soil chemical and physical properties and also
to reduce the mobility and bioavailability of contaminant. Slag, which consists of
calcium oxide, phosphorus oxide, silicon oxide, iron oxide, and other metal oxides, is an
alkaline by-product of metallurgical processes or a residue of incineration processes.
Slags have been successfully used to soil reclamation and soil fertiliser. It has been used
as a soil additive to remove various metals contaminated soil by precipitation and
adsorption on the surface of metal oxide.

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 The objectives of this Ph.D study were to evaluate the physical, chemical soil
properties and the distribution of trace elements in contaminated soil. Also to evaluate
the characteristics of two different slags samples, a basic slag (BS) and a basic slag
phosphate (BSP) which are alkaline by-products of the French steel industry and which
used as a soil amendments to improve soil properties and for the in situ immobilisation
of copper and metals in chromated copper arsenate (CCA) contaminated soil. Topsoil
(0-25 cm) samples were collected from a former wood preservation site, south
Bordeaux, France. Four soil treatments (1 kg air-dried weight) were prepared and
mixing with 0 %, 1 %, 2 % and 4 % of BS and BSP. The BS and BSP effects on
physical, chemical and mineralogy soil properties were investigated. In addition, the
concentration and accumulation of metals in biomass beans plants were also evaluated
to change the availability and mobility of these metals in contaminated soil and metal
uptake by plants.

The following main results have been achieved:

1. Physico-chemical soil properties and distribution trace elements in thesoil

The results indicate that the soils of the study area are mostly coarse in texture
(mainly sand and loamy sand), the sandy texture dominates in most soil samples
followed by loamy sand and all soil samples were very low contents in fine materials
(silt + clay). The gravel contents of the soil study ranged between 12 to 87 % by weight.
In some cases, very gravely soil texture (gravel content > 50%) occurs in the surface,
subsurface and deepest layer of soil profiles. Organic matter content in soil samples
ranges between 0.67 to 3.01%. Most soil profiles show a clear decrease of OM with
depth indicated that little amount accumulation in the surface soil and the low amounts
of OM in most soil samples are the result of poor vegetation cover and indicating poor
soil fertility. Calcium carbonate distribution in soil samples showed that the range is
between 1.34 and 2.3% and the decrease of calcium carbonate in soil samples may be
due to the absence of the basic cations such as Ca, Mg, and K. The pH soil varied from
4.04 to 7.11 and decreases with depth. All soil samples are extremely acid, slightly acid
and very slightly alkaline. Thus, extremely and strongly acid soils (pH 4.0-5.0) can have

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high concentrations of soluble metals which may be toxic towards the growth of some
plants and also effect on the availability of some nutrients such as phosphorus,
potassium, calcium, sodium and magnesium. The EC values of the soil study ranged
from 0.02 to 0.44 dS/m and all soil samples are non saline (0-4 dS/m). The much lower
salinity level in soil profiles study may be causing by the effect of rainfall and leaches
basic cations (e.g, Ca, Mg, K) into drainage water. Cation exchange capacity (CEC)
indicates that the soil study ranged between 1 and 10.6 cmol (+)/kg and decreased with
depth. The low value of CEC in soil study is probably due to the high content of coarse
texture and low clay and organic matter contents.

The distribution of trace elements in our study indicate that, from all soil
samples study, Cu is the dominate followed by Cr, Zn, As, Ni then Co and they ranged
from 4.2 to 1970, 10.9 to 114, 15.4 to 95.7, 1.93 to 51.1, 5.22 to 14 and 1.66 to 4.81
mg/kg respectively. The concentrations of many contaminants tend to accumulate in the
soil surface. Therefore, the distribution of Cu, Cr, As and Zn increases in the surface
layer of soil profiles and then decreases with depth in all soil profiles. In contrast Co
and Ni were decreased in the surface layer of soil profiles and then increased with depth
in all soil profiles. In general As, Cu, Cr, and Zn can be found in excess in contaminated
soils at wood treatment facilities, especially when Cu sulphates and chromated copper
arsenate (CCA) were used as a preservative against insects and fungi, which may result
in soil phytotoxicity. Our study indicates that copper is highly phytotoxic at higher
concentrations above 30 mg/kg. Therefore, this is probably causing a problem of
toxicity to plants then animals and humans. Higher concentration of Cu found in all
surface layers of soil profiles and then decreases with depth. It can be noticed that, Cu
concentration was exceeded 100 mg/kg in all surface soil profiles and some subsurface
and deepest layers of soil profiles indicating that all soil profiles were contaminated.
The results of PCA indicates that there was a relationship between copper
concentration and clay content for the soil samples but it is weak causing by the low
clay content in soil profiles (r2= 0.24). In fact, copper was low strongly associated with
OM of soil samples (r2= 0.22) due to the low amount of OM in studied soil. There was
no relationship between copper content and pH soil. This is possibly resulted from the
anthropogenic contamination influence probably related to the input of CCA-C in the

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soil study. The top layer (0-25 cm) has been mainly contaminated by Cu originated
mainly from Cu sulphate and in a lesser extent from standard CCA type C (copper oxide
11.1 % w/w, chromium trioxide 30 % w/w, arsenic pentoxide 19.9 % w/w) used as
wood impregnation from an industrial site.

