Elaboration et caractérisation d’une membrane d’ultrafiltration à base

d’un coproduit de l’industrie de la transformation des phosphates

Mouna khemakhem, Sabeur Khemakhem and Raja Ben Amar

Laboratoire des Sciences de Matériaux et Environnement, Université de Sfax, Faculté des Sciences de Sfax,
Route de Soukra Km 4, Sfax, Tunisie.

Résumé- Au cours de ce travail, de nouvelles membranes d’ultrafiltration ont été élaborés à base de la boue de
l’hydrocyclonage des laveries des phosphates. Les supports tubulaires ont été obtenus par extrusion d’une pâte
obtenue après optimisation de sa composition en termes d’ajout d’additifs organiques et de poudre de boue. Ils
ont été consolidés par frittage à 900°C. Ces derniers possèdent une bonne tenue mécanique et chimique. Une
membrane d’ultrafiltration en boue d’épaisseur 12 µm et dont le diamètre de pores présente une distribution
autour de 10.57 nm a été déposée sur le support élaboré. Le dépôt est réalisé par la technique classique de
coulage d'une suspension de poudre de boue, puis consolidée par traitement thermique à 650°C. Pour la
caractérisation dynamique de la membrane, la perméabilité à l’eau a été déterminée.

1. Introduction

Les membranes minérales présentent plusieurs avantages par rapport aux membranes organiques. Elles ont très
bonne tenue chimique et une excellente inertie vis à vis des solvants organiques et des milieux corrosifs. La
plupart de ces membranes sont préparées à partir d’oxyde de titane, d’alumine ou de zircone [1,2]. Cependant le
prix de revient de ces membranes reste très important par rapport à celui des membranes organiques. Depuis
quelques années, des membranes inorganiques à base de matériaux naturels (argile, apatite, carbone…) ont été
développées dans un souci de réduire le coût des membranes céramiques. La boue de l’hydrocyclonage des
laveries des phosphates est un matériau naturel très abondant issu d’un lavage de roches de phosphates à l’état
naturelle afin d’éliminer les marnes et les composés inertes, des déchets siliceux et sous forme de calcaire. Cette
boue peut être valorisée dans la fabrication de membranes en céramique.

2. Elaboration et caractérisation de nouveaux supports à base de boue

de l’hydrocyclonage des laveries des phosphates

L’élaboration d’une céramique macroporeuse se réalise par façonnage d’une poudre fine, suivi de la
consolidation par frittage. Le procédé d’élaboration est décrit dans la figure1. La poudre broyéee é été tamisée à
l’aide d’un tamis de 250µm. L’ajout des liants et les plastifiants (méthocel, amijei) confèrent à la pate les
propriétés de plasticité permettant la mise en forme. L’agent de porosité (amidon) est introduit afin d’augmenter
le volume poreux. La composition de la pate a été optimisée pour permettre une bonne mise en forme [4].

1
 FiG 1- Différentes étapes d’élaboration d’une céramique poreuse

*Méthocel ( The Dow Chemical company), est un dérivé cellulosique contenant de 20 à 25 % de groupements
méthyl et de 10 à 15% de groupements hydroxypropyl.
*Amijel ( Cplus 12072, Cerestar), est un produit dérivé constitué d’amidon prégélifié.
*Agent de porosité: amidon de maïs RG 03408, Cerestar.
2.1. Résistance mécanique

La figure 2 représente l’évolution de la valeur du module de la contrainte à la rupture (σ) en flexion trois points
en fonction de la température de frittage.

25

20
Cont FL 3 Pts (MPa)

15

10

0
700 750 800 850 900 950 1000 1050 1100
2 (°C)
Température
 Fig 2- Evolution des valeurs du module de la contrainte à la rupture (σen flexion trois points en fonction de la
température

On remarque l’augmentation du module de la contrainte à la rupture (σ) en flexion trois points en

fonction de la température de frittage de 9.8 MPa à 800 °C vers 22.9 MPa à 1000 °C. , ce qui traduit une
augmentation progressive de la résistance mécanique du matériau.

2.2.Caractérisation par porosimètrie à mercure

Le support obtenu après extrusion à base la boue de l’hydrocyclonade des laveries des phosphates possède une
bonne tenue mécanique et chimique [3]. La température optimale de 900°C donne des supports de diamètre
moyen de pores de 1.07µm. Ce résultat est affirmé par la courbe d’intrusion différentielle en fonction de
diamètre de pore suivante (figure3) :

0,5
0,45
0,4
Log Différentiel intrusion (ml/g)

0,35
0,3
0,25
0,2
0,15
0,1
0,05
0
1000 100 10 1 0,1 0,01 0,001
Diamètre des pores (µm)

FIG.3-Répartition des diamètres de pores du support tubulaire élaboré à partir de la formulation optimisée et
fritté à 900°C.

2.2. Analyse par microscopie électronique À balayage

L’observation au microscope électronique à balayage nous affirme aisément que l’aspect de

surface du support élaboré à base de boue de l’hydrocyclonage est homogène, ainsi la distribution des
diamètres des pores et du volume poreux est bien symétrique comme l’indique la figure 4.

3
 Vue en coupe Surface

FIG.4- Morphologie de support élaboré et fritté à 900°C.

3. Elaboration et caractérisation d’une membrane d’ultrafiltration

symètrique à base de la boue

La membrane en boue est réalisée par la technique de coulage de barbotine dans laquelle la force motrice du
dépôt de matière est la succion capillaire du support (figure 5). La barbotine est constituée d'une poudre de boue
dispersée dans une solution aqueuse à laquelle on ajoute une solution de polymère permettant à la fois de
contrôler la viscosité et de servir de liant organique. La formulation d’une barbotine à caractéristique finale est
représentée comme suit :

30% d’APV
65% d’eau
5% de boue de l’hydrocyclonage de laveries des phosphates tamisé à 63µm.
Le processus d'enduction est caractérisé par le temps de contact entre la barbotine ; le temps t = 0 correspond à la
fin du remplissage du tube. Le temps de contact suivit dans notre cas est 5min chaque (remplissage/ vidange),
puis laisser 24 heures temps de séchage.

4
 FIG 5- Schéma explicatif du procédé de Slip Casting

3.1. Analyse par MEB

L’observation de la morphologie et de l’état de surface de la couche mince d’ultrafiltration par microscope

électronique à balayage (figure 6), nous montre une céramique bien homogène et dense de surface bien fermée
pour la température de 650°C. L’épaisseur de la couche est de l’ordre de 12µm. On peut noter également une
excellente adhérence de la membrane sur le support.

650°C 650°C

FIG.6- Etude de la texture par M.E.B de la couche d’ultrafiltration à base de la boue de l’hydrocyclonage de
laverie de phosphates.

3.2. Porosimètrie à mercure

La figure 7 donne la répartition des diamètres de pores obtenue pour la couche frittée à 650 °C.

5
 FIG.7- Répartition des diamètres de pores mesurés par porosimétrie à mercure de la membrane boue /boue
frittée à650°C.

3.3. Test de filtration

Le test de filtrationa été effectué sur un pilote de filtration tangentielle. Pour obtenir une stabilité rapide du flux
de perméation, les membranes sont immergées dans l’eau pendant 24 heures qui précèdent la filtration. Le flux
de perméation en fonction du temps pour notre membrane se stabilise au bout de 15 min (figure8).

600 600
1 bar
500 P=2 500
P=3
400 P=4 400
Flux (L/h m2)

Flux (L/h m2)

300 P=5 300

P=6
200 P=7 200
P=8
100 100

0 0
0 20 40 60 80 0 5 10
Temps (min) Pression (bar)

FIG.8- Evolution du flux (l/h.m2) en fonction du temps et de la pression.

La pente de la droite (Evolution du flux (l/h.m2) en fonction de la pression nous indique la valeur de perméabilité
est environ 100 l/h.m2.

6
Références

[1] G.E. Romanos, Th. Steriotis, A. Kikkinides, E.S. Kanellopoulos, N.K. Kasseelouri, J.D.F. Ramsay , P.
Langlois, S. Kallus., Innovative methods for preparation and testing of Al 2 O 3 supported silicalite-l membranes,
J. Eur. Ceram. Soc. 21 (2001) 119-126.
[2] R.F.S. Lenza, W.L. Vasconcelos, Synthesis and properties of microporous sol–gel silica membranes, J. Non-
Cryst. Solids 273 (2000) 164.
[3] T.V. Gestel, C. Vandecasteele, A. Buekenhoudt, C. Dotremont, J. Luyten, R. Leysen, et al., Alumina and
titania multilayer membranes for nanofiltration: preparation, characterization and chemical stability, J. Membr.
Sci. 207 (2002) 73-89.
[4] M. Khemakhem, S. Khemakhem, S. Ayedi, R. Ben Amar, Study of ceramic ultrafiltration membrane support
based on phosphate industry subproduct: application for the cuttlefish conditioning effluents treatment. Ceramics
International, 37 (2011) 3617-3625.

Summary
The development and the characterisation of a new ultrafiltration membrane based on the mud of the
hydrocyclone laundries of phosphate are presented. The choice of this material is based primarily on its low cost.
The elaboration of the mesoporous layer was performed by the slip-casting method using a suspension made of
the mixture of the mud powder, water and polyvinyl alcohol (PVA). The obtained membrane was submitted to a
thermal treatment which consists in drying at room temperature for 24 h then a sintering at 650° C.
SEM photographs indicated that the membrane surface was homogeneous and did not present any macrodefects
The average pore diameter of the active layer was 10.57 nm and the thickness was around 12µm. The membrane
permeability was 96 l/h.m2 bar.

7
EFFICIENT DEGRADATION OF CONGO RED OVER CuBi 2 O 4 /SnO 2 NANOCRYSTALLINE
HETEROJUNCTION PHOTOCATALYST UNDER UVA LIGHT IRRADIATION

A. Elaziouti 1,2*, N. Laouedj 1,2 , A. Bekka2 and RN. Vannier3.

1 1*
Dr. Moulay Tahar University, Saida, Algeria E-mail : elaziouti_a@yahoo.com
2*
LCMIA Laboratory of Inorganic Materials Chemistry and Application, University of the Science and
the technology of Oran (USTO M.B). BP 1505 El M’naouar 31000 Oran, Algeria.
2
E-mail : bekka_ahmed@yahoo.com
1
Email : nlaouedj@yahoo.fr
Unit of Catalysis and Solid State Chemistry of Lille University. Cité Scientifique, Bâtiment C7 Avenue
Mendeleïev, B.P. 90108, F-59652 Villeneuve d’Ascq, Lille, France.
3
Email: rose-noelle.vannier@ensc-lille.fr

ABSTRACT. A novel p-CuBi 2 O 4 /n-SnO 2 nanocrystalline heterojunction photocatalyst has been

successfully synthesized by the solid state technique. The as-synthesized catalyst was characterized by X-
ray diffraction, scanning electron microscopy and UV–Vis diffuse reflectance spectroscopy. The results
showed that p-CuBi 2 O 4 /n-SnO 2 nanocomposite catalyst exhibited strong photocatalytic activity as
compared with precursor’s compounds. The photodegradation reactions were satisfactory correlated
with the pseudo-first-order kinetic model. The optimum amount of doped CuBi 2 O 4 was 05 wt % as a
result of 58.06% of photoactivity for decomposition of Congo red within 100 min under UVA irradiation
at pH=8 and 25°C. On the basis of the calculated energy band positions, the mechanism of the increased
photocatalytic activity was discussed by the p–n heterojunction charge separation model and the valance
band theory.

RESUME. Un nouveau photocatalyseur nanocrystalline de jonction hétérogène p-CuBi 2 O 4 /n-SnO 2 a

été synthétisé avec succès par la voie des réctions à l'état solide. Le catalyseur synthétisé a été
caractérisé par diffraction des rayons X, la microscopie électronique à balayage et spectroscopie UV-
Visible en réflexion diffuse. Les résultats ont montré que le catalyseur nanocomposite p-CuBi 2 O 4 /n-
SnO 2 présente une excellente activité photocatalytique par rapport aux composants précurseurs. Les
réactions de photodégradation ont parfaitement décrit le modèle cinétique de pseudo-premier ordre. Une
activité maximale est enregistrée pour 5% CuBi 2 O 4 , résultat de 58,06 % de dégradation de rouge Congo
au bout de 100 min sous irradiation UVA à pH 8 et 25°C. Sur la base des positions des bandes d'énergie
mesurées, le mécanisme d’augmentation de l'activité photocatalytique a été examinée parle modèle de
séparation des charges dans l'hétérojonction et la théorie de la bande de valence .

KEY WORD: CuBi 2 O 4 /SnO 2 photocatalyst, p–n heterojunction, Congo red, photocatalytic activity,
band theory, synergy effect.

MOTS-CLÉS: Photocatalyseur CuBi 2 O 4 /SnO 2 , hétérojonction p/n, rouge Congo, activité

photocatalytique, théorie des bandes, effet synergique.