2. Slags characteristics used as remediation technology for contaminated soils

Two different type of slags, basic slag (BS) and basic slag phosphate (BSP) were
used as soil amendments to remediate trace elements contaminated soil. Slag
characterization was carried out using the following analytical techniques: chemical
composition analyzed by an atomic adsorption spectrophotometer, mineralogical
analysis examined by X-ray diffraction (XRD), microstructure observed by optical
microscope, scanning electron microscope (SEM) coupled with an energy
dispersive(EDX) and electron microprobe analysis (EMPA). The results indicate that
the major compound of BS is mainly consists of Ca (60.69 wt % CaO), Fe (14.61 wt %
Fe2O3), Si (12.54 wt % SiO2), Al (5.91 wt % Al2O3) and Mg (2.51 wt % MgO). Other
compounds such as TiO2, MnO, P2O5 and K2O are low contents; they represent
respectively 1.47, 1.06, 1.05 and 0.15 wt%. The major compound of BSP is mainly
composed of Ca (30.71 wt % CaO), Fe (21.4 wt % Fe2O3), Si (14.63 wt % SiO2), P (14
wt % P2O5), Mg (9.55 wt % MgO), Al (5.56 wt % Al2O3) and Mn (2.53 wt % MnO2).
Other compounds such as, TiO2 and K2O are observed in few amounts; they represent
respectively 1.09 and 0.53 wt %. It can be noticed that the amounts of phosphorus
oxide in the BSP is very much higher than in the BS indicating that BSP is rich in
phosphorus oxide.

The results of XRD analysis of both slag samples revealed that many phases
such as larnite, wustite, brownmillerite, calcite and merwinite are generally found in
both slag samples. Some phases were observed in BS compared with BSP such as
mayenite, portlandite, melilite, grossular, imandrite and calcium silicate oxide. In
addition, some crystallized compounds were detected in BSP than BS phases such as
rodolicoite, calcium silicon, calcium aluminum iron oxide, calcium phosphate, titanium
hydrogen phosphate, amonium hydrogen phosphate oxide and whitlockite. Similar

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results were obtained by SEM and EDS analysis and electron microprobe analysis
(EPMA) reported that the level of P in BS is very low compared with the P content in
BSP indicating that the BSP is rich in this element.

3. Effect of the basic slag addition on soil properties, growth and leaf mineral
composition of beans in a Cu-contaminated soil

Basic slag (BS) is an alkaline by-product of the steel industry with potential
properties to ameliorate nutrient supply and metal stabilization in contaminated soils.
The BS effects on soil pH, soil conductivity, growth and chemical composition of beans
were investigated using an acid, sandy soil from a wood treatment facility containing
630 mg Cu kg-1. Pot experiments were carried out on a 2-week period with Phaseolus
vulgaris L. An uncontaminated, sandy soil was used as a control (CTRL). BS was added
into the soil (1 kg soil/pot) to constitute four treatments in triplicates: 0 % (T1), 1 %
(T2), 2 % (T3) and 4 % (T4) BS/kg air-dried soil.

The results indicate that the soil pH, soil conductivity, and plant growth
increased compared to the untreated soil. The soil pH was increased from 5.6 in the
untreated soil up to 9.8 for the 4 % BS-amended soil. The soil conductivity rose from
0.14 mS/cm in the untreated soil to 0.38 mS/cm, 0.46 mS/cm, and 0.82 mS/cm in the
1%, 2%, and 4% BS-amended soils respectively. These increases in soil pH and EC in
all BS-amended soils likely resulted from the BS composition and in particular its high
Ca content. At 1 % and 2 % BS addition rate, highest shoot yields (dry weight, DW)
occurred. Foliar Cu concentration varied from 5.6 mg kg-1 to 53.1 mg kg-1 in the
treatments. The foliar Cu concentration likely caused a phytotoxic effect in plants
grown in the untreated, Cu-contaminated soil The highest decrease in the foliar Cu
concentration, 2.3 times was obtained for the T2 plant. BS addition at 1% rate into the
Cu-contaminated soil promoted beans growth with the lowest foliar Cu concentration.
Foliar Ca concentration was enhanced in the T2, T3 and T4 treatments whereas the
foliar P concentration was not promoted by the BS incorporation into the Cu-
contaminated soil. Instead, foliar K accumulation in primary leaves was restored up to
control level. Therefore this by-product was effective at 1% addition rate as a liming

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material but not as a P fertilizer in this short-term experiment. The BS incorporation in
the contaminated soil did not increase the foliar concentrations and accumulations for
Cd, Cr, and Zn.

4. In situ remediation of trace elements in chromated copper arsenate (CCA)-

contaminated soil using a basic slag phosphate (BSP)

Basic slag phosphate (BSP) which consists of calcium oxide, phosphorus oxide,
iron oxide and other metal oxides, is an alkaline by-product from the steel
manufacturing. BSP was used as a soil additive for improve physical and chemical soil
properties and for the in situ immobilisation of copper and other trace elements in a
chromated copper arsenate (CCA) contaminated soil to change the availability and
mobility of trace elements in soil and metal uptake by plants. The effect of BSP on soil
pH, soil conductivity, growth and biomass of beans plant were investigated using an
acid, sandy topsoil (0-25cm). The soil was strongly Cu-contaminated (630 mg Cu kg-1)
from a wood treatment facility using solutions of Cu sulphates and chromated copper
arsenate. The pot experiments was carried out with dwarf beans (Phaseolus vulgaris L.)
grown on the contaminated soil. BSP was added into the pots (1 kg soil) with four
different treatments in triplicates: 0 % (T1), 1 % (T2), 2 % (T3) and 4 % (T4) BSP/kg
air-dried soil. An uncontaminated, sandy soil was used as a control (CTRL). After a two
weeks period, soil and plant samples were collected to determine soil pH and EC,
growth and mineral analysis of plants. The mineralogical of clay and silt fractions of
soil treatments were also determined by X – ray powder diffraction analysis (XRD) to
identify the form of copper in soil.