1
1. Introduction

Advanced oxidation processes are of great scientific and practical interest in terms of ecology and
sustainable development (Fujishima, 1972; Zhang and Zhu, 2005). The heterogeneous photocatalysis of
organic pollutants on semiconductor surfaces has attracted much attention as a ‘green’ technique. Most
researches consider heterogenic systems based on TiO 2 (Degussa P25, Hombriat UV-100, Aldrich, etc.)
owing to their high photocatalytic activity and stability as well as their widespread uses for large-scale
water treatment (Wang et al., 2006). However, the intrinsic band gap of TiO 2 is 3.2 eV, which requires
the excitation wavelength longer than 387.5 nm. It is a major disadvantage of TiO 2 using as a
photocatalyst working under visible light (≥420 nm). The high rate of electron-hole recombination often
results in a low quantum yield and poor efficiency of photocatalytic reactions. Therefore, to develop
highly efficient, non toxic and chemically stable photocatalyst under visible light irradiation is required.
SnO 2 , with a wide band gap of 3.6 eV at 300K (Derbal et al., 2008), is known as n-type semiconductor
and exhibits excellent optical, electrical and chemical properties and high thermal stability. Research has
shown that the semiconductor SnO 2 material has wide potential applicability such as solid-state gas
sensors (Ying et al., 2004) , transparent conducting electrodes (Chopra et al., 1983) , rechargeable Li
batteries and optical electronic devices ( Aoki and Sasakura, 1970) . The tin dioxide (SnO 2 ) has low cost
and toxicity, in addition to high availability. This oxide is among the few with the band gap energy near
to visible light (Yang et al., 2006; Zhang et al., 2006). During the past decade, SnO 2 nanostructures have
been one of the most important oxide nanostructures due to their properties and potential application
(Cheng et al., 2004) . Recently its composites have been studied as promising semiconductors in the
photocatalytic decolouration of wastewaters (Xi et al., 2008; Wang et al., 2006; Nayral et al., 2000;
Mukhpadhyay et al., 2000; Teeramongkonrasmee and Sriyudthsak, 2000). Although photocatalytic
activity of SnO 2 has intensively been investigated, the broad band gap energy and the electronic potential
position in the conductance and valence bands of this material seriously limit its further application as a
photocatalyst utilizing solar energy (Li et al., 2009).
Various strategies in liquid-phase system have been adopted for size-controlled synthesis of various
functional nanomaterials, including transition metals doping (Couselo et al., 2008), noble metals
deposition (Sasahara et al. 2006) doping non-metallic elements (Geng et al., 2008), doping transition
metals surface photosensitization (Mora-Sero et al., 2007) and coupled polycrystallites or colloidal
semiconductors ( Bian et al., 2008) . Thus, the combination of semiconductor has become hot topic
among researchers in the last decade to improve the photostimulated electron-hole separation and
effectively inhibits their recombination. The major characteristic of this technique is to assemble a
heterojunction interface between wide and narrow band gap semiconductors with matching energy band
potentials. In this way, electric field assisted transportation of charges from one particle to the other
through interfaces is favorable for the electron–hole separations in the composite materials, and thus the
electron and hole could transfer from catalyst to adsorbed substrate can be obtained ( Li and Yan, 2009;
Liu et al., 2010). The extensive search published on n-n type junction semiconductors systems were
mostly focused on SnO 2 -based photocatalyst materials, such as ZnO /SnO 2 ( Wang et al., 2002),
Fe 2 O 3 /SnO 2 , (Zhuang et al., 2008), SrNb 2 O 6 /SnO 2 (Xinping et al., 2008), TiO 2 -SnO 2 /Fe+3 (Sikong et
al., 2010), Ag 3 PO 4 /SnO 2 (Zhang et al., 2011), RGO/SnO 2 (Zhang et al., 2012), Nb 6 O 17 /SnO 2 (Wang et
al., 2010), TiO 2 /SnO 2 ( Hou et al., 2007; Sasikala et al., 2009 ), CeO 2 /SnO 2 (Foletto et al., 2012),
Cr 2 O 3 /SnO 2 (Bhosale et al., 2013), and so on. The results showed that nearly all the n–n junction
composite semiconductors exhibited better photocatalytic properties than single ones. However, to the
best of our knowledge, the use of the p–n type composite semiconductors has been rarely reported in the
literature and only few examples of the p–n junction photocatalysts, such as CuO/SnO 2 (Xia et al.,
2007), CuFeO 2 /SnO 2 (Derbal et al., 2008), n-SnO 2 nanorodes /p-Si (Yang et al., 2009; Wang et al.
2010; Mohamed et al., 2012), have been studied. Theoretically, when p-type semiconductor and n-type
semiconductor are connected to each other, the p-n heterojunction composite semiconductors will be
formed; the inner electric field will also be produced in the interface. Once optical excitation occurs, a
free electron (e-) and an electronic vacancy-a hole (h+) are formed, separate and migrate effectively in a
semiconductor being partially localized on structural defective centers of its crystalline lattice, hence
improving the electrical properties of semiconductor.

2
 So, the aim of this study is to clarify the photocatalytic efficiency of this novel p–n type composite
semiconductor p-CuBi 2 O 4 /n-SnO 2 prepared by a physical mixing process through doping CuBi 2 O 4 into
SnO 2 matrix. The as-prepared p-CuBi 2 O 4 /n-SnO 2 nanoparticles were characterized by a number of
techniques such as X-ray diffraction, scanning electron microscopy and UV–visible diffuse reflectance
spectroscopy. The photocatalytic degradation of Congo red (CR) dye under UV light irradiation was
investigated over nanosized photocatalyst p-CuBi 2 O 4 /n-SnO 2 at different operating parameters such as,
reaction time and the amount of doped CuBi 2 O 4 . The experimental data were quantified by applying the
pseudo-first order kinetic model. The mechanisms of the increase in the photocatalytic activity were also
discussed through the p–n junction principle and the valance band theory.

1. Experimental

1.1. Materials

The starting materials used in the synthesis: α-Bi 2 O 3 (99.99%), CuO (99.99%) and SnO 2 (99.99%)
were all obtained from Aldrich chemical company ltd. Congo red (C.I. 22020, MW = 696.67 g mol-1,
C 32 H 24 N 6 O 6 S 2 .2Na, λ max =497 nm and pKa=4) and other chemicals used in the experiments (NH 4 OH
and H 2 SO 4 ) were purchased from C.I.S.A Espagne. Distilled water was used for preparation of various
solutions.
1.2. Preparation of p-CuBi 2 O 4

The p-CuBi 2 O 4 powder was prepared according to the previously reported procedure (Arai et al.,
2007; Liu et al., 2010; Elaziouti et al., 2012). α-Bi 2 O 3 and CuO were used as starting materials. The
stoichiometric proportion mixture of Bi 2 O 3 and CuO was previously ground for a period of time in an
agate mortar, and then heated at the rate of 5°C/min in a muffle oven (Linn High Therm) and thermally
treated at 750°C for 72 h in air. After the muffle oven was naturally cooled to room temperature, the
black CuBi 2 O 4 powder was ground in the agate mortar and then was collected as the precursor to prepare
the composite photocatalyst p-CuBi 2 O 4 /n-SnO 2

2.3. Preparation of semiconductor p-CuBi 2 O 4 /n-SnO 2

Combined semiconductors CuBi 2 O 4 /SnO 2 were prepared by a physical milling technique. Different
CuBi 2 O 4 / SnO 2 powder samples were prepared in a ratio (mass concentration) of 5%, 10%, 20%, 30%,
40% and 50% respectively, by varying the amount of CuBi 2 O 4 and subsequently milled in an agate
mortar for 30 minutes. The final samples were used for the determination of characterization and
photocatalytic activity. .

2.4. Characterization

Phase evolution and crystalline of the resulting powders were characterized by X-ray diffraction
(XRD) in an automatic D8 Bruker AXS diffractometer using CuKα radiation (λ=1.5406 Å). XRD
diffractogrammes were collected in the 10-70° intervals with a scan speed of 10°/min. The crystalline
average size (d DRX ) calculation using the Scherrer ( Pullar, 1988) equation as follows Eq. ( 1):

Where and λ is the X-ray wavelength (1.5406 Å). FWHM is the full-width
at half maximum and θ is the Bragg angle. FWHM was calculated from the peak having highest
intensity in all the samples. The lattice constants of the samples calculated from their corresponding XRD
pattern data are obtained by Fullprof program. The crystallite sizes of the pure nanoparticles were
deduced from the XRD patterns by calculation of the Scherrer equation.

3
Scanning electron microscopy (SEM) (Hitachi S-4800N) is used to characterize the morphology of the
particles.
UV-Vis diffuse reflectance spectroscopy measurements were carried out using a Perckin Elmer Lambda
650 spectrophotometer equipped with an integrating sphere attachment. The analysis range was from 200
to 900 nm, and polytetrafluoroethylene (PTFE, Teflon) was used as a reflectance standard.
The residual RC concentrations during de course of degradation were monitored with UV mini-1240
Spectrophotometer (Shimadzu UV mini-1240) in the range 200 - 800 nm, using 1 cm optical pathway
cells.

2.5. Photocatalytic study measurements

The photodegradation of CR catalyzed by the p-CuBi 2 O 4 /n-SnO 2 samples was investigated under
UV-light irradiation. 100 mg of catalyst was suspended in an CR solution (200 mL, 20 mg/L) in quartz
cell tube. The suspension pH value was previous adjusted at 8 using NaOH/ H 2 SO 4 solutions using
(Hanna HI 210) pH meter. Prior to UV light irradiation, the suspension was stirred with magnetic stirrer
(SpeedsafeTM Hanna) for 30 min under dark conditions at 298 K to ensure the establishment of
adsorption/desorption equilibrium between the catalyst and CR. The sample was then irradiated at 298 K
using 6 W ultraviolet (λ=365 nm, BLX-E365) photoreactor under continuous stirring. As the reaction
proceeded, a 5 ml suspension was taken at 20 min intervals during the catalytic reaction and was
centrifuged using centrifuge (EBA-Hetlich) at 3500 rpm for 15 min to completely remove photocatalyst
particles. The residual RC concentrations during de course of degradation were monitored with UV mini-
1240 Spectrophotometer (Shimadzu UV mini-1240) in the range 200-800 nm, using 1 cm optical pathway
cells. The experiments were also performed by varying the amount of CuBi 2 O 4 from 0 to 100 wt% at
room temperature (25°C).

The data obtained from the photocatalytic degradation experiments were then used to calculate the
degradation efficiency η’ (%) of the substrate Eq. (2):

where C i : dye initial concentration (mg·L-1) and C f : dye residual concentration after certain intervals
(mgL-1).
According to the Planck’s Law and some further calculation, we can find that the absorption wavelength
of the photoreactor can be done by determining its’ band gap value Eq. (3):

where h is Planck’s constant (4.13566733 10-15 eV. s); c is the speed of light (2.99792458 10 17 nm/s)
and λ is the UVA- light wavelength (355-375 nm). From the calculation, in order to absorb a UVA-light
wavelength, the band gap value of the photoreactor has to be below 3.49 eV and above 3.30 eV.
The photocatalytic degradation efficiency of catalyst for the degradation CR was quantified by
measurement of dye apparent first order rate constants under operating parameters.
Surface catalyzed reactions can often be adequately described by a monomolecular Langmuir–
Hinshelwood mechanism, in which an adsorbed substrate with fractional surface coverage θ is consumed
at an initial rate given as follow Eq. (4) (Vasanth Kumar et al., 2008) :

where K 1 is a specific rate constant that changes with photocatalytic activity, K 2 the adsorption
equilibrium constant, and Co is the initial concentration of the substrate . Inversion of the above rate
equation is given by Eq.(5):

4
Thus, a plot of reciprocal of the apparent first order rate constant 1/K app against initial concentration of
the dye C 0 should be a straight line with a slope of 1/K 1 and an intercept of 1/K 1 K 2 . Such analysis
allows one to quantify the photocatalytic activity of catalyst through the specific rate constant K 1 ( with
larger K 1 values corresponding to higher photocatalytic activity) and adsorption equilibrium constant K 2 (
K 2 expresses the equilibrium constant for fast adsorption-desorption processes between surface of catalyst
and substrates). The integrated form of the above equation (Eq. 4) yields to the following Eq. (6):

where t is the time in minutes required for the initial concentration of the dye Co to decrease to C. Since
the dye concentration is very low, the second term of the expression becomes small when compared with
the first one and under these conditions the above equation reduces to Eq. (7 ).

where k app is the apparent pseudo-first order rate constant, C and Co are the concentration at time ‘t’ and
‘t=0’, respectively. The plot of ln Co/C against irradiation time t should give straight lines, whose slope is
equal to K app .
The half-life of dye degradation at various process parameters was raised from Eq. (8).

Where half-life time, t 1/2 , is defined as the amount of time required for the photocatalytic degradation of
50% of CR dye in a aqueous solution by catalyst.

3. Results and discussions

3.1. XRD Analysis of (x wt%) CuBi 2 O 4 /SnO 2 Nanocomposites

Fig. 1 shows the XRD patterns of the as-synthesized (5 wt%) CuBi 2 O 4 /SnO 2 nanocomposites in
comparison with those of CuBi 2 O 4 precursor and pure SnO 2 . Diffraction peaks of pure SnO 2 (Fig. 1a) at
2θ of 26.63°, 33.73°,37.94°, and 51.79° can be indexed as the (110), (101), (200), and (211) planes of
tetragonal rutile structure of stannic oxide ( lattice constant a=4,7373(2) Å et b=3,1865 (3) Å), which is in
good agreement with standard value (JCPDS file No. 41-1445). The crystallite sizes of pure SnO 2 , d XRD ,
deduced from the XRD patterns by calculation of the Scherrer equation, was found to be 50nm.
The diffraction peaks of the Cubi 2 O 4 precursor (Fig. 1b) at 2θ of 28.03°, 29.73°, 30.73°, 32.54°,
33.36° and 46.71° were respectively indexed as (211), (220), (002), (102), (310), and (411) planes of pure
tetragonal phase of crystalline Cubi 2 O 4 , according to the Joint Committee Powder Diffraction Standards
(P4 2 /mnm, JCPDS file no 42-0334) with lattice constants (a = 8.5004 A˚ , c = 5.819 A˚ ) calculated from
their corresponding XRD pattern data are obtained by Fullprof program. Both precursor CuBi 2 O 4 and
pure SnO 2 show preferred (002) crystallographic orientation owing to the preparation route of the sample
during the XRD analysis. On the other hand, the XRD patterns of (5 wt%) CuBi 2 O 4 /SnO 2 nanocomposite
exhibited characteristic diffraction peaks of both CuBi 2 O 4 and SnO 2 crystalline phases, suggesting that
CuBi 2 O 4 and SnO 2 are coexistent in the composites as separate phases. It can be seen from Fig. 1c, that
at 5% mass concentration of Cubi 2 O 4 , the diffraction pattern of the nanocomposite materials was
approximately similar to that of pure SnO 2 . This is probably due to the high crystallinity of the SnO 2

5
phase and to the lowest amount of CuBi 2 O 4 present in the composites (5 wt%), thus appearing as the
dominant peaks in the XRD spectra of the nanocomposite sample.

(110)
(101)
CuBi2O4 (211)
(002 CuBi2O4
CuBi2O4

(200) (220) (112)

(c) (321)
(002) (310) (301) (202)

(b)

(a)

0 20 30 40 50 60 70 80

Figure 1. XRD patterns of pure SnO 2 (a) precursor CuBi 2 O 4 (b) and the synthesis (5
wt%)CuBi 2 O 4 /SnO 2 (c).

3.2. UV–Vis Diffuse Reflectance Spectra and Band Gap Energy.

Fig. 2, shows the UV-vis absorbance spectra of CuBi 2 O 4 synthesized by solid-state reaction at 750
◦C for 24 h and pure SnO 2 . It is clear from the recorded UV-visible spectrum of SnO 2 two absorption
bands are observed in the UV region at 210-245 nm and at 270 nm. Generally, the absorption band at
210-245 nm of SnO 2 in the UV region originates from the charge-transfer transition between the O 2p
and Sn 4d states in O2- and Sn4+. The band at 270 nm is attributed, either to the inter-valence transition
of Sn4+/Sn2+ (Shen et al., 1994), or to the charge-transfer transition s→p of Sn2+ ions (Teegarden et al.,
1966).
The UV–visible spectrum of CuBi 2 O 4 sample has strong and broad absorption in the range of 200–
900nm. This suggests that the prepared sample absorb both UV and visible light. Obviously, for CuBi 2 O 4
nanostructures, the broad absorption band observed in the UV-visible region was attributed to the charge-
transfer transition between the O 2p and Cu 3dx2-y2 states in O2- and Cu2+ respectively (Nathan et al.,
2012). Fig. 3 shows UV–Vis diffuse reflectance spectra of a series of photocatalysts (x wt%) CuBi 2 O 4 /
SnO 2 for 0≥x≥20wt%. A progressive red shift in the band gap absorption is observed with the increase
the amount of x wt% of CuBi 2 O 4 in the SnO 2 matrix.
Pure SnO 2 has a negligible absorption in the range of UVA light ( 355 nm ≤ λ ≤ 375 nm) because the
catalyst is only effective under ultraviolet irradiation ( λ ≤ 345 nm). With the increase of amount of x
wt% of CuBi 2 O 4 , the absorption edge of the sample has some red shift. The red-shift observed in the
nanocrystalline SnO 2 would be explained to the formation of localized states within the band gap owing
to oxygen vacancies and increase Sn2+ ion concentration. This phenomenon is due to the shift of
absorbance band shift towards the longer wavelength ( Lu et al., 2009; Charitidis et al., 2005) . The red
shift is presumably ascribed to the homogeneous dispersion of CuBi 2 O 4 particles within SnO 2 matrix.
The onset absorption edges and band gap energies of the as-synthesized CuBi 2 O 4 particle, pure SnO 2
nanoparticle and series of (x wt%) CuBi 2 O 4 /SnO 2 nanocomposites are shown in Figs. 4 and 5
respectively.

6
 The absorption onsets of crystalline semiconductor were determined by linear extrapolation from the
infection point of the curve (Absorbance versus λ Absorp. Edge ) to the baseline and Eg = 1240/λ Absorp. Edge
as shown in Figs. 2 and 3. The as-synthesized CuBi 2 O 4 exhibits an absorption onset at 900 nm, which
correspond to band gap energy of 1.38 eV. This value is lower than that reported in the literature; 1.5 eV
(Arai et al., 2007; Liu et al., 2010).

1.4 SnO2

1.2

1
Absorbance

0.8

0.6
Eg=1.38 eV
0.4
Eg=3.59 eV

0.2

0
200 250 300 350 400 450 500 550 600 650 700 750 800
Wavelength λ (nm)

Figure 2. UV-visible absorbance spectra of SnO 2 and CuBi 2 O 4 synthesized by solid-state reaction at
750 ◦C for 24 h.

7
 1.4 5%CuBi2O4-95%SnO2 1.4 5%CuBi2O4-95%SnO2

10%CuBi2O4-90%SnO2
1.2 1.2
20%CuBi2O4-80%SnO2
1 1
SnO2

Absorbance
Absorbance

0.8 0.8 Eg=3.54 eV

0.6 0.6

0.4 0.4

0.2 0.2

0 0
200 250 300 350 400 450 500 550 600 650 700 750 800 200 250 300 350 400 450 500 550 600 650 700 750 800

Wavelength λ (nm) Wavelength λ (nm)

Eg=3.12
Eg=3.12 eV eV Eg=3.12 eV Eg=3.12
Eg=3.12 eV eV

1.6 10%CuBi2O4-90%SnO2 1.6 20%CuBi2O4-80%SnO2

1.4 1.4

1.2 1.2

1 1
Absorbance

Absorbance

0.8 0.8
Eg=3.49 eV
0.6 Eg=3.54 eV 0.6

0.4 0.4

0.2 0.2

0 0
200 250 300 350 400 450 500 550 600 650 700 750 800 200 250 300 350 400 450 500 550 600 650 700 750 800
Wavelength λ (nm) Wavelength λ (nm)

Figure 3. UV-visible absorbance spectra of a series of (x wt%) CuBi 2 O 4 /SnO 2 nanocomposites.

It is clear from the recorded spectrum that the pure SnO 2 nanocrystalline has an absorption onset at
345 nm, which match to band gap energy of 3.59 eV, attributing to stannic oxide (SnO 2 ). These results
are in well agreement with values reported in the literature (Casey and Stephenson, 1990). The optical
properties of the as-synthesized CuBi 2 O 4 and pure SnO 2 nanoparticles are reported in table 1.

It is widely accepted that electronic transport properties depend on the physical and structural
characteristics of photocatalyst, such as crystallite size, morphology, phase structure and amount of
CuBi 2 O 4 loaded (Yu et al., 2008). As reported from the UV-visible results in Fig.5 and Table 1, for the
series of (x wt%)CuBi 2 O 4 / SnO 2 nanocomposite materials, the band gap energy decreased from 3.59 to
3.49 eV as the amount of CuBi 2 O 4 was increased up to 20 wt % on the SnO 2 matrix, suggesting that the
physical preparation of nanocomposite powders will result in good particle-to-particle connections,
especially in cases where a high electrical conductivity. So, the decrease of the band gap energy with an
enhanced absorption intensity of the (5wt%)CuBi 2 O 4 / SnO 2 nanocomposites upon loading the amount of
CuBi 2 O 4 could be ascribed to the homogeneous dispersion of CuBi 2 O 4 within the SnO 2 matrix in the
bulk of the catalyst and the formation of conducting network at very low temperature ( Pany et al., 2009).

Chun-Ming et al. (Chun-Ming et al., 2007) have already reported band gap narrowing effect for
doped SnO 2 nanoparticles. However there is no clear understanding of this phenomenon. A direct–
indirect transition has been proposed by Rakhshani et al. (Rakhshani et al., 1998). In order to explain the
band gap narrowing effect, many groups have suggested that alloying effect of parent compound with
some impurity phases may be responsible for the band gap narrowing ( Barreau et al., 2002). So we think
that for the samples containing up to 5wt % CuBi 2 O 4 concentration, SnO 2 –SnO 2-x alloying effect may be
8
responsible for the band gap narrowing effect. For the SnO 2 nanoparticles above 5wt % CuBi 2 O 4
concentration there is a huge drop in the band gap. This may be due to the formation of sub- bands in
between the band gap and the conduction band and sub-bands are merging with the conduction band to
form a continuous band. This is perfectly in agreement with the XRD analytical results and consistent
with the previous reported work (Chun-Ming et al., 2007 ).

Table 1. Optical properties of the as synthesized CuBi 2 O 4 and pure SnO 2 nanoparticles.
Band gap Eg (eV)
Systems λ (nm) Charge-transfer transition
Experimental Literature Ref.
CuBi 2 O 4 900 2p (O)→ 3dx -y (Cu)
6 2 2
1.38 1.5
(Arai et al., 2007; Liu et al., 2010)
SnO 2 345 2p (O) →5s ( Sn)
6
3 .59
05 350 2p6 (O) →5s ( Sn) 3.54 3.5-4.1
10 350 2p (O) →5s ( Sn)
6
3.54 (Casey and Stephenson, 1990)
20 355 2p6 (O) →5s ( Sn) 3.49
λ : Wavelength, Ref. : Reference
SEM analysis

Fig. 4a, illustrates typical SEM images of CuBi 2 O 4 , pure SnO 2 and (5 wt%)CuBi 2 O 4 /SnO 2
nanocomposites. It can be seen that, for the CuBi 2 O 4 , the appearance is shapeless sheet, and the particle
size of the CuBi 2 O 4 is about 10-20µm. Fig. 4b shows typical high-resolution SEM image of CuBi 2 O 4
powder to further show the details of the nanoparticles. As shown in Fig. 4b, it clearly shows two
different crystal shapes on the CuBi 2 O 4 surface, corresponding to two different particle sizes of
CuBi 2 O 4 . The appearance of CuBi 2 O 4 is a shape sheet and a well-defined tetragonal phase with the
crystallite diameter of the CuBi 2 O 4 is about 5µm, where as groups of smaller particles do not have any
specific shape with size up to 500 nm tend to cover the bigger particles. However, pure SnO 2 from SEM
analysis (Fig. 4c) clearly shows two different tetragonal-shaped nanoparticles structures on the SnO 2
surface, which can be assigned to SnO 2 (ion radius Sn4+: rSn4+ = 0.071 nm) with a particle size in the
range of 0.1µM and SnO (ion radius Sn2+ : rSn2+ = 0.112 nm nm) with approximately 0.2 µm
dimensions, which agrees with the UV –Vis Diffuse Reflectance Spectrum of SnO 2 in figure 2. Both
nanoparticles are close to each other in the form of chains. The as synthesized (5 wt%)CuBi 2 O 4 /SnO 2
nanocomposite via physical milling synthesis method (Fig. 4d) clearly shows the presence of SnO 2
nanoparticles deposited onto the CuBi 2 O 4 surface, displaying a particle size of 0.1-0.2µM and strong
assembly of the nanoparticles measuring from 0.2µM to 1µm. Such aggregation can be explained by the
solid-state synthesis route, which generally requires repeated mechanical mixing process and a high
temperature process.

9
 (a) (b)

(c) (d)

Figure 4. SEM images of (a) low-resolution of CuBi 2 O 4 (b) high-resolution of precursor CuBi 2 O 4 (c)
pure SnO 2 (d) (5 wt%)CuBi 2 O 4 /SnO 2 nanocomposites.

3.4. Effect of the amount of CuBi 2 O 4 on the photocatalytic activity of (5wt%)CuBi 2 O 4 /SnO 2

The effect of the amount of CuBi 2 O 4 on photocatalytic degradation of CR was conducted over a
range of catalyst amount from x=0 to x=100 wt%. As observed in Fig.5, it is evident that the
photocatalytic redox of CR greatly depends on the amount of doped CuBi 2 O 4 . The photocatalytic activity
increased drastically from 25.62 to 58.06% as the catalyst amount was raised from x=0 to x=5 wt%.
Further increase in the CuBi 2 O 4 amount beyond of x=5 wt%, the photocatalytic activity decreased
gradually, almost reaching 3.13% at x=100wt%. The maximum photocatalytic activity of
(xwt%)CuBi 2 O 4 /SnO 2 (58.06%) under UVA light irradiation was achieved within 100 min of light
illumination time when the amount of doped CuBi 2 O 4 x was 5 wt%, which is obviously about 2.3 times
higher than the value of 25.62% over pure SnO 2 . So there is an optimum CuBi 2 O 4 contents for high
dispersion morphology of nanoparticles CuBi 2 O 4 on the SnO 2 surface with high activity.
But until now, there are no reports about synergistic effect between SnO 2 and CuBi 2 O 4 in the
(5wt%)CuBi 2 O 4 /SnO 2 nanocomposite under UV light excitation. From Fig. 6, it is clear that the
photocatalytic activity of SnO 2 is significantly increased under the presence of an amount of CuBi 2 O 4 (5
wt%) compared to SnO 2 and CuBi 2 O 4 precursors. These results strongly suggest the existence of a
synergistic effect between SnO 2 and the CuBi 2 O 4 in the (5wt%)CuBi 2 O 4 /SnO 2 nanocomposite under
UVA light excitation. However, at higher amount of doped CuBi 2 O 4 than 5wt%, the photocatalytic redox
activity of (xwt%) CuBi 2 O 4 /SnO 2 photocatalyst was obviously decreased on further increase in amount
10
of CuBi 2 O 4 . Thus, such an above occurrence in the present experiment is primarily attributed to
overlapping of adsorption sites of SnO 2 particles as a result of overcrowding of the CuBi 2 O 4 granule
owing to the decrease in screening effect and interfering of light. Similar trends were reported in
preparation and characterization of p–n heterojunctionphotocatalyst p-CuBi 2 O 4 /n-TiO 2 with high
photocatalytic activity under visible and UV light irradiation ( Lin et al., 2008).

Figure 5. Effect of the amount of CuBi 2 O 4 on the photocatalytic redox of CR under UV light irradiation (
[(xwt%)CuBi 2 O 4 /SnO 2 ]=0.5g/L, [CR]= 20mg/L, pH=8, T=298K, λ max =365 nm, I=90 J /cm2 and
irradiation time=100 min).

3.5. Effect of UV light and catalyst

The photocatalytic activities of all three CuBi 2 O 4 , SnO 2 and (5wt%) CuBi 2 O 4 /SnO 2
photocatalysts were assessed by the photocatalytic redox reaction of Congo red (CR) aqueous solution
under UVA light irradiation. Variations of CR reduced concentration (C/C 0 ) versus irradiation time (t)
over different catalysts under different experimental conditions through UVA light alone, UVA/CuBi 2 O 4 ,
UVA/SnO 2 and UVA/(5wt%) CuBi 2 O 4 /SnO 2 are presented in Fig.6. The synergistic effect between
SnO 2 and CuBi 2 O 4 in the (5wt%)CuBi 2 O 4 /SnO 2 nanocomposite under UVA light excitation showed that
(5wt%)CuBi 2 O 4 /SnO 2 exhibited higher photocatalytic efficiency, as compared to the single phases
CuBi 2 O 4 and SnO 2 . The highest efficiency was obtained, under UVA irradiation over
(5wt%)CuBi 2 O 4 /SnO 2 , as a result of 58.06% degradation of CR for 100 min of irradiation time.
However, the photocatalytic degradation of CR over single phases CuBi 2 O 4 and CeO 2 were only 3.13
and 25.62% respectively. When 20 mg/L of CR in the direct photolysis for the same optimum irradiation
time, disappearance of dye was negligible (0.49%). On the basis of these results, the high decomposition
of CR dye in the presence of (5wt%) CuBi 2 O 4 /SnO 2 , catalyst is exclusively attributed to the
photocatalytic reaction of the combined semiconductor particles under UVA light irradiation. A similar
result was reported in the heterojunction semiconductor SnO 2 /SrNb 2 O 6 with an enhanced photocatalytic
activity: The significance of chemically bonded interface (Gurlo, 2006).

3.6. Kinetic modelling

The photocatalytic degradation of CR over different experimental conditions was displayed in Table 2.
As it can be seen, the straight lines for the entire as-prepared samples of the plots of lnC/C 0 versus t with
11
high regression coefficients (R2=0.945-0.991), for the pseudo-first-order kinetic model strongly suggest
that all the photodegradation systems were a pseudo-first-order model. Exception was observed in the
cases of direct photolysis and photocatalysis reaction in the presence of the single phase CuBi 2 O 4
respectively.

Figure 6. Photocatalytic degradation kinetics of CR at different experimental conditions

([Catalyst]=0.5g/L, [CR]= 20mg/L, pH=8, T=298K, λ max =365 nm, I=90 J /cm2 and irradiation
time=100 min).

Table 2. Kinetic parameters of photocatalytic degradation of CR on (5wt%)CuBi 2 O 4 /SnO 2 , compared

to the pure and combined catalysts systems ( [Catalyst]=0.5g/L, [CR]= 20mg/L, pH=8, T=298K,
λ max =365 nm, I=90 J /cm2 and irradiation time=100 min).