The results show that BSP increased soil pH in relation with the addition rate,
from 5.7 in the untreated contaminated soil to 7.0, 7.4 and 7.9 in the soils amended at
1%, 2% and 4 % BSP addition rate respectively. The BSP incorporation increased the
soil electrical conductivity (EC) from 0.15 mS/cm in the contaminated soil to 0.47
mS/cm, 0.51 mS/cm and 1.17 mS/cm in the 1%, 2% and 4% BSP addition rate
respectively. All BSP addition rates to the copper contaminated soil increased the root
and shoot DW yield compared with the untreated contaminated soil (T1). The foliar Al
concentration decreased in plants from all BSP-amended soils. The foliar Ca

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concentration was enhanced in the all treatments BSP-amended soils whereas the foliar
Mg, K and P concentrations were not increased by the BSP addition. The foliar Cu
concentration decreased with the application of BSP for all treatments compared with
the untreated contaminated soil (T1). The foliar Cu concentration varied from 6.23 to
35.73 mg kg-1 DW with lowest and highest values for the CTRL and T1 treatments
respectively. This indicated that the beans plants were not able to grow on the excessive
copper contaminated soil (630mg/Kg). Similar results indicated that the Zn and Cr
availability decreased with the incorporation of the BSP into the soil. According to
these results, we conclude that the BSP addition at 2% and 4% rate incorporation into
copper contaminated soil promoted highest root and shoot DW yields with the highest
Ca concentrations and lowest foliar Cu concentration.

The mineralogical form of copper in soil fractions by XRD analysis indicated

that copper was detected in the form of cuprite (Cu2O), arsenic copper (AsCu9), and
plancheite (Cu2(CO3)(OH)2) in silt fraction contaminated soil (T1). While in the clay
fraction contaminated soil (T1) shows that copper and other trace elements such as As
and Cr were observed in the form of cuprite (Cu2O), arsenic copper (AsCu9), malachite
(Cu2(CO3)(OH)2), magnesium chromium oxide (MgCr2O4 ) and chromium arsenate
(CrAsO4). The stabilization of metals contaminated soil by amended soil does not
reduce the total content of contaminants but lower the amounts of mobile and
bioavailability of the fractions. According to changes the soil pH, the application of
BSP addition rate in copper contaminated soil (T1) can reduce copper mobility by
adsorption or precipitation on the BSP surface. The mechanism of copper removal using
BSP may be is precipitation with hydroxide dissolved from slag rather than adsorption
on slag surface. Thus, the presence of carbonate, silicate, oxy-hydroxides and phosphate
in the soil-BSP can form relatively insoluble complexes with metal ions and cause
metals to precipitate in their presence. Therefore, it seems that in all amended soil BSP
addition rate, copper was observed in the forms of silicate, carbonate and oxy-
hydroxides and complex precipitation with calcium, sodium, iron and phosphate in the
soil fractions. We conclude that the precipitation amount of copper was highly
depending on pH and slag compounds. These indicate that most of copper mobile was
precipitated on the surface slag causing by the compound of BSP in particularly the

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high Ca and P contents which able to make of it a potential liming agent to sorb and
precipitated metals in soil.

From all achieved results, it can be concluded that the soil studied is an acid
sandy soil with a low in organic matter, clay, and cations exchange capacity and a high
level of metals contaminated soil. Thus the application of alkaline materials such as
basic slag and basic slag phosphate in soil is promising tool for reduction the mobility
and bioavailability of trace elements contaminated soil by adsorption or precipitation on
the slag surface as well as for remediation of the soil to improve their physical, chemical
and mineralogical properties and also to improve plant production.

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 RÉSUMÉ

Nouvelle Technique Pour L'amélioration Et La Conservation Des Sols:

Stabilisation In Situ De Métaux Trace Dans Les Sols Contaminés

Les objectifs de cette étude étaient d'évaluer la phytoremédiation assistée dans le

cas de sols pollués par des métaux traces en plus ou moins forte teneur. Par
phytoremédiation assistée, il s’agit de coupler les capacités de remédiation offertes par
les plantes à celles d’un amendement de synthèse qui peut avoir un effet dual (sur la
pousse végétale en agissant comme un engrais mais aussi en adsorbant ou en
manifestant des capacités d’échanges entre le milieu et la matrice. L’étude a donc été
réalisée sur un site contaminé, en l’occurrence il s’agit d’une ancienne exploitation de
traitement de bois au Cuivre-Chrome-Arsenic (CCA) sur lequel différentes stratégies de
remédiation on été testées (Bes et Mench, 2008; Mench et Bes, 2009). Le traitement
CCA de type C est un produit à base d’oxyde de cuivre (11,1% w / w), trioxyde de
chrome (30% w / w), et de pentoxyde d'arsenic (19,9% w / w). Ainsi une partie de la
thèse a porté sur les caractéristiques géologiques, pédologiques et physico chimiques de
la zone contaminée d’une part, et d’autre part sur l’étude et le test de l’emploi
d’amendements inorganiques (matrice minérale) vis-à-vis d’un protocole de
phytoremédiation en vue de d’infirmer ou non l’intérêt de ce type d’apport pour aider à
la dépollution de sols contaminés par des éléments traces types métaux. Les
amendements testés sont tout deux des matrices minérales issues des coproduits de
l’industrie sidérurgique en l’occurrence des scories de laitiers. Le premier produit est
une scorie de base (BS) type scorie Thomas©, tandis que le second est un laitier de
centrale thermique qui a été soumis à un traitement de phosphatation en vue de le doper
en phosphates pouvant jouer un double rôle (BSP). Ce produit de synthèse ou matrice
duale doit en principe, du fait de sa richesse en minéraux phosphatés avoir un impact
positif sur la pousse végétale (engrais) mais aussi capter et intégrer dans son réseau
cristallin certains métaux traces ; améliorant ainsi l’efficacité du traitement par les