η η' K1 t 1/2 R2
Systems
(%) (%) (min-1) (min) (%)
CR/UV-A - 0.49 - - -
CR /SnO 2 / UVA 2.92 25.62 0.0045 154.032 0.945
CR /CuBi 2 O 4 / UVA 0 3.130 0.0002 3465.736 -
CR/(5wt %)CuBi 2 O 4 -SnO 2 /UVA 31.38 58.06 0.052 13.329 0.991
η : Adsorption activity; η’ : Photocatalytic activity
3.7. Discussion of Mechanism

The above analysis shows that the migration direction of the photogenerated charge carrier depends on
the band edge positions of the two semiconductors. There are three methods to determine the band edge
positions: experiments based on photoelectrochemical techniques, calculation according to the first
principle, and predicting theoretically from the absolute (or Mulliken) electronegativity (Kim et al., 1993;
Butler and Ginley, 1978; Xu and Schoonen, 2000).The first one is not always easy to handle, and the
second one cannot obtain the absolute energy of band edges with respect to vacuum and always has large
discrepancies between calculated and measured values. The third one is a simple approach with

12
reasonable results for many oxides photocatalysts (Xu and Schoonen, 2000). The conduction band edge
of a semiconductor at the point of zero charge (pHzpc) can be predicted by Eq. (9):

E0 CB = χ − E C − 1/2Eg. [9]

where χ is the absolute electronegativity of the semiconductor (χ is 4.75 eV and 6.25eV for CuBi 2 O 4 and
SnO 2 respectively). EC is the energy of free electrons on the hydrogen scale (4.5eV) and Eg is the band
gap of the semiconductor. The predicted band edge positions of CuBi 2 O 4 and SnO 2 by the above
equation are shown in Table 4. Photocatalytic reaction proceeds owing to holes and electrons generated
in materials by absorbing light energy. The photogenerated holes have oxidation ability and the
photogenerated electrons have reduction ability. For decomposition of organic pollutants by
photocatalytic reaction, the oxidation potential of hole needs to be more positive than +1 V that is redox
potential of general organic compounds as well as of hydroxyl radical (E 0 (H 2 O/•OH)) = 2.8 V vs. NHE
at pH 7). In addition, the redox potential of electrons needs to be more negative than that of superoxide
radical (E 0 (O 2 /O 2 • -) = -0.28 V vs. NHE at pH 7).

Table 3. Absolute Electronegativity, estimated band gap, energy levels of calculated conduction band
edge, and valence band at the point of zero charge for CuBi 2 O 4 and SnO 2 .

Systems χ (eV) λ (nm) Eg (eV) E0 BC (eV) E0 BV (eV)

CuBi 2 O 4 4.75 900 1.38 -0,44 +0.94

SnO 2 6.25 345 3.59 -0.05 +3.55

Fig. 7 depicts reaction schemes of CuBi 2 O 4 (a) and SnO 2 (b) as the p and n an type respectively for
charge separation for the reductivity/oxdizability improvement model. CuBi 2 O 4 is a p-type
semiconductor, which always exhibits good stability under UVA visible illumination, and SnO 2 is
determined as an n-type material. It was reported previously that that the band gap of CuBi 2 O 4 is 1.38
eV, which can be excited by photons with wavelengths below 900 nm, whereas SnO 2 with band gap of is
about 3.59 eV can be excited by photons with wavelengths of 345 nm.
Under UVA (λ UVA = 355–375 nm→ Eg_ = 3.3–3.49 eV) light irradiation, the energy of the excitation
light is too small to directly excite the SnO 2 (λ= 345 nm → Eg = 3.59 eV) portion of the photocatalyst,
but it is large enough to yield an excited state of CuBi 2 O 4 (λ = 900 nm → Eg = 1.38 eV) semiconductor.
According to the band edge position (Table 3), for the p-CuBi 2 O 4 alone (Fig. 7 a), the electronic
potential of the conduction band of p-CuBi 2 O 4 is around −0.44 eV (vs. NHE at pH 7) which is more
negative than that of superoxide radical (E 0 (O 2 /O 2 • -) = -0.28 V vs. NHE at pH 7). This indicated that the
electron photoproduced at the conduction band directly reduced O 2 into O 2 • - . These reduced O 2 •- can
subsequently transfer the charge to the species present in the reaction medium that are preferentially
adsorbed onto the p-CuBi 2 O 4 particles. Hence, the superoxide radical (O 2 • -) reduce the recombination of
the charge carriers enhancing the activity in the UVA light. However, the p-CuBi 2 O 4 valence band of +
0.94 eV (vs. NHE at pH 7), which is too negative than that of hydroxyl radical (E 0 (H 2 O/•OH)) = +2.8 V
vs. NHE at pH 7). The holes photogenerated in the p-CuBi 2 O 4 are not able to oxidize H 2 O to •OH. But it
is approximately enough to decompose organic pollutants.
p-CuBi 2 O 4 powder formed in our laboratory by the solid-state reaction of CuO and α-Bi 2 O 3 at 750 °C
for 24 h, exhibits a black color. The presence of non stoechiometric regions of the nominally p-CuBi2O4
particles or small domains of binary oxide phases of Cu x O or Bi x O, undetected by XRD data, as unstable
impurity phases which could be originated from a number of processes such as reduction of the p-
CuBi 2 O 4 , could be responsible for higher recombination rates. Thus, the result is consistent with the
previous study in electrochemical synthesis and characterization of p-CuBi 2 O 4 thin film photocathodes
(Magesh et al., 2009). Therefore, CuBi 2 O 4 alone shows negligible photocatalytic activity under UVA
13
light. As a result, less efficient charge-carrier separation, and thus the increment of photocatalytic activity
was restricted.
For pure n-SnO 2 (Fig. 7b) which is only effective under ultraviolet irradiation ( λ= 345 nm), shows
little photocatalytic activity under UVA light. These observations can be explained as follows: The
reduction of Sn+4 to Sn+2 requires a potential of +0.15 V(vs NHE pH 7) and the oxidation of Sn+2 to Sn+4
needs -0.15V (vs NHE pH 7). The SnO 2 valence band of SnO 2 is around of +3.55 eV (vs. NHE at pH7)
which is more positive than Sn+2 to Sn+4 oxidation potential. The valence electron of SnO 2 can hence
oxidize Sn+2 to Sn+4 . But the conduction band of SnO 2 has a potential of -0.05eV (vs. NHE at pH 7),
which is more negative than Sn+4 to Sn+2 reduction potential. Hence, the conduction band electrons of
SnO 2 may be able to reduce Sn+4 to Sn+2. These reduced Sn+2 and oxidized Sn+4 species can
subsequently transfer the charge to the species present in the reaction medium. Hence, the Sn ions can
suppress the recombination of the charge carriers, enhancing the activity in the UVA light.

(a) p-CuBi2O4 (b) n-SnO2

-2 -2
CB CB
-1 -1
O2/O2• -

0
Potential /V (vs. NHE)

0 Sn+2/Sn+4
O2/O2• -
Sn+4/Sn+2

1 1

2 2

3
VB H2O/•OH
3

4 4 VB

Figure 7. Reaction schemes of CuBi 2 O 4 (a) and SnO 2 (b) as the p and n type semi-conductor
respectively for charge separation for the reductivity/oxdizability improvement model (electron and
hole ).

In a contrast experiment, p-CuBi 2 O 4 /n- SnO 2 composite exhibits higher activity than phases p-
CuBi 2 O 4 and n- SnO 2 . So we should continue with a further discussion on the mechanism in the
photocatalysis. The possible reason for the remarkably enhanced photocatalytic performance of p-
CuBi 2 O 4 /n-SnO 2 in the course of the photocatalytic redox of Congo red can be explained by p-n type
heterojunction formation model of the electron–hole separation process under UV light irradiation. The
schematic diagram p–n heterojunction formation model is depicted in Fig. 8.
Photocatalyic degradation schemes for an azo-dye such as Congo red, are characterized by nitrogen to
nitrogen double bonds (N=N) that are usually attached to two radicals of which at least one but usually
both are aromatic groups (benzene or naphthalene rings). The color of azo-dyes is determined by the azo
bonds and their associated chromophores and auxochromes. Azo bonds are the most active bonds in azo-
dye molecules and can be oxidized by positive hole or hydroxyl radical or reduced by electron in the
conduction band. The cleavage of N=N bonds leads to the decoloration of dyes (Pardeshi and Patil,
2009).
CuBi 2 O 4 is a p-type semiconductor, which always exhibits good stability under UV visible
illumination, and SnO 2 is determined as an n-type semiconductor. The band gap of p-CuBi 2 O 4 was 1.38
eV, which could be excited by photons with wavelengths below 900 nm, whereas n- SnO 2 with band gap
of is about 3.59 eV can be excited by photons with wavelengths of 345 nm. So at the interfaces of p-
CuBi 2 O 4 loaded n- SnO 2 composite, a p-n heterojunction would be formed.

14
 According to the band edge position (Table 3), as the conduction band of SnO 2 is lower than that of
CuBi 2 O 4 , the former functions as a substrate for the photogenerated electrons, and the later acts as
sensitizer in the p–n heterojunction system. The electronic potential of the conduction band of n- SnO 2 is
slightly more anodic than that of p-CuBi 2 O 4 , whereas, the hole potential of the valence band top of n-
SnO 2 , which is more positive than that of p-CuBi 2 O 4 . Under UVA a part of the photogenerated charge
carriers, free electron (e-) and electronic vacancy-a hole (h+), recombines in the bulk of the
semiconductors, while the rest transfer in the photocatalyst surfaces being partially localized on structural
defective centers of its crystalline lattice.
So, when p-type semiconductor CuBi 2 O 4 and n-type semiconductor SnO 2 were connected to each
other, p–n heterojunction will be formed between p-CuBi 2 O 4 and n-SnO 2 , and at the equilibrium the
inner electric field will be also produced at the same time in the interface. So a number of micro p–n
heterojunction CuBi 2 O 4 /SnO 2 photocatalysts will be formed after doping p-CuBi 2 O 4 powder into n-
SnO 2 granule. The electron-hole pairs will be created under UV light illumination. With the effect of the
inner electric field, the holes produced in the CuBi 2 O 4 valence band will remain in the CuBi 2 O 4 valence
band, while the electrons transfer to the conduction band of the SnO 2 . In this way, the photoinduced
electron (e−)–hole (h+) pairs in the CuBi 2 O 4 co-catalyst were effectively separated by the p–n junction
formed in the (5wt%) p-CuBi 2 O 4 /n-SnO 2 nanocomposite and transferred to the semiconductor/substrate
interfaces, thus the probability of electron–hole recombination was reduced. As a result, a larger amount
of electrons on SnO 2 surface and a larger amount of holes on CuBi 2 O 4 surface acting as powerful
oxidants respectively Eq. (10-11). The stepwise photocatalytic mechanism is illustrated below:

p-CuBi 2 O 4 /n-SnO 2 +hν→ p-CuBi 2 O 4 (e- BC + h+ BV )/n-SnO 2 [10]

→ p-CuBi 2 O 4 (e- BC +h+ BV ) / n-SnO 2 (e- BC ) [11]
+4 +2
The electrons at the conduction band of n-SnO 2 can directly reduced Sn to Sn Eq. (12) and react
with the adsorbed molecular O 2ads. on the p-CuBi 2 O 4 /n-CeO 2 catalyst sites, reducing it to superoxide
anion (O.- 2ads ), hydroperoxide (HO 2ads ) radicals and hydrogen peroxide (H 2 O 2 ads ) Eq. (14-16), while the
electron at the valence electron of n-SnO 2 can hence oxidize Sn+2 to Sn+4 Eq. (13). However, the
photogenerated holes at the valance band of p-CuBi 2 O 4 can directly oxidize the CR dye molecules
adsorbed on the photocatalyst surface forming the organic cation-radicals (R.+ ads ) Eq.(17). These
processes could be represented in the following equations:
Sn+4 + 2 e- → Sn+2 [12]
Sn+2 → Sn+4 + 2e- [13]
e- + O 2 ads. → O•- 2 ads [14]
O •-
2 ads + 2H 2 O ads → HO 2ads +OH
• -
ads [15]
•
HO 2ads + H 2 O ads → H 2 O 2 ads + OH ads .•
[16]
R ads + h+
→ R•
ads
+
[17]
• •
The peroxide (H 2 O 2 ads ), hydroxylic ( OH ads ) , hydroperoxide ( HO 2ads ) and organic cation-radicals
(R.+ ads ) formed on the illuminated p-CuBi 2 O 4 /n-SnO 2 catalyst surface via either an effect of Sn+4 /Sn+2
redox couple or photosensibilization of p-CuBi 2 O 4 and organic molecules adsorbed on the
photocatalyst surface are highly effective oxidizing agent in the p-CuBi 2 O 4 /n-SnO 2 mediated
photocatalytic oxidation of Congo red Eq. (30).
The organic cation-radicals (R•+ ads ), the reduced Sn+2 and oxidized Sn+4 species formed on the
illuminated p-CuBi 2 O 4 /n-SnO 2 catalyst surface via either a photosensibilization of organic molecules or
and/ CuBi 2 O 4 are highly effective oxidizing agent in the p-CuBi 2 O 4 /n-SnO 2 mediated photocatalytic
oxidation of Congo red Eq. (18).

(H 2 O 2ads , •OH ads , O•- 2ads , R. ads +) + CR dye → degradation of the CR dye [18]

The primary raison for the observed maximum photocatalytic actibity of the p-CuBi 2 O 4 /n-SnO 2
nanocompsites can be attributed to p-CuBi 2 O 4 being less active than n-SnO 2 . At 5wt% p-CuBi 2 O 4
15
loading, the amount of Sn+4 /Sn+2 present on the p-CuBi 2 O 4 /n-SnO 2 nanocompsites surface is favorable
for faster charge transfer and at the same time allows light to reach the p-CuBi 2 O 4 /n-SnO 2 surface.
Similar trend was reported in the photocatalytic behavior of CeO 2 /TiO 2 system for degradation of
methylene blue (Magesh et al., 2009).

p-CuBi2O4 n-SnO2

Figure 8. Reaction scheme of CuBi 2 O 4 /SnO 2 as the p-n type charge separation for the
reductivity/oxdizability improvement model (electron and hole ).

Conclusion

Novel p-CuBi 2 O 4 /n-SnO 2 nanocomposite photocatalysts with different mass ratios were synthesized
via the solid state technique, and was characterized by a number of techniques such as a X-ray diffraction
, scanning electron microscopy and UV–vis diffuse reflectance spectroscopy technique. The as-prapared
p-CuBi 2 O 4 /n-SnO 2 photocatalysts were assessed based on the photodegradation of Congo red (CR) dye
as a probe reaction under UVA (365 nm) light irradiation. Experimental results indicated that the phase
composition, surface morphology of particles, and optical absorption of the sample were found to vary
significantly with the mass ratios. The p-CuBi 2 O 4 /n-SnO 2 catalyst exhibited higher exhibited higher
photocatalytic activity as compared with precursor’s compounds. The photodegradation reactions were
satisfactory correlated with the pseudo-first-order kinetic model. The highest efficiency was observed at
5 wt% p-CuBi 2 O 4 content as a result of 58.06 % of photoactivity for 100 min of exposure irradiation
under UV light at pH 8 and 25 °C. The effective electron-hole separation at the physically bonded
interfaces was believed to be mainly responsible for the remarkably enhanced photocatalytic activity of
5wt% CuBi 2 O 4 /SnO 2 in the course of the photocatalytic redox conversion of CR.

Acknowledgments

We are greatly indebted to the University of Science and Technology of Oran (Mohamed Boudiaf),
and the University of Science and Technology of Saida (Moulay Tahar) for their material support. We
gratefully acknowledge the support for X-ray diffraction (XRD), scanning electron microscopy (SEM)
and UV–vis diffuse reflectance spectroscopy (DRS) by Mrs. Professor Rose-Noëlle Vannier of the Unit
of Catalysis and Solid State Chemistry of Lille 1 University.

References

16
 Aoki A., Sasakura H., Tin oxide thin film transistors, Japanese Journal of Applied Physics », vol. 9 n° 5, 1970, p.
582
Arai T., Yanagida M., Konishi Y., Iwasaki Y., Sugihara H., Sayama K., « Efficient complete oxidation of
acetaldehyde into CO 2 over CuBi 2 O 4 /WO 3 composite photocatalyst under visible and UV light irradiation »,
Journal of Physical Chemistry C, vol. 111, n° 21, 2007, p. 7574–7577.
Barreau N., Bernede J.C., Marsillac S., Mokrani, A., « Study of low temperature elaborated tailored optical band
gap β-In2S3−3xO3x thin films », Journal of Crystal Growth, vol. 235, n° 1-4, 2002, p. 439-449.
Bhosale R., Pujari S., Muley G., Pagare B., Gambhire A., « Visible-light- activated nanocomposite photocatalyst
of Cr 2 O 3 /SnO 2 », Journal of Nanostructure in Chemistry, vol. 3, n° 46, 2013, p. 1-7.
Bian Z., Zhu J., Wang S., Cao Y., Qian X., Li H., « Self assembly of active Bi 2 O 3 /TiO 2 visible photocatalyst
with ordered mesoporous structure and highly crystallized anatase », Journal of Physical Chemistry C, vol. 112
n° 16, 2008, p. 6258–6262.
Butler M.A., Ginley D.S., « Prediction of Flatband Potentials at Semiconductor‐Electrolyte Interfaces from Atomic
Electronegativities», Journal of Electrochemical Society, vol.125, n° 2, 1978, p. 228-232.
Casey V., Stephenson ML., « A study of undoped and molybdenum doped, polycrystalline, tin oxide thin films
produced by a simple reactive evaporation technique », Journal of Physics D: Applied Physics, vol.23, n°
9, 1990, p. 1212-1215.
Cheng B., Russell J.M., Shi W., Zhang L., Samulski E.T., « Large-Scale, solution-phase growth of single- crystalline
SnO 2 nanorods. Journal », American Chemical Society, vol. 126, n° 19, 2004, p. 5972-5973.
Charitidis C., Patsalas P., Logothetidis S., « Optical and mechanical performance of nanostructured cerium
oxides for applications in optical devices », Journal of Physics: Conference Series 10 , 2005, p. 226–229.
Chun-Ming L., Li-Mei F., Xiao-Tao Z., Wei-Lie Z., « The influence of nickel dopant on the microstructure
and optical properties of SnO 2 nano-powders », Chinese Physics, vol. 16, n° 1, 2007, p. 95–99.
Chopra K.L., Major S., Pandya D.K., « Transparent conductors—A status review », Thin Solid Films, vol.102, n°1
1983, p. 1-96.
Couselo N., Garcia Einschlag F.S., Candal R.J., Jobbagy M., « Tungsten-doped TiO 2 vs pure TiO 2 photocatalysts:
effects on photobleaching kinetics and mechanism », Journal Physical Chemistry C, vol.112, n°4, 2008,
p.1094–1100.
Derbal A., Omeiri S., Bouguelia A., Trari M., « Characterization of new heterosystem CuFeO 2 /SnO 2
application to visible-light induced hydrogen evolution », International journal of Hydrogen Energy, vol. 33,
n° 16, 2008, p. 4274 – 4282.
Elaziouti A., Laouedj N., Bekka A., « Synthesis, characterization and UV-A light photocatalytic activity of
20 wt%SrO–CuBi 2 O 4 composite », Applied Surface Science,vol. 258, n° 12, 2012, p. 5010– 5024.
Fernandez J., Kiwi J., Lizama C. Freer J., Baeza J., Mansilla H.D., « Factorial experimental design of
Orange II photocatalytic decolouration », Journal of Photochemistry and Photobiology A: Chemistry, vol. 151,
n° 1-3, 2002, p. 213-21
.Fujishima A., Honda, K., « Electrochemical photolysis of water at a semiconductor electrode », Nature, 238,
1972, p. 37–38.
Geng J.Q., Jiang Z.Y., Wang Y.B., Yang D., « Carbon- modified TiO 2 nanotubes with enhanced photocatalytic
activity synthesized by a facile wet chemistry method », Scripta Materialia, vol. 59, n° 3, 2008, p. 352–355.
Gurlo A., « Interplay between O 2 and SnO 2 : Oxygen ionosorption and scpectroscopic evidence for adsorbed
oxygen
», European journal of Chemical Physics and physical Chemistry, vol. 7, n° 10, 2006, p. 2041- 2052.
Kim Y.I., Atherton S. J., Brigham E. S., Mallouk T. E., « Sensitized layered metal oxide semiconductor particles
for photochemical hydrogen evolution from nonsacrificial electron donors », Journal of physical Chemistry, vol.
97, n° 45, 1993, p. 11802- 11810.
Li H., Liua G., Duana X., « Monoclinic BiVO 4 with regular morphologies: hydrothermal synthesis, characterization
and photocatalytic properties », Materials Chemistry and Physics, vol.115, n° 1 , 2009, p. 9−13.
Li L., Yan B. J., « CeO 2 -Bi 2 O 3 nanocomposite: Two step synthesis, microstructure and photocatalytic activity »,
Journal of Non-Crystalline Solids, vol. 355, n° 13, 2009, p.776−779.
Lin X., Huang F., Xing J., Wang W., Xu F., « Heterojunction semiconductor SnO 2 /SrNb 2 O 6 with an enhanced
photocatalytic activity: The significance of chemically bonded interface », Acta Materialia, vol. 56, n° 12 ,
2008, p. 2699–2705.
Liu R., Ye H., Xiong X., Liu H., « Fabrication of TiO 2 /ZnO composite nanofibers by electrospinning photocatalytic
and their property », Materials Chemistry and Physics, Vol. 121, n° 3, 2010, p. 432−439.
Liu W., Chen S., Zhang S., Zhao W., Zhang H., Yu X., « Preparation and characterization of p–n heterojunction
photocatalyst p-CuBi 2 O 4 /n-TiO 2 with high photocatalytic activity under visible and UV light irradiation »,
Journal of Nanoparticle Research, vol. 12, n° 4, 2010, p. 1355−1366.
Lu X., Li X., Chen F., Ni C., Chen Z., « Hydrothermal synthesis of prism-like mesocrystal CeO 2 », Journal of
Alloys and Compounds, vol. 476, n° 1-2, 2009, p. 958–962.
Magesh G., Viswanathan B., Viswanathan R.P., Varadarajan T. K., « Photocatalytic behavior of CeO 2 -TiO 2
system for degradation of methylene blue », Indian Journal of Chemistry. Vol. 48A,n°.4, 2009, p. 480-488.
Mohamed R.M., Aazam E.S., « Photocatalytic Oxidation of Carbon Monoxide over NiO/SnO 𝟐 Nanocomposites
17
 under UV Irradiation », Journal of Nanotechnology, vol. 2012, 2012, p. 1-9.
Mora-Sero I., Bisquert J., Dittrich T., Belaidi A., Susha A.S., Rogach,A.L., Photosensitization of TiO 2 layers with
CdSe quantum dots: correlation between light absorption and photoinjection », Journal Physical Chemistry C,
vol. 111, n° 40, 2007, p. 14889–14892.
Mukhpadhyay A.K., Mitra P., Chatterjee A.P., Maiti H.S., Tin Dioxide thin Film Gas Sensor », Ceramics
International, vol. 26, n° 2, 2000, p. 123-132.
Nathan T. H., Holmberg C. V., Korgel B. A., Mullins C. B., « Electrochemical Synthesis and Characterization
of p-CuBi 2 O 4 Thin Film Photocathodes », Journal Physical Chemistry C, vol. 116, n° 10, 2012, p. 6459−6466.
Nayral, C., Viala, E., Collière, V., Fau, P., Senocq, F., Maisonnat, A., Caudret, B., « Synthesis and use of a
novel SnO 2 nanomaterial for gas sensing », Applied Surface Science, vol.164, n°1-4, 2000, p. 219-226.
Pany W, Zhang H, Chen Y., « Electrical mechanical properties of PMMA/nano- ATO composites », Journal of
Materials Science and Technology, vol. 25, n°, 2, 2009, p. 247–250.
Pardeski S.K., Patil A.B., « Solar photocatalytic degradation of model endocrine disrupter in water using zinc oxid
»,Journal of Hazardous Materials, vol. 163, n° 1, 2009, p. 403-409.
Pullar R.C., Taylor M.D., Bhattacharya AK., « The manufacture of yttrium aluminium garnet (YAG) fibres by blow
spinning from a sol-gel precursor », Journ al European of Ceramics Society, vol. 18, n°. 12, 1988, p.
1759-1764.
Rakhshani A.E., Makdisi Y., Ramazaniyan H.A., « Electronic and optical properties of fluorine- doped tin oxide
Films », Journal of Applied Physics, vol. 83, n° 2, 1998, p. 1049-1057.
Sasahara A., Pang C.L., Onishi H., « Local work function of Pt clusters vacuum-deposited on a TiO 2 surface »,
Journal of Physical Chemistry B, vol. 110, n° 35, 2006, p. 17584–17588.
Shen J., Cortright R.D., Chen Y., Dumesic J.A., « Microcalorimetric and infrared spectroscopic studies of γ-Al 2 O 3
modified by tin oxides », Catalysis Letters, vol. 26, n° 3-4, 1994, p. 247-257..
Sikong, L., Kongreong, B., Kantachote, D., Sutthisripok, W., « Photocatalytic Activity and Antibacterial Behavior
of Fe3+-Doped TiO 2 /SnO 2 Nanoparticles », Energy Research Journal, vol. 1, 2010, p.120-125.
Teegarden K., « Halide lattices », Luminescence and In-organics Solids, 1966, p. 53-118.
Teeramongkonrasmee A., Sriyudthsak M., « Methanol and ammonia sensing characteristics of sol–gel derived
thin film gas sensor », Sensors and Actuators B: Chemical, vol. 66, n° 1-3, 2000, p. 256-259.
Vasanth Kumar K., Porkodi K., Rocha F., « Langmuir–Hinshelwood kinetics – a theoretical study », Catalysis
Communication, vol. 9, n° 1, 2008, p. 82–84.
Wang X., Lian W., Fu X., Basset J.M., Lefebvre F., « Structure, preparation and photocatalytic activity of
titaniumoxides on MCM-41 », Journal of Catalysis, vol. 238, n° 1, 2006, p. 13–20.
Wang C., Zhao J., Wang X., Mai B., Sheng G., Peng P., Fu J., « Preparation, characterization and photocatalytic
activity of nano-sized ZnO/SnO 2 coupled photocatalysts » Applied Catalysis B: Environmental, vol. 39, n° 3,
2002, p. 269–279.
Xi L., Qian D., Tang X., Chen C., « High surface area SnO 2 nanoparticles: Synthesis and gas sensing properties »,
Material Chemistry and Physics, vol. 108, n° 2-3, 2008, p. 232-236.
Xu Y., Schoonen M.A.A., « The absolute energy positions of conduction and bands of selected semiconducting
Minerals », American Mineralogy, vol. 85, n°3-4, 2000, p. 543-556.
Yang H., Ouyang J., Tang A., Xiao Y., Li X., Dong X., « Eletrochemical synthesis and photocatalytic
property of cuprous oxide nanoparticles », Material Resources Bulletin. Vol.41, 2006, p. 1310–1318.
Yang H.Y., Yu S. F., Cheng C. W., Tsang S. H., Liang H. K., Fan H. J., « Randomly packed n-SnO 2
nanorods/p-SiC heterojunction light-emitting diodes », Applied Physics Letters, vol. 95, n° 201104, 2009, p. 1-3
Ying Z., Wan Q., Song Z.T., Feng S.L., « SnO2 nanowhiskers and their ethanol sensing characteristics »,
Nanotechnology, vol. 15, n°. 11, 2004, p.1682-1684.
Yu J., Su Y., Cheng B., Zhou M., « Effects of pH on the microstructures and photocatalytic activity of mesoporous
nanocrystalline titania powders prepared via hydrothermal method », Journal of Molecular Catalysis A:
Chemical, vol. 258, n° 1-2, 2008, p. 104–112.
Zhang C., Zhu YF., « Synthesis of square Bi 2 WO 6 nanoplates as high-activity visible-light-driven photocatalysts »,
Chemical Materials, vol.17, n° 13, 2005, p. 3537–3545.
Zhang L., Li J., Chen Z., Tang Y., Yu Y., « Preparation of Fenton reagent with H 2 O 2 generated by solar light-
illuminated nano- Cu 2 O/MWNTs composites », Applied Catalysis A: general,, vol. 299, n° 1, 2006, p. 292–
297.
Zhang J., Xiong Z., Zhao XS., « Graphene–metal–oxide composites for the degradation of dyes under visible light
Irradiation », Journal of Materials Chemistry, vol. 21, n° 11, 2011, p. 3634-3640.
Zhang, L., Zhang, H., Huang, H., Liu, Y., Kang, Z., « Ag 3 PO 4 /SnO 2 Semiconductor Nanocomposites with
Enhanced Photocatalytic Activity and Stability », New Journal of Chemistry, vol.36, 2012, p.1541-1544
Zhang F., Zhao J., Shan T., Hidaka H., Pelizzetti E., Serpone N., « TiO 2 -assisted photodegradation of dye pollutants :
II. Adsorption and degradation kinetics of eosin in TiO 2 , dispersions under visible light irradiation », Applied
Catalysis B: Environmental, vol. 15, n° 1-2, 1998, p. 147-156.
Zhuang H. S., Xia H.L., Zhang T., Xiao D.C., « Synthesis, characterization, and visible-light photocatalytic activity
of Fe 2 O 3 /SnO 2 nanocomposites », Materials Sci-Poland, vol. 26, 2008, p. 517-526.