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plantes de sols pollués par des Métaux Traces (MT). Le couplage amendement et
plantes ayant un potentiel d’extraction et de fixation des métaux traces du sol dans leur
système végétatif est une alternative au traitement de type physique ou chimique pour
des sols contaminés. L’intérêt de la démarche de ce travail est d’aborder les aspects
caractérisations du site, des amendements et des plantes lors d’une campagne qui aura
duré un peu plus de trois ans. L’approche envisagée est originale en proposant
d’apporter un amendement, considéré comme un déchet de l’industrie « lourde », qui
pourrait avoir un aspect bénéfique pour la remédiation de sites pollués. Cela permettrait
de valoriser ce type de coproduits autrement qu’en tant que source potentiel de granulat.
Néanmoins et c’est une des grosses limites de cette étude, car si la phytoremédiation
assistée (scories Thomas) bénéficie d’un retour d’expérience de plusieurs dizaines
d’années, la durée de l’expérimentation avec nos laitiers phosphatés est trop courte pour
pouvoir conclure définitivement sur leur capacité duale (amendement et rétention des
MT). Il est nécessaire de poursuivre l’étude sur dix ans afin d’avoir un retour suffisant
sur la pérennité et la viabilité des espèces végétales se développant sur ce type de sols
pollués.

La thèse est divisée en chapitres dont le premier porte sur la pédologie du site, le
second sur la caractérisation des amendements type scorie, le troisième et quatrième
chapitre traitent respectivement des essais pour évaluer l’impact des deux amendements
testés, respectivement les scories de base (BS) et les scories phosphatés (BSP) vis-à-vis
de la contamination dans le sol mais aussi dans la plante test : Phaseolus vulgaris L. (ou
haricots). Le choix de cette plante a plusieurs raisons mais les principales sont ses
capacités à immobiliser des quantités de MT dans son système racinaire et aérien d’une
part mais aussi son cycle végétatif assez court qui permet de mesurer rapidement
l’évolution de la plante vis-à-vis des conditions expérimentales. L’ensemble des tests
ont été réalisés dans les règles de l’art en se référant lors de chaque campagne de tests à
un sol de contrôle (nommé control ou CTR) non contaminé, en l’occurrence un sol
sablonneux proche du point de vue pédologique du sol issu du site. Le plan
d’expérience est le suivant : constituer quatre traitements en triple exemplaire: 0% (T1),
1% (T2), 2% (T3) et de 4% (T4) BS / kg de sol séché à l'air.

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1. Caractéristiques du sol contaminé et distribution des métaux traces

L'objectif de cette recherche a été (1) d'étudier les propriétés physico-chimiques,

la pédologie d'un sol contaminé par le CCA et (2) d'identifier la répartition des métaux
traces du site en vue (3) d’évaluer les zones contaminées et notamment apprécier le
gradient vertical de la pollution par le CCA et son évolution en fonction de paramètres
comme la distribution granulométrique des particules, la matière organique, le pH du
sol et la capacité d'échange cationique. Ces paramètres sont connus pour être les
principaux facteurs pédologiques contrôlant la diffusion des métaux traces dans le sol.
Les résultats indiquent que les sols de la zone d'étude sont des sables limoneux à texture
grossière avec de faibles teneurs en matières fines (limon + argile). Il existe également
un peu de calcaire sous forme de carbonate de calcium avec des teneurs allant de 1,3 à
2,3 %. Les teneurs en Matières Organiques (MO) varient de 0,67 à 3,01% avec une
nette diminution avec la profondeur, de même que le pH variant de 4,04 à 7,11) et
diminuant avec la profondeur. Les sols fortement acides (pH 4.0-5.0) ont présenté de
fortes concentrations de métaux solubles. La Conductivité Electrique (CE) a varié de
0,02 à 0,44 dS/m. La capacité d'échange cationique (CEC) diminue avec la profondeur
(valeurs allant de 1 à 10,6 cmol/kg). La distribution des éléments traces indique une
abondance en ET tels que Cu (4,2 à 1970 mg/kg), Cr (10,9 à 114, 15), Zn (4 à 95.7), As
(1.9 à 51.1), Ni (5.22 à 14) et Co (1,66 à 4,81 mg/kg). L'accumulation de métaux
toxiques dans le sol est héritée de l’usage du site pour le traitement du bois par le CCA.
La distribution des métaux traces, suivant un gradient vertical dans le sol, n’est pas la
même pour tous les métaux. En effet, Cu, Cr, As et Zn augmentent dans la couche
superficielle du sol et diminuent ensuite en profondeur. En revanche, Co et Ni
diminuent dans la couche superficielle du sol et augmentent avec la profondeur. La
mobilité du cuivre dans le sol est contrôlée par différentes caractéristiques physico-
chimiques du sol comme le pH et la Force Ionique par exemple. En outre, le cuivre est
complexé avec la MO et est adsorbé à la surface de la fraction argileuse, influençant
fortement la mobilité et la biodisponibilité du Cu dans le sol (Adamo et al., 1996;
Chaignon et al., 2003; Sterckeman et al. , 2006).