18
19
Contribution a l’efficience d’utilisation du phosphore chez
le blé dur (triticum durum desf.) dans la région de Biskra
Naima Mebrek * , Zohra Melakhessou *
Soumia Fadlaoui **, Fairouz Zerroug **

* Département des Sciences Agronomiques, Université Mohamed Kheidar Biskra, Algérie

email :mebrekn@yahoo.fr
email :zmelakhessou @yahoo.fr
** Département des Sciences Agronomiques, Université Mohamed Kheidar Biskra, Algérie

Résumé. La fertilisation a pour but essentiel de maintenir ou d’accroitre la ri-

chesse d’un sol en éléments organiques ou minéraux notamment le phosphore
qui exerce plusieurs fonctions physiologiques et métaboliques sur la plante à
titre d’augmenter la production.
Une expérimentation a été réalisée sur l’efficacité d’utilisation du phosphore
portant sur quatre variétés de blé dur (Triticum durum Desf.) soumises à quatre
doses différentes d’engrais phosphatés (0 ,40 ,80 ,120 U de P2O5) sous forme
de superphosphate triple (46%) pour objectif d’étudier leur effet sur ses quatre
variétés (Waha, GTA dur, Vitron, Cirta). Dans cette étude, nos résultats mon-
trent que la plus importante accumulation de phosphore a été remarquée au
stade fin tallage au niveau de la dose 40 U de P2O5 avec une moyenne de
1.18%. Par contre, la dose 80 U a entrainé une amélioration du rendement en
grains (46,89 qx/ha) et la dose 120 U affecte mieux ses composantes principa-
lement le nombre de grains /épis (37,87grains /épis) et nombre d’épis
/m2(267,29 épis/m2) ainsi que la production de la biomasse sèche totale
(1227,08 g/m2). La variété GTA dur valorise mieux les apports appliqués de
P2O5 avec un meilleur rendement en grains et une production de la matière
sèche totale respectivement 49,72qx/ha ;1227,08g/ m2.
Mots clés : Blé dur, Fertilisation phosphatée, efficience, Région aride (Biskra).

1
Contribution a l’efficience d’utilisation du phosphore chez le blé dur dans la région de Biskra.

1. Introduction
La culture des céréales est la spéculation prédominante de l’agriculture Algérienne.
Elle s’étend sur près de six millions d’hectares dans un système biennal dominant jachère -
céréale (Saraoui, 2011). La situation actuelle de l'Algérie nécessite une meilleure prise en
charge de l'amélioration de la production agricole principalement celle de cette culture straté-
gique de large consommation. Le pays figure actuellement parmi les premiers importateurs
mondiaux de blé dur en s’accaparant de près de 50 % du marché mondial (CIC, 2007) in
(Saraoui, 2011). La production nationale de blé est faible ne permet de satisfaire qu’environ
30 % des besoins nationaux d’une population de plus en plus croissante estimés à plus de 7
millions de tonnes (Ministère de l'Agriculture, 2008).
Cette spéculation est confrontée à plusieurs contraintes biotiques et abiotiques dont no-
tamment le faible usage des engrais .Selon le recensement l’Algérie utilise peu d’engrais
comparativement au Maroc. L’utilisation se stabilise autour de 45 unités d’éléments
fertilisants par hectare, mais reste au-dessous des normes d’intensification et
d’amélioration de la production (FAO, 2005) et aussi par l’impact négatif de l’irrégularité
des précipitations sur la volonté d’investissement des agriculteurs (notamment en en-
grais) et par la faible rentabilité de certaines productions. Parmi les principaux éléments
nutritifs limitant la production des blés, le phosphore.
L’intérêt accordé, dans cette étude au phosphore tient aussi à sa nature en tant qu’élément
peu mobile dans le sol (Munns et Mousse ,1980 cité par Daoui ,2007), et donc peu acces-
sible pour les plantes .Environ 80% du phosphore est immobilisé et devient indisponible pour
les plantes (Holford, 1997 in Daoui, 2007).
De ce fait, le raisonnement de la fertilisation phosphatée devrait tenir compte non seule-
ment des besoins de la plante en cet élément mais aussi des mécanismes de sa mise à la dis-
ponibilité et de son utilisation par celle-ci, pour l’élaboration du rendement économique.
Notre étude porte sur l’efficience d’utilisation du phosphore vis-à-vis différentes variétés
de blé dur et de rechercher la variété qui valorise mieux le phosphore et la dose de phos-
phore convenable pour l’obtention de bon rendement.

2. Matériels et méthodes
L’analyse chimique montre que notre sol expérimental est moyennement faible en phos-
phore (148ppm=0.148%) (Soltner 2005a).Quatre variétés de blé dur (Waha, GTA dur, Vi-
tron et Cirta) soumises à des apports ou non de P 2 O 5 (0,40,80 et 120 kg /ha ) apportés avant
le semis sous forme de super triple phosphate (Ca (H 2 Po 4 /H 2 O de 46%) selon un dispositif
expérimental de type split plot à quatre répétitions où le traitement phosphaté à la grande
parcelle ( facteur principal) et la variété à la petite parcelle ( facteur secondaire).

2.1. Paramètres retenus

- Teneur en phosphore total de la biomasse sèche aérienne (dosage de phosphore à l’aide
du spectrophotomètre atomique au stade fin tallage, épiaison et remplissage des grains),

2
 N. Mebrek et al.

-Rendement et ses composantes (nombre d’épis /m2, nombre de grains par épis poids de
1000graines)
-Indice de récolte et teneur du phosphore ans les graines

2.2. Outil statistique :

L’analyse de la variance à trois critères de classification (bloc, phosphore, variété) a été
effectuée à l’aide du logiciel Excel Stat. La comparaison des moyennes a été faite selon le
test de Newman –Keuls au seuil de probabilité de 5%.

3 Résultats et discussion
3.1. Effet de l’apport du phosphore sur la production de la biomasse
sèche aérienne de blé dur aux différents stades
Romer (1985) in Mihoub (2009), a montré que l’application précoce de phosphore
augmente la matière sèche de blé.
Les variétés qui accumulent mieux le phosphore sont celui qui élaborent plus de matière
sèche).Vitron et Waha accumulent plus de biomasse aux stades fin tallage (avec environ 29
g/100g de matière fraiche) et épiaison (Waha 25.15 g/100g de matière fraiche, Vi-
tron24.28 g/100g de matière fraiche MF).
Au stade remplissage des grains Cirta et Waha accumulent mieux la matière sèche que les
deux autres variétés avec respectivement (56.76g, 50.22g/100gr de MF).
L’apport de phosphore a un effet bénéfique sur la production de la matière sèche surtout
au stade fin tallage, puis il migre vers les graines ce qui influe sur l’augmentation de la
quantité de biomasse aérienne produite.
Au stade fin tallage, épiaison: l’apport du 40U de P2O5 a entrainé des meilleurs ren-
dements en matière sèche respectivement 29,08 g/100g; 24,84 g/100g de MF.
Au stade remplissage des grains, l’apport de 120U de P2O5 a révélé une valeur élevée
d’une moyenne de 52,85 g/100g de MF où la variété Cirta réalise la meilleure moyenne de
matière sèche avec 56,75 g/100g de MF.

3
Contribution a l’efficience d’utilisation du phosphore chez le blé dur dans la région de Biskra.

Figure 01 : Effet de l’apport du P et de la variété sur la teneur en MS (g /100gr de MF) au

cours de différents stades de développement.

3.2. Les composantes du rendement

2
3.2.1. Nombre d’épis/m

Le nombre d’épis le plus élevé est remarqué chez la variété Waha avec environ
280épis/m2 suivis par les deux variétés Vitron et GTA dur avec respectivement 262 et
245épis/m2 et la variété Cirta en troisième groupe avec une moyenne de 220
épis/m2.L’apport de 120U de P2O5 augmente le nombre d’épis /m2 par une moyenne remar-
quable de 267,29 épis /m2 (un gain d’environ 12% par rapport à la dose 40U de P2O5).

3.2.2. Nombres des grains /épis

Le nombre de grains par épis se constitue à partir du début de tallage environ et il est fixé
à la floraison .Il est en fonction de la fertilité de l’épi. Cette dernière dépendra de
l’alimentation minérale surtout en éléments essentiels NPK. Cette composante est une ca-
ractéristique variétale, très influencée par le nombre d’épis/m² elle est fortement liée au
rendement grains.
Romer (1985) cité par Mihoub(2009), a montré que l’application précoce du phosphore
augmente le nombre d’épillets par épi et le nombre de grains par épi.
La variété a un effet sur le nombre de grains par épi.GTA dur avec une moyenne
d’environ 39.82 graines / épi, suivis par Vitron, Cirta et Waha avec respectivement
33,78 ;30 et 29 .75 grains/ épi. Cependant le nombre de grains /épi passe de 37.87 pour la
dose120Ude P2O5 à 28.67 grains / épi pour la dose 40Ude P2O5

4
 N. Mebrek et al.

3.2.3. Poids de 1000 graines

Est un caractère essentiellement variétal (Borojevic et Williams, 1980 in

Guelfen,2009).Le meilleur poids de 1000 graines est enregistré avec la variété Waha par
une moyenne de 54.86 gramme et la variété Cirta avec un poids de 1000graines bas de 43.38
gr (un gain d’environ 21%)

3.2.4. Rendement en grains

La variété GTA dur a fourni le meilleur rendement grain avec une moyenne de
497,2gr/m2 (49 ,7qx/ha) suivis par les deux variétés Waha et Vitron avec respectivement 484
,7 et 424,9gr/m2, la variété Cirta présente le plus faible rendement avec une moyenne de 302
,66g/ m2 (tableau 01).

Doses GTA-dur Waha Vitron Cirta Moyenne

0 U P2O5 516.1 457 382.4 299.6 413.8
40 U P2O5 469 410.7 330.6 256.2 366.6
80 U P2O5 464.1 613.8 466 332.1 469
120 U P2O5 489.4 507.4 520.4 322.8 460
Moyenne 484.7 ***a 497.22 ***a 424.9 ***a 302.66 ***b 427.35

TAB. 1- Variations moyenne du rendement grain en fonction de différentes doses de P2O5

et les différentes variétés de blé dur et test de Newman et Keuls (5%).

3.3. Indice de récolte

Concernant l’indice de récolte qui définit comme étant le rapport entre le
rendement en grain et le rendement en matière sèche totale. La variété Vitron à réaliser la
meilleure translocation de la matière sèche totale vers le grain avec un indice de récolte (IR)
de 47.20%. Les deux variétés Waha et GTA dur présentent des indices de récoltes de l’ordre
de 42.87 et 41.88% respectivement et la variété Cirta présente le plus faible indice de
récolte (30 .15%). Ainsi, l’apport de 80U de P2O5 a permis l’amélioration, bien que non
significative de la translocation de la matière sèche vers le grain avec un indice de récolte
de 47 .47% et la dose 40U de P2O5 enregistre le faible indice de récolte 36.34%.

3.5. Teneur du phosphore dans les grains

Lorsqu’une espèce est cultivée pour ses graines, l’essentiel du phosphore prélevé par
la culture est présent dans le grain et donc exporté. Les variétés qui présentent des teneurs
en phosphore élevés sont respectivement Cirta (0 ,532% de matière sèche MS), Vitron
(0,519% de MS) suivis par la variété GTA dur (0,456% de MS) et la variété qui
n’accumulent pas beaucoup du phosphore Waha avec une teneur du phosphore dans le
grain de 0,348% de MS) .La dose du phosphore n’a pas un effet significatif sur la teneur du

5
Contribution a l’efficience d’utilisation du phosphore chez le blé dur dans la région de Biskra.

phosphore dans la graine mais sans oublier que la dose 40U P 2O5 donne la meilleure
quantité du phosphore (0,496% de MS) par rapport au témoin (sans apport de P2O5) (un gain
de 14% de phosphore par rapport au témoin sans phosphore).

4. Conclusion
Partant d’une teneur initiale du sol en phosphore égale à 0,148%, et d’après Soltner
(2005b) notre sol est moyennement faible en phosphore. C’est pour cette raison nous
avons réalisé notre expérimentation avec des apports croissant de P 2O5.
La réponse de la production (biomasse aérienne) aux différents stades de la culture (Tal-
lage, épiaison et remplissage des grains) aux apports supplémentaires du phosphore a été
nulle. En plus un apport de 40 U, on a assisté à l’élévation de la production de la
matière sèche aérienne d’environ 29%. La teneur en phosphore au moment du fin tallage
est significative avec un apport de 40 U (1,19% du phosphore). La teneur en phosphore de la
plante diminue régulièrement du stade tallage jusqu’au stade floraison voir même
le remplissage des grains, ceci s’explique par la migration du phosphore des organes
végétaux vers les organes producteurs (grain de blé).
L’apport du phosphore a eu un effet sur le nombre de grains / épis avec une
moyenne d’environ 38 grains / épis à la dose 120 U. mais cette amélioration ne s’est
traduite par l’amélioration du rendement en grains. Le nombre de grains par épis a été
positivement corrélé au rendement grains (r= 0,6*), ce qui montre une compensation entre
ces deux composantes.
Le comportement variétal a été déterminant dans le rendement et ses composantes et
2
aussi par la teneur du phosphore dans la graine (nombre d’épis/ m , nombre de
2
grains/épis, poids de 1000 graines, , rendement grains/m ).
2
La variété GTA dur qui a réalisé le meilleur rendement grains (497,2g/m ) a assuré une
translocation des photos assimilas vers les grains (0,64% de phosphore) et un indice
de récolte acceptable (47,21%). Si on ajoute à ceci que cette variété présente le meilleur
nombre de grains /épis(environ 40 grains /épis), un poids de 1000 graine important (50,86g)
ceci s’explique que la variété GTA dur est considéré comme un bon génotype d’un point de
vue efficience d’utilisation du phosphore (peut exporter 56,45kg/ha du phosphore)en compa-
raison avec Waha qui exporte faiblement le phosphore (environ 41kg/ha).

Références
Daoui. K., 2007 .Recherche des stratégies d’amélioration de l’efficience d’utilisation du
phosphore chez la fève (Vicia faba L.) dans les conditions d’agriculture pluviale au Ma-
roc. Thèse .Doc .Université Catholique de Louvain. Pp. 22-42.
FAO., 2005 Utilisation des engrais par culture en Algérie, Première édition, Organisa-
tion des Nations Unies pour l’alimentation et l’agriculture, Rome : Pp.27, 28,33.
Guelfen. M., 2009 .Etude des différences génotypiques sur l’absorption de l’azote chez le blé
tendre (Triticum aestivum Desf.), Thèse. Mag. INES. Agronomie .Batna : 61p.

6
 N. Mebrek et al.

GC ; ITCMI ; ITDAS et ITAFV., 2010 .Manuel d’utilisation des engrais, Ed. Société De
Fertilisants D’Algérie FERTIAL SPA : Pp.4-7.
Mihoub . A., 2008 .Effet de la fertilisation phosphatée sur la nutrition azotée et la
productivité d'une culture de blé dur (Triticum durum L.) Var Carioca dans la région d'El-
Goléa. Thèse d’ingénieur .Université de Kasdi- Merbah Ouargla : Pp.11, 12.
Saraoui . T., 2011 .Etude de la variabilité morphologique de populations F2 de blé
dur(Triticum durum Desf.): Utilisation d’un indice de sélection. Thèse .Mag. Université
Hadj Lakhdar .Batna : Pp.10 -11.
Soltner , D. 2005a .Les bases de la production végétale.Tome I .Le sol et son amélioration
,24e Edition. Collection Sciences Techniques et techniques agricole : Pp. 113-115,375,
379,383.
Soltner , D. 2005b .Les bases de la production végétale Tome III la plante et son amélio-
ration ,4e Edition. Collection Sciences et Techniques Agricole : Pp.144-149.

Summary
Fertilization essential to maintain or increase the richness of soil organic elements or
minerals including phosphorus has several physiological and metabolic functions of the plant
as to increase production.
An experiment was conducted on the efficient use of phosphorus on four varieties of du-
rum wheat (Triticum durum Desf. ) Subjected to four different doses of phosphate fertilizers
(0 , 40, 80 , 120 U P2O5 ) as triple superphosphate ( 46%) aims to study their effect on the
four varieties ( Waha , GTA hard Vitron , Cirta ) . In this study, our results show that the
greater accumulation of phosphorus was noticed at the end of tillering at the dose of 40 U
P2O5 with an average of 1.18 %. For cons , the dose 80 U resulted improved grain yield (
46.89 quintals / ha) and 120 U dose best components mainly affect the number of grains / ear
( 37.87 grains / ear ) and number of ears / m² ( 267.29 épis/m² ) and the production of total
dry biomass ( 1227.08 g/m²) . GTA hard variety best values the contributions of P2O5 ap-
plied with better grain yield and production of total dry matter respectively 49.72 quintals /
ha , 1227.08 g / m².
Keywords : Durum wheat, phosphate fertilization , efficiency , Arid Region ( Biskra ) .

7
 Pesticides in Morocco: knowledge attitude and
safety
Benaboud. J1, Elachouri. M1 ; Oujidi. J3; Chafi. A1
1 : University Mohammed I Sciences Faculty, Department of Biology Laboratory of Envi-
ronment.
2: University Mohammed I Sciences Faculty, Department of Biology Laboratory of Eth-
nopharmacology
2: Municipal Office of Public Health Berkane
Corresponding author: Benaboud Jamal University Med I
Faculty of Sciences Oujda
Departement of Biology
Laboratory of environment and hydrobiology
Tel: +212665662404
Mail: jamalbenaboud@yahoo.fr

Abstract. Despite their toxicity toward Human health and environment, the pesticides are
widely used in developing countries. Evaluating the pattern of their use would be interesting to
assess the appropriateness of adequate intervention. In this paper, results are presented from a
study with 140 farmers using a standardized questionnaire, to assess their knowledge, attitude,
and practice toward these chemicals. We found that they had a low level of education, and the
knowledge on pesticide and the preventive measure taken were low in correlation with the edu-
cational level. We highlighted also the use of contraband pesticides in this area. The common
pictograms used on pesticides labels weren’t known by many farmers and the worst 33% give
false interpretation or misunderstood of these pictograms. Pesticide safety education is neces-
sary in order to induce protective behavior among farmers, and the comprehension of picto-
grams on pesticides labels in order to reduce the risk of poisoning. The government must ensure
a proper legislation toward phytosanitary product to fight the use of smuggled product and
sensitize the users about their danger.

Keywords : Pesticides, knowledge, preventive measures, contraband pesticide

I- Introduction :
Pesticides are widely used around the world, especially in agriculture for crop protection. Ac-
cording to the WHO, developing countries use about 20% of the pesticides in the world, and
this use is increasing (WHO and UNEP, 1990): this intrinsically dangerous technology is being
promoted in a setting without technical and human resources to control it properly (Wesseling
et al., 1997).
Farm workers, particularly in developing countries, are at a high risk of experiencing short- and
long-term health effects from exposures to pesticides (Yassin et al., 2002; London et al., 1997;
London and Myers, 1995). The health risks linked to pesticide use in agriculture have been
highlighted in numerous research studies and range from acute mild to severe symptoms (e.g.,
headaches, vomiting, skin rashes, respiratory problems, eye irritations, seizures, coma, death) to
various chronic effects (e.g., cancer, asthma, dermatitis, endocrine disruption, birth defects)
(Kishi, 2005; Strong et al., 2004; Alvanja et al., 2004; Kamel and Hoppin, 2004; Colosio et al.,
2003; Dalvie et al., 2004). Studies on knowledge, attitudes, and practices (KAP) indicate that
Pesticides in Morocco: knowledge attitude and safety

unsafe use of pesticides is common in developing countries, with a further need for research
focusing on simple methods for surveillance, in order to develop and evaluate rapid local inter-
ventions (Wesselinget al., 1997). The workers’ knowledge of hazards, which must be factual
and correct, is important for the prevention of acute poisoning: erroneous beliefs can seriously
impair workers’ capacity to protect themselves against risks (Koh and Jeyaratnam, 1996). In
addition from 1988 in an effort to target pesticide risk communication at illiterate populations,
the United Nations Food and Agricultural Organization (FAO) and the then International Asso-
ciation of Agrochemical Manufacturers (GIFAP; now referred to as Crop Life International)
began promoting the use of pictograms on pesticide labels used in developing countries (Forget
et al., 1990; FAO, 2002). These pictograms were viewed as a mechanism for communicating
technical risk assessment data for specific pesticides in a perceived simple format, without
words, that would be universally understood by semi- and illiterate populations (FAO, 2005).
In Morocco pesticide organization started early by the Decree of 1922 ho classify the toxic
substance designed for agricultural use, after that in 1966 come the decree to classify the orga-
nochlorine, and define the endosulfan being a highly toxic substance. Despite of a promoted
liste by the minister of agriculture in 1984, of the officially forbidden pesticides and the Dahir
of 1997 who control the sell and commercialization of phytosanitary product, government con-
trol and law enforcement are still weak.
The objective of our study was to assess the knowledge of pesticide applicators; the protection
measures taken by them, and at last evaluating the understanding of pictograms on pesticide
label by the farmers.
I- Materials and methods

2-1- Area of study

The area of Eastern Morocco is located, as shown in Fig1, in East north of Morocco. It is
limited to North by the Mediterranean, the East and the South by the Algerian borders, in the
West by the provinces of Alhoceima, Taza, Boulmmane and Errachidia. The Eastern Morocco
is the second largest region in the kingdom, on term of superficies; it covers an area of 52,820
km2 or 11.6% of the total area of the country. The majority of agriculture within the area of
Eastern Morocco concentrates on the level of lower Moulouya irrigated perimeter (fig2) which
extends on 160.000 ha of arable land, including 80.000 ha irrigated. The province of Berkane,
when we conduct our inquiry, is about 60.000 ha of arable land with 40.000 ha irrigated so the
half of irrigated land in this perimeter.
 I. Benaboud et al.

Fig 1: The oriental Morocco

Fig 2: the perimeter of lower Moulouya in the box region of 'Berkane'

2-2- Methodology:
Berkane is divided in 9 commune, we take a randomly sample of farmers from 5 communes:
Laatamna, Madagh, Boughriba, Reggada and Chwihia; because they contain the major agricul-
tural activity in the region of study. A standardized questionnaire was applied, in Order to ob-
Pesticides in Morocco: knowledge attitude and safety

tain data on subjects’ degree of knowledge and prevention measures regarding pesticides, also
they knowledge about the pictogram used in pesticides label; and additional parameter was
investigated: the use of black-market pesticides. Subjects gave their oral informed consent to
participate in the study, after hearing the explanation of the study’s objective, a technician from
the Regional Office of Agriculture (ORMVAM) was our guide, 20 min maximum was allowed
to perform one questionnaire, and 140 farmers participated to the query. The data was analyzed
statistically on the EPIINFO Software release 7 distributed by the Center for Disease Control
and Prevention, Chi2 test for dichotomous or multinomial qualitative variables with an admit-
ted error of 5%, ANOVA for quantitative variables of normal distribution and homogeneous
variances.

II- Result:
3-1 Demographic of study from farmers:

The study involve 140 individuals, the result are shown in figure 1. From the farmers only one
woman was met in the field the age vary from 23 to 71, the global education level was in rela-
tion with the age of the farmers, the more aged was the subject the lower was his level of educa-
tion.
Niveau d'étude

5,8%
8,7% illetrate
illéteré
26,8% Less than 6 years school
primaire
secondaire
More than 6 years school
universitaire
Uiversity
spécialiste
Specialist( (agronomy
ingenieur agro, technicien
technician, agro)
or engineer

36,2%

22,5%

Fig 3: Demographic characteristics of population

3-2- Origin of the pesticide used:
The area of study is known for the high smuggling activity, because of the near border with
Algeria, so we asked the farmers the origin of the phytosanitary product used, if they are ap-
proved pesticide sold by society and resellers or black-market pesticides. Despite the fact that
 I. Benaboud et al.

more than 81% affirmed the use the approved pesticide, 32% from them use in addition product
from contraband (figure 4) indeed the questionnaire give them the possibility to answer if they
use only approved phytosanitary product or beside them also use smuggled one or only illicit
product sold in black-market.

Fig 4: Origin of pesticides used by farmers

3-3 Pesticides knowledge and prevention measures:

In fact 80% of farmers considered pesticide as toxic product, and in the meanwhile 55% think
they need appropriate education about pesticide, however more than 2/3 do not use effec-
tive/any measure of security (table 4), and 50% not respect the dose prescript when they spread
the phytosanitary product on their crop; only 20% affirmed they respect both the manufacturer
notification of use and the dose. More than 40% do not use any special prevention measure
while they manipulate the pesticide, and 30% of them affirm they think only by washing hand
or shower after use they will be no harm, and 88% do not know about the list of forbidden pes-
ticide (Decree of 1997). In addition container fate was also investigated indeed 70% of the sub-
jects would discard pesticide container wastes into the environment (soil or water) or with other
trash. Indeed the correspondences analysis shows that having a lower general educational level
was associated with lower prevention measure and lack of knowledge about pesticides toxicity
(fig5).
Pesticides in Morocco: knowledge attitude and safety

N= 140 %

Know that the pesticide are toxic

Think he need pesticide education 112 80
77 55
Respect the manufacturer notification of use and dose 28 20
Respect notification of security of use only 12 8.6
Respect dose only 41 29.3
Do not respect any 59 42.1
Eat and smoke while they use the pesticides 35 25
Take useless prevention measures 42 30
Do not know about the list of forbidden pesticides 123 88
Table 1: pesticide knowledge of the farmers

3-4- comprehension of pictograms used on pesticides labels:

In order to assess how the label played a role in farm workers analysis of a pesticide’s potential
risk, they were asked if they can identify the common pictograms on the pesticides labels (fig-
ure 5); indeed the skull and cross bones symbol and the flame label was by far the most fre-
quently identified component of the label . The oxidizer pictogram was the least identified by
the farmers (figure 6) and the corrosive was only acknowledged by 2%, 33% gave a false inter-
pretation of the pictograms and 0.5% affirms they didn’t know any of the pictograms on pesti-
cides labels. We conduct a chi-squared test to assess the level of education role in the interpreta-
tion of the pictograms; in fact the higher was the level of education the better was the
comprehension of the pictograms (table 6).
 I. Benaboud et al.

University Specialist

Respect the manufacturer notification of use and dose

Respect notification of security of use only

More than 6 years school

Respect dose only

Less years school

Do not respect

Illiterate

Fig 5: the map of repartition of the observation analyzed by the correspondence analysis.
Pesticides in Morocco: knowledge attitude and safety

Fig 6: Commons Pictograms used on pesticides labels

Fig 6: Pictograms knowledge of the farmers. (N= 140).

III- Discussion:

From this study, we noted that a high proportion of the subjects is lacking in knowledge about
pesticide danger and the measure of prevention against the potential risk of using this chemical.
In fact the level of education was a determining factor toward the knowledge of the farmers and
the measure of prevention. A pressing need of pesticide education and training on the use of
pesticides label as a risk communication tool Basic objectives of education are to ensure that
farmers understand the health hazards of used pesticides, become familiar with them and adopt
proper work practices, use protective measure and equipment properly, practice personal hy-
giene measures, recognize early symptoms of overexposure or poisoning, and obtain first aid at
the earliest time possible. Indeed the WHO has recommended the use of pesticides only by
trained people (WHO, 1991).In most developing countries; a number of important obstacles to
agrochemical safety can be identified: there is insufficient legislation for pesticide use and reg-
istration in addition to a lack of technical regulatory research facilities to monitor pesticide
residues and effects (Kimani and Mwanthi, 1995). Illiteracy, poverty, and medical care stand-
ards result in higher health risks during occupational, accidental, and long-term exposure to
pesticides and their residues (Kimani and Mwanthi, 1995). In addition to that come the use of
illicit product, ho in fact are more toxic than the approved pesticides because of their unknown
origin and composition and they have any information of use and the more important the expi-
ration date is falsified or inexistent.
Result similar to our study have already been reported in other developing countries, indeed in
Lebanon a cross-sectional KAP study among agricultural workers, the general worker popula-
tion, and a group of pesticide distributors revealed that the agricultural worker, ho have a cer-
tain exposure to pesticide, lack in knowledge about pesticide danger and take useless prevention
measures, and had low level of education (P.R Salameh et al 2004). In Gaza strip, an assess-
 I. Benaboud et al.

ment of KAP was done on 189 farm workers: they reported high levels of knowledge of pesti-
cides, but the use of protective measures was poor (Yassin et al,2002). In Kenya, knowledge
about pesticides and awareness regarding their safety in handling and storage was limited in a
rural agricultural community (Kimani and Mwanthi, 1995). An action oriented approach to farm
workers’ education has been undertaken in Nicaragua and Puerto Rico: teaching farm workers
about the hazards and safe use of pesticides, as well as empowering them to take preventive and
protective actions gave a positive result (Weigner and Lyon 1992). In china a safety educational
program decreased the prevalence of pesticide poisoning from 1.05% to 0.25% in one village
taken as leading experience (Chen et al 1998).