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2. Caractérisation des scories utilisées comme technologie d'assainissement de sols
contaminés

Deux types d'échantillons de laitier : une scorie de base (BS) et un laitier

phosphaté (BSP), ont été utilisés comme amendement et ainsi assainir le site contaminé
par des Métaux Traces (MT). Cette partie vise à évaluer les propriétés chimiques et
minéralogiques des scories par plusieurs techniques d'analyse spectroscopique et
d’imagerie. La composition chimique a été déterminée par un spectrophotomètre
d'absorption atomique sur scorie dissoute dans l’acide et par microsonde électronique de
Castaing (EMPA) sur lame mince. La minéralogiques a été obtenue par diffraction des
rayons X (XRD) sur poudres et microscopie optique polarisante sur lame mince. Cette
approche couplant analyse spectroscopique statistique, et analyse directe et ponctuelle
(imagerie) permet de corréler et de valider les résultats obtenus d’une part mais aussi de
préciser la microstructure associée à la chimie locale des phases minérales. Cette
microstructure a été étudiée par microscopie électronique à balayage (MEB) couplée à
l'énergie dispersive (EDX).

Les résultats indiquent que les principaux composés de BS sont Ca (60,69% en

poids de CaO), Fe (14,61% en poids Fe2O3), Si (12,54% en poids de SiO2), Al (5,91
wt% Al2O3) et de Mg (2,51% en poids MgO). D’autres éléments comme Ti, Mn, P et K
sont présents à des teneurs pondérales (en poids d’oxydes) respectivement de 1,47, 1,06,
1,05 et 0,15 %. Comparée aux scories d'acier classiques qui sont principalement
composées des oxydes suivants: CaO, Fe2O3, SiO2, Al2O3, MgO, MnO et P2O5 (Cha et
al., 2006, Shen et Forssberg, 2003, Shi et Qians, 2000; Tossavainen et al., 2007;
Tsakiridis et al., 2008), notre matériau est appauvri en P. Cette composition se traduit
minéralogiquement par des cristaux d’opaques comme l’Ilménite, la Magnétite,
l’Hématite et la Limonite pour les formes oxydes mais aussi par de la Pyrite pour les
formes sulfures. Ils représentent environ 80% de l’ensemble des cristaux tandis que les
20% restants sont des microlites de Feldspaths (Plagioclase et Orthoclase), du Quartz,
des Grenats de la Calcite, quelques Rutiles et Tourmaline. L’ensemble est pris dans une
mésostase aphanitique majoritaire. Les XRD ont confirmé l’aspect cryptocristallin du
matériau avec comme phases identifiables sous forme de microcristaux
submillimétriques : Larnite, Wurstite, Brownmillerite, Calcite, Merwinite, Mayenite,

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Portlandite, Mélilite, Grossulaires, Imandrite et un composé d’oxyde de calcium et de
silice non identifié. Cet ensemble minéralogique rend compte de la chimie du matériau
de type calco-silicate riche en métaux traces mais aussi des conditions d’élaboration qui
sont de type haute température (>1400°C) et moyenne pression en condition plutôt
oxydante comme l’atteste la présence de Wurstite, de Brownmillérite, de Mélilite, de
Portlandite et du Grossulaire.

Les résultats obtenus par SEM/X-EDS et EPMA confirme que le matériau BS

est composé de Ca, Fe et Si pour 90% et le plus souvent sous forme d’une mésostase
aphanitique dans laquelle baigne des microcristaux calco-silicatés et des oxydes de fer
essentiellement, traduisant un refroidissement rapide. Il semble que l’ensemble des
éléments traces soient présents dans les formes cristallines comme l’atteste les
nombreux minéraux différents (Wurstite, Browmillérite, Méllilite, Grossulaire)
observés par XRD, MO et SEM. En revanche, la phase amorphe est calco-silicatée et
plus ou moins riche en Fe. Cet ensemble de caractéristiques rapproche ce type de laitiers
BS d’une scorie Thomas fortement appauvrie en P mais riche en métaux. A priori cette
composition peut être un handicap pour leur utilisation en tant qu’amendement sur des
sols de sites pollués par des métaux traces. Néanmoins le fait que les métaux traces
soient inclus dans le système cristallin des phases cristallisées réduit fortement
l’hypothèse d’un transfert depuis la matrice BS vers le sol, et a fortiori l’existence d’une
phase aphanitique riche en Fe permet d’envisager soit un piégeage des métaux traces du
sol par cette phase par le biais des oxydes de Fe ou la capacité supposée et espérée de
l’inertage des MT par la phase cryptocristalline selon le schéma suivant (* mésostase
amorphe).

*[Fev, Six,Aly]0z + H2O *[Six,Aly]0z + (FeO, FeOH2)

(FeO, FeOH2) + MT (Fe0w, MTx) + (FeOH2)MTy
*[Six,Aly]0z + MT *[Six,Aly, MTu]0z par adsorption

Ce matériau dérivé de BS est enrichie en phosphore (par réaction de

phosphatation en milieu acide). Les résultats de l’analyse chimique montrent
effectivement que la composition chimique de BSP est Ca (30,71 wt % CaO), Fe (21,4

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wt % Fe2O3), Si (14,63 wt % SiO2), P (14 wt % P2O5), Mg (9,55 wt % MgO), Al (5,56
wt % Al2O3), Mn (2,53 wt % MnO2) et quelques traces de Ti et K (1,09 wt% TiO2 et
0,53 wt% de K2O). Comparativement à BS, BSP est enrichie en P et se traduit du point
de vue minéralogique en microscopie optique polarisante par la présence de Zircons et
d’Epidotes (non observés dans BS) et bien sur par des minéraux phosphatés pris dans
une mésostase aphanitique. On retrouve les microlites de Feldspaths, de Quartz, des
Grenats, de la Calcite, du Rutile et des Tourmalines. Les DRX ont permis d’identifier
du phosphate de calcium, du phosphate hydrogéné de titane, de la whitlockite associée à
des phases de rodolicoïte, des silicates de calcium et des oxydes calco–alumino- ferreux.
L’analyse SEM/X-EDS et par EPMA de la mésostase montre que sa composition est à
plus de 95% (masse pondérale) formée de Ca, P, Fe et Si confirmant donc
l’enrichissement net en P comparé au laitier BS. Les éléments Mn, K, Mg et Al ont été
identifiés mais à de faibles teneurs de l’ordre du pourcent. La présence de minéraux
phosphatés sub- millimétriques dans BSP permet d’envisager une double action vis-à-
vis de sols pollués par des MT. En effet, ces minéraux phosphatés vont participer à
l’apport en nutriment phosphoré pour le sol mais sont connus comme étant d’excellents
capteurs de MT lors des réactions d’hydrolyse (Pierzynski and Schwab, 1993; Mench et
al., 1994a, b; Mench et al., 1998 ; Hettiarachchi et al., 2001 ; Wang et al., 2001; Liu
and Zhao, 2007 ; Bes and Mench, 2008). On peut donc attendre, lors de l’apport de
quelques pourcents (de 2% à 10% pondéral par kilogramme de sol) de laitier BSP broyé
sur les parcelles une meilleure pousse végétale tout en observant une décroissante des
teneurs en MT dans le sol mais aussi au niveau de la plante. C’est ce que ce travail doit
mettre en évidence c'est-à-dire l’effet dual de la matrice de laitier enrichie en P.

3. Effet des scories de base sur le sol et la mobilité des métaux traces du site pollué

Cette étude vise à enquêter sur l’intérêt ou non (aspect positif) d’amender un sol
contaminé par une pollution de type CCA. Le seul ajout d’un amendement ne suffisant
pas bien sur à dépolluer un sol contaminé par des MT, mais associé à une stratégie de
phytoremédiation, l’apport de scories (BS et BSP) peut modifier certains paramètres
pédologiques et contribuer ainsi au succès (rendement de phytoremédiation amélioré ou
pas). Il permet aussi de vérifier si l’apport de scorie peut également abaisser le cortège

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des métaux traces labiles (fraction mobile) par sa seule présence. Il sera alors possible
de considérer un double effet de l’apport de scorie sur un site pollué. Cet apport joue sur
certaines caractéristiques du sol telles que le pH et la conductivité électrique (CE) et
donc sur la mobilité potentielle du pool de métaux labiles du sol et captés par la plante
(analyse des racines et du cortex supérieure de la plante (tige et feuille). De plus, il est
important de réduire ce pool labile de MT au niveau de l’environnement proche de la
rhizosphère (réseau racinaire du sol) afin de minimiser le transfert depuis ce système
vers les tiges de la plante (type haricot dans nos tests). Les expériences en pots ont été
réalisées sur une période de deux semaines avec Phaseolus vulgaris (plants de haricots).
Un sol sablonneux a été utilisé comme contrôle (CTRL). Sur une série de quatre
traitements (en triple) en pots de 1 kg de sol chacun, nous avons ajouté le laitier BS à
raison de : 0% (T1), 1% (T2), 2% (T3) et de 4% (T4) BS / kg de sol séché à l’air. Le
pH, la CE, la croissance des plantes, la production de biomasse foliaire et les
concentrations des éléments nutritifs et les métaux traces dans les feuilles primaires ont
été suivis. Les résultats indiquent que l'incorporation de BS dans le sol se traduit par une
augmentation du pH tout comme de la CE. Cette augmentation est la conséquence de la
nature alcaline des scories qui se dissolvent en partie dans le sol assurant leur fonction
d’amendement. L'effet de BS sur la biomasse des feuilles primaires des haricots varient
selon les traitements. Si la croissance végétative est maintenue dans ce contexte de sol
pollué pour certains tests, la répartition des MT dans les haricots suivant les tests sont
complexes, traduisant des mécanismes antagonistes entre éléments. De manière
générale, l’apport de BS (au taux de chaulage de 1% pondéral) se traduit par une
augmentation de la concentration du Cu dans les extrémités foliaires sans impact
notable sur les concentrations de métaux tels que Cd, Cr, et Zn. Il y a là une sélectivité
des MT traduisant une sorte de spéciation biologique complexe ou affinité sélective de
la plante vis d’un cortège de MT présent dans un sol, qui reste à étudier sur le long
terme.

4. Effet de l'ajout de base de phosphate de scories sur les métaux trace dans un sol
contaminé

Dans cette étude, un laitier d’aciérie a été enrichi en phosphate (BSP) et testé
comme adjuvant ou amendement pour l’assainissement de sols contaminé par des MT

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(issus du traitement au CCA). Les objectifs de cette étude étaient les suivants: (1)
évaluer l'influence de BSP sur les fonctions pédologiques du sol (pH et la CE), (2)
évaluer l'effet de BSP sur le rendement végétatif des plantes tests et (3) déterminer le
potentiel de BSP pour réduire le cuivre et les autres métaux traces dans le sol. Les
résultats montrent que l’apport de BSP augmente le pH du sol de 5,7 à 7,9, ainsi que la
conductivité électrique (CE) de 0,15 mS/cm à 1.17 mS/cm. Les plants de haricots ne
sont pas en mesure de se développer dans des sols contaminés par de fortes teneurs en
Cu comme par exemple celui ou des teneurs de plus de 630mg/Kg ont été mesurées,
même si l’apport de BSP induit une baisse de la teneur en Cu dans le sol et une
augmentation dans la masse foliaire. Des résultats similaires ont été observés pour le Zn
et Cr labile et dont les teneurs dans le sol ont diminué avec l'apport de BSP. Les fortes
teneurs en Cu dans le sol se traduisent par la précipitation, en milieu pédologique
légèrement acide, de phases minérales telles que la cuprite (Cu2O), associée à l’arsenic
de cuivre (AsCu9), la planchéite [Cu2 (CO3) (OH)2], la malachite [Cu2 (CO3) (OH)2]
comme l’ont démontré les analyses par DRX. Lorsque les teneurs en CCA sont
importantes (certaines zones sur le terrain), le chrome peut également précipiter pour
donner des oxydes type oxyde de chrome magnésium (MgCr2O4) et d'arséniate de
chrome (CrAsO4). La répartition de ces phases dans le sol contaminé est complexe.
Ainsi dans le cas du test T1 (sol contaminé sans apport d’amendement), la distribution
de phases néoformées est fonction de la minéralogie du sol et l’on ne trouve pas tout à
fait les mêmes formes entre les fractions argileuses et silteuses. L’apport de BSP sur le
sol contaminé se traduit par un changement de pH et de la CE qui affecte la mobilité du
cuivre labile. Ce dernier se retrouve ainsi précipité ou adsorbé à la surface du laitiers
BSP broyé. Ainsi le Cu, quel que soit la teneur en BSP, se retrouve, au niveau de la
fraction silteuse sous frome de cuprite (Cu2O), d’arsenic de cuivre (AsCu9), associés
avec les carbonate et les oxy-hydroxydes sous forme d’azurite [Cu3 (CO3)2(OH)2], avec
les silicates tels que la planchéïte (Cu3SiO3.H2O), mais également sous forme de
complexe de fer et de phosphate tel que le chloro phosphate hydro-nitrogéné de
[Cu4.72H3.2(P12N18O6)Cl2], l’hentschélite [CuFe3+2(PO4)2(OH)2] et de phosphate d’oxyde
de cuivre [Cu4O(PO4)]. Dans la fraction argileuse les formes observées en DRX sont
similaires avec l’existence d’un plus grand nombre de variétés comme la malachite
[Cu2(CO3)(OH)2], la pseudomalachite [Cu5(PO4)2(OH)4], le phosphate de cuivre nickel

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[Cu Ni2(PO4)2], le phosphate hydrogéné de cuivre calcium (Ca Cu HPO4), ou bien
l’oxyde de calcium cuivre titane (CaCu3Ti4O12). Ces phases minéralogiques rendent
compte des mécanismes chimiques complexes et variés qui se produisent à l’interface
sol contaminé et amendement BSP. Ces résultats confirment que la plupart du Cu labile,
du Cr labile et de l’As labile précipite à la surface de l’amendement par sorption ou co-
précipitation associée au Ca et au P (apportés par l’amendement).

Conclusion

De tous les résultats obtenus, il peut être conclu que l’apport d’un amendement
alcalin comme les scories de base ou d’un laitier phosphaté dans un sol sablo limoneux
aquitain contaminé par des métaux traces issus d’activités industrielles de traitement du
bois par imprégnation au Cuivre Chrome Arsenic (CCA) est intéressant. Cet
amendement est un outil prometteur pour la réduction de la mobilité et la
biodisponibilité des métaux traces (MT) des sols contaminés. Les mécanismes qui
contrôlent cette baisse des teneurs en MT sont des réactions d’adsorption-précipitation
de phases minérales riches en MT. Elles se traduisent par la précipitation de phases
minérales néoformées en surface des scories. La présence de phosphates sous forme de
minéraux submillimétriques dans les scories semble améliorer ces réactions. Les teneurs
en MT sur le site étudié sont à certains endroits (tâches de léopard sur le site) tellement
élevées que l’on observe des formes minéralisés - comme la Cuprite, la Malachite, des
Arséno-cuivre, des oxydes de chrome – révélant donc des mécanismes de précipitation
et de croissance cristalline suffisants pour être détectées en DRX. La présence de ces
phases minérales traduit que le traitement par le CCA de bois conduit à des teneurs
telles que les capacités pédologiques d’un sol sont fortement dégradées et conduisent
par la rémanence des apports à une sur-saturation en MT (Cu, Cr et As) qui avec le
temps va conduire à ces précipitations. Cependant, aux échelles de temps auxquels le
site est confronté (activité industrielle sur un demi-siècle) il est étonnant de trouver ces
minéraux. Cela suppose que d’une part les résidus de CCA sont faiblement mobiles
suivant le gradient vertical, ce qui est étonnant sur ce type de sol (grave sablo limoneuse
à faible horizon humique) connu pour leur capacité drainante. Mais d’autre part, le

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passage de MT labile sous forme d’oxydes, d’hydroxydes traduit une activité
bactérienne capable de catalyser les réactions minéralogiques conduisant à la
précipitation de ces phases. En effet les seuls mécanismes physico chimiques sont
insuffisants, étant donné l’échelle de temps, pour générer des phases cristallisés. Les
cinétiques chimiques, sur la base d’une approche classique (équation d’Arhénius, de
Fick) ou plus récente (Lasaga & al), ne peuvent à elles seules expliquer la nucléation et
la croissance cristalline. Il est donc nécessaire d’évoquer des réactions biologiques
(activité bactérienne par exemple) pour obtenir de tels cristaux comme pour les lixiviats
de déchets miniers par exemple où l’on observe des minéraux néoformés en présence de
bactéries (Exemple du site de Rio Tinto en Espagne ou de Carnoulès en France). Il
faudrait donc pouvoir continuer sur de plus longues périodes ce type d’approche de
phytoremédiation assistée par des matrices minérales issues de l’industrie sidérurgique
pour valider le procédé. Les essais sont en cours et devront permettre de valider ou
d’invalider les premières conclusions de ce travail.

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 Appendixes

Appendix 1: EPMA analysis composition of BS and BSP

Elements BS BS BS BS BSP BSP BSP BSP
(wt. %) (1) (2) (3) (4) (1) (2) (3) (4)
Al 3.76 1.54 0.16 0.22 0.29 6.31 0.33 0.62
Ca 20.91 31.78 8.44 5.45 34.95 28.77 3.51 23.17
Cr 0.04 0 0 0 0 0.41 0 0.11
Fe 37.36 6.6 3.08 11.27 2.72 33.05 1.27 14.55
Mg 2.37 1.48 0.77 4.48 0.06 2.35 0.15 0.05
Mn 3.45 2.8 0 1.02 0.02 1.52 0.43 0.77
P 0 0.23 0.28 0 10.23 0 0 1.62
Si 1.7 11.49 1.13 4.18 3.71 17.01 0.9 1.84
Ti 0.04 0.16 0 0 0.06 3.26 0 0.89
C 6.77 18.32 64.46 62.4 11.83 0.41 83.54 3.13
O 23.6 25.6 21.68 10.98 36.11 6.71 9.87 53.25
Total 100 100 100 100 100 100 100 100

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Appendix 2: Elemental distribution of BS and BSP by EPMA analysis

BS BSP

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BS BSP

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BS BSP

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 SCIENTIFIC DISSEMINATION

Communications
1- Negim, O., Eloifi, B., Mench, M., Le Coustumer, P. “Phytoremediation assisted
dual matrix for stressed soil (hydrous and trace elements contamination type)” - Poster.
Pnetox, Colloque De Restitution Du Programme National d’Ecotoxicologie. Lille, 13-
14 Octobre 2008.
2- Negim, O., Eloifi, B., Mench, M., Bes, C., Le Coustumer, P. “Effects of Basic
Slags on Soil Properties and Plant Biomass in a Trace Element-Contaminated Soil.
Environmental Technologies-Sediment and Landfills.” (ECOR-5, EC-DNAPL-3 and
EC-RSSG-1), Amsterdam October 21-23, 2008.
3- Negim, O., Mench, M., Motelica-Heino, M., Guegan, R., Le Coustumer, P. “In
Situ Remediation of Trace Metals in a Cu-Contaminated Soil by Addition of Basic Slag
Phosphate”. The Second International Environmental Best Practices Conference.
Cracow, Poland (Septembre 2009)
Articles
1- Negim O., Eloifi B., Mench M., Bes C., Gaste H., Motelica-Heino M., Le
Coustumer P. 2009. “Effect of basic slag addition on soil properties, growth and leaf
mineral composition of beans in a Cu-contaminated soil.” International Journal of Soil
and Sediment Contamination. (BSSC-2009-0044.R1).
2- Negim O., Eloifi B., Mench M., Bes C., Motelica-Heino M., Le Coustumer P. “In
situ remediation of trace metals in chromated copper arsenate (CCA)-contaminated soil
using basic slag phosphate”. International Journal of Soil and Sediment Contamination
(accepted, under revision, 2009)
3- Negim O., Mench, M., Motelica-Heino M., Fabre R., Gauthier A., Le
Coustumer, P. “Physico-chemical soil properties and trace elements distribution in
contaminated soil”. International Journal of Soil and Sediment Contamination (Submit
2009).
4- Negim O., Amin F., Huneau F., Motelica-Heino M., Le Coustumer, P. “Slag
characteristics used as an alternative technology for copper contaminated soil
remediation” .Waste Journal (Submit 2009).

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