The study highlighted also that the risk information in the pictogram are often not understood as
intended, and the risk for the farmers health are increased and this misunderstanding is highly
influenced by the farmers’ specific socio-economic, cultural environment and level of educa-
tion. In South Africa the farm workers’ not only misunderstood the pictograms they often con-
fuse interpretations which lead to inducing even riskier behaviors (H-A Rother 2008). Picto-
grams are less likely to fall victim to misinterpretations if they are developed with the target
audience and are context specific (Christopher et al., 2005; Hoffman, 2000). In some countries
(e.g., the USA, Italy, Japan) there are attempts to develop risk communication tools through a
participatory process of engaging the target population in designing the tools (Quandt, 2004;
Fukuzono et al., 2006; Mereu et al., 2007). Ideally, this process should be addopted in develop-
ing countries, especially with pesticide label development and farmers.
In conclusion the farmers in Eastern Morocco seem to be unaware of real pesticide danger and
lack safety education, and not really know how to deal with the pictogram on the pesticides
label. In addition to that the use of smuggled chemicals ho increases the risk for human health
and the environment. Ho the necessity of an integrated educational and awareness program
from the government toward the farmers, and ensure a proper legislation regarding use of phy-
tosanitary product and public health and hazards.
Acknowledgements
The authors wish to thank the study participants for their contribution to the research. The Au-
thors would specifically like to thanks Dahmani Miloud, Azouzi Mohamed and Boukheffa
Driss for their valuable help in the field investigation near the farmer’s.

Ethical approval
This work was done according to international guidelines for the protection of human subjects
and ethical considerations

Funding
None

Competing interest
None declared

References:
Alvanja, M.C.R., Hoppin, J.A., Kamel, F., 2004. Health effects of chronic pesticide exposure:
cancer and neurotoxicity. Annu. Rev. Public Health 25, 155–197.
Chen, S., He, F., Zhang, Z., et al., 1998. Evaluation of a safety educational program for the
prevention of pesticide poisoning. Med. Lav. 89 (Suppl. 2), S91–98.
Christopher, S., Smith, A., McCormick, A.K.H.G., 2005. Participatory development of a cervi-
cal health brochure for Apsaalooke women. J. Cancer Educ. 20 (3), 173–176.
Pesticides in Morocco: knowledge attitude and safety

Colosio, C., Tiramani, M., Maroni, M., 2003. Neurobehavioral effects of pesticides: state of the
art. Neurotoxicology 24 (4–5), 577–591.
Dalvie, M.A., Myers, J.E., Thompson, M.L., Dyer, S., Robins, T.G., Omar, S., Riebow, J.,
Molekwa, J., Kruger, P., Millar, R., 2004. The hormonal effects of long-term DDT expo-
sure on malaria vector-control workers in Limpopo Province, South Africa. Environ. Res.
96 (1), 9–19.
FAO,2005,.International code of conduct on the distribution and use of pesticides—revised
version. In: Adopted by the 123rd Session of the FAO Council inNovember2002.Food and
Agriculture Organization of the United Nations, Rome.
Food and Agricultural Organization of the United Nations (FAO), 2002. International Code of
Conduct on the Distribution and Use of Pesticides (Revised Version). FAO, Rome.
Forget, G., Goodman, T., de Villiers, A., 1990. Impact of pesticide use on health in developing
countries. In: Proceedings of a Symposium held in Ottawa, Canada, 17–20 September. In-
ternational Development Research Centre, Ottawa.
Fukuzono, T., Sato, T., Takeuchi, Y., Takao, K., Shimokawa, S., Suzuki, I., Zhai, G., Terumoto,
K., Nagasaga, T., Seo, K., Ikeda, S., 2006. Participatory flood risk communication support
system (Pafrics). In: Ikeda, S., Fukuzono, T., Sato, T. (Eds.), A Better Integrated Man-
agement of Disaster Risks: Toward Resilient Society to Emerging Disaster Risks in Mega-
Cities. TERRAPUB and NIED, Tokoyo, pp. 191–211.
Hoffman,V.,2000. Picture Supported Communication in Africa—Fundamentals, Examples and
Recommendations for Appropriate Communication Processin Rural Development Pro-
grammes in Sub-Saharan Africa. Margraf Verlag, Weikersheim,Germany.
Kamel, F., Hoppin, J.A., 2004. Association of pesticide exposure with neurologic dysfunction
and disease. Environ. Health Perspect. 112 (9), 950–958.
Kimani, V., Mwanthi, M., 1995. Agrochemicals exposure and health implications in Githunguri
location, Kenya. East Afr. Med. J. 72,531–535.
Kishi, M., 2005. The health impacts of pesticides: what do we now know? In: Pretty, J. (Ed.),
The Pesticide Detox: Towards a More Sustainable Agriculture. Earthscan, London.
Koh, D., Jeyaratnam, J., 1996. Pesticide hazards in developing countries. Sci. Total Environ.
188 (Suppl. 1), S78–S85.
London, L., Myers, J.E., 1995. Critical issues in agrichemical safety in South Africa. Am. J.
Ind. Med. 27 (1), 1–14.
London, L., Myers, J.E., Nell, V.N., Taylor, T., Thompson, M.L., 1997. An investigation into
neurological and neurobehavioral effects of long-term agrichemical use among deciduous
fruit farm workers in the western cape, South Africa. Environ. Res. 73, 132–145.
Mereu, A., Sardu, C., Minerba, L., Sotgiu, A., Contu, P., 2007. Participative risk communica-
tion in an industrial village in Sardina. J. Epidemiol. Community Health 61, 122–127.
Pascale R. Salameh, Isabelle Baldi, Patrick Brochard, and Bernadette Abi Saleh 2004. Pesti-
cides in Lebanon : Knowledge Attitude and Practice study. Environmental Research 94 1-
6.
Quandt, S.A., Doran, A.M., Rao, P., Hoppin, J.A., Snively, B.M., Arcury, T.A., 2004. Report-
ing pesticide assessment results to farmworker families: development, implementation,
and evaluation of a risk communication strategy. Environ. Health Perspect. 112, 636–642.
Rother.H.A 2008 South African farm workers’ interpretation of risk assessment data expressed
as pictograms on pesticide labels. Environmental Research 108 419-427.
Strong, L.L., Thompson, B., Coronado, G.D., Griffith, W.C., Vigoren, E.M., Islas, I., 2004.
Health symptoms and exposures to organophosphate pesticides in framworkers. Am. J.
Ind. Med. 46, 599–606.
Weinger, M., Lyons, M., 1992. Problem-solving in the fields: an action-oriented approach to
farm workers education about pesticides. Am. J. Ind. Med. 22, 677–690.
 I. Benaboud et al.

Wesseling, C., McConnell, R., Partanen, T., Hogstedt, C., 1997, Agricultural pesticide use in
developing countries: health effects and research needs. Int. J. Health Servey 27, 273–308
WHO, 1991. Safe use of pesticides. Technical Report Series 813, 1–26, WHO, Geneva.
WHO, UNEP, 1990. Public Health Impact of Pesticides Used in Agriculture. WHO, Geneva.
Yassin, M.M., Abu Mourad, T.A., Saffi, J.M., 2002. Knowledge, attitude, practice, and toxicity
symptoms associated with pesticide use among farm workers in the Gaza Strip. Occup.
Environ. Med. 59, 387–393.
Identification of soil salinity within a semi-arid region using
spectral salinity indices

Triki Hela*, Bouaziz Moncef*, **, Benzina Mourad*, Bouaziz Samir*

*National School of Engineers of Sfax- Laboratoire Eau-Energie-Environnement

B.P.W., 3038 Sfax, TUNISIA
** Faculty of environmental sciences, Institute of Geography, TU-Dresden, Helmholtzstr.
10, D- 01069 Dresden, Germany

Abstract. Soil salinity, is an environmental problem that threatens lands

mainly in arid regions. Traditionally, monitoring of salty soils has been a hard
task, due to the high expenses of soil samples analysis. Recently, remote
sensing techniques provide new alternative to assess and monitor salt affected
soil rapidly and over larger areas.
The investigation area is a semi-arid region located in southern Tunisia. This
study aims to identify classes of soil salinity, explore the potential of
multispectral data to discern soil features and patterns of saline soil and predict
soil salinity. For this purpose, Landsat 8 data were used to generate seventeen
spectral indices. Correlations between reflectance indices and Electrical
Conductivity measured on laboratory show that the Short Wave Infrared offers
the best correlation with -0.57 %. Three salinity classes are obtained from
image classification, with an overall accuracy 73%. The calibration model
gives a moderate coefficient of determination R² =33%.

Keywords: soil salinity, remote sensing, Landsat8, spectral salinity

indices, partial least square regression.
Identification of soil salinity using spectral salinity indices

1 Introduction
Salinity is one of the most widespread soil degradation processes on the earth and it
occurs particularly in arid and semi-arid regions (UNEP, 1991). According to the Food and
Agriculture Organization (FAO, 2007) more than 77 mha (million hectares) of land are salt-
affected and about 43 mha are attributed to secondary salinization. Estimations indicate that
about one third of the irrigated lands in the major countries is badly affected by salinity or is
expected to be salinised in the near future (Abbas, A and Khan S., 2007). In Tunisia, salinity
is estimated to 10 % of land which is located mainly in the center and the south parts of the
country (Hachicha M., 2007).
This degradation induces changes in land use. Consequently, monitoring tools are needed
for advancing soil conservation. Conventional soil sampling and laboratory analysis cannot
be effective because they are slow, expensive and could not retrieve all temporal and spatial
variabilities (Zribi M. et al. 2011).
In this context, remote sensing shows a high potential in soil characterization. It uses
electromagnetic energy reflected from objects to obtain data about earth’s features.
Relationship between salt concentration and spectral characteristics of salt-affected soils has
been the subject of research for decades. Several studies aim to discriminate saline areas
from the space (Farifteh J. et al., 2007). Recently, a major challenge of remote sensing, as a
potential alternative technique, is to detect different levels of salinity and sodicity (Allbed A.,
Kumar L., 2013) (Bannari A., 2007). In fact, a large variety of remote sensing techniques
have been used for identifying and monitoring salt affected zones, including aerial photos,
spectro-radiometric measurements, multispectral and hyper-spectral images (Bannari A.,
2007) (Metternicht, G. I. and Zinck J. A., 2003).
On the other hand, different studies have successfully used indirect indicators by spectral
indices to detect and to map soil salinity. According to Allbed A. and Kumar L. (2013) these
indices present a variable degree of success.
This study aims to determine the potential and the limits of spectral salinity indices for
the discrimination of the different soil salinity levels of the study area and predict soil
salinity from ground- truth measurements and spectral indices.

2 Materials and Methods

2.1 Study area
The investigated region is located in Gabes, at the southern east part of Tunisia. It
extends between longitude 10° 0’ 42.59’’-10° 6’ 41.79’’ E and latitudes 33° 46’ 36.20’’- 33°
58’ 14.75’’ N (figure 1). It covers an area of 170 km². It belongs to the Jeffara plain which is
characterized by quaternary deposits. Due to its geographical position, its arid climate is
influenced by the mediterranean sea and the saharian desert. The annual rainfalls are
irregular and vary extremely, with an average of 189 mm/year. 90 % of precipitation occurs
from October to April (Kaabi M., 2013). The annual temperature is high and exceeds 20 °C
(Ferchich A.).
Sample collection was carried out at the end of May 2013. At this time of year the ground
has weak vegetation cover, which disappears completely in some zones. This period is
 Triki et al.

characterized by high temperature that induces accumulation of high amounts of salt at the
soil surface. During field investigations, 61 samples were taken from the soil upper layer (10
cm deep). For each sample, we marked the land use, soil color, texture, surface aspect,
landscape characteristics. The salinity of samples was analyzed in the laboratory using 1/5
(soil: water) diluted extracts. The soil salinity classes were then determined by referring to
the salinity scale proposed by Durand J.H. (1983) (Mathieu et al. 2003).

FIG.1 - Location of the study area.

2.2 Spectral salinity indices

In order to highlight and to detect the different soil salinity levels, several indices are
used. Bouaziz et al. (2011) proposed several spectral salinity indices, such as: SI-1, SI-2 and
SI-3, calculated in MODIS Terra bands and mentioned the power of SI-2 to detect soil
salinity. On the other hand, Abbas et al. (2007) tested salinity indices which, incorporate the
first four bands of IRS-1B LISS-II satellite, but they found that the salinity index (SI) with
just the three first bands shows high performances in identification of saline soils (A.
Benchallal A. et al. 2009). The Indo-Dutch Network Project (IDNP, 2002) employed three
salinity indices SI1-IDNP, SI2-INDP and SI3-INDP. The last, is similar to the ASTER-SI
index (Bannari A. et al., 2008). Douaoui A. and Lepinard P. (2010), developed (IS-vir)
spectral salinity index and showed its potential to reveal salinity measured in the field.
Moreover to these spectral indices, Bouaziz et al. (2011) used three intensities indices
(Int 1, Int 2) and BI (Brightness Index) for MODIS Terra data.
Identification of soil salinity using spectral salinity indices

In this study, we applied 3 intensity indices and 7 spectral salinity indices (table1). The
following abbreviations: B, G, R, NIR, SWIR1, SWIR2 are reflectance in Blue, Green, Red,
Near- Infra-Red, Short Wave Infra-Red 1 and Short Wave Infra-Red 2.

Salinity index

SI1
SI2
SI3
SI
SI1-IDNP

ASTER-SI
SIvir
Int 1
Int2
BI

TAB.1 - Spectral salinity indices.

Vegetation indices

NDVI

SAVI

TAB.2 - Spectral vegetation indices.

2.3 Landsat 8 data

Remote sensing is a promising tool to acquire important information over a large area.
For this study we used data from OLI (Operational Land Imager) sensor implanted on
Landsat8 satellite. Within preprocessing, we removed panchromatic, cirrus and long
wavelength infra red bands. In addition to salinity indices, we used the bands 1, 2, 3, 4, 5, 6
and 7 (centered respectively at: 440 nm, 480 nm, 560 nm, 655 nm, 865 nm, 1610 nm and
2200nm), to highlight performances of Landsat spectral bands in discerning saline soil
features and patterns. Preprocessing and processing of Landsat 8 image was conducted using
ENVI4.5 software.
 Triki et al.

2.4 Vegetation indices

As halophytic vegetation grows naturally in saline soils, it can be used as indicator of
saline soils. Consequently, it’s used as an indirect tool to predict and map soil salinity
(Allbed A., 2013). Several vegetation indices have been applied such as NDVI, SAVI, and
RVI. The Normalized Difference Vegetation Index (NDVI) (table 2) is related to biomass,
chlorophyll content and water stress (Bannariet A. al., 2008). The Soil Adjusted Vegetation
Index (SAVI) (table 1.b) eliminates noise from soil induced variation. It’s employed in areas
where soil backgrounds differed and low canopy cover was present (Metternicht, G. I. and J.
A. Zinck, 2003). The L factor depends of crop density and ranges between 1 (for higher
density) and 1 (for lower density). For the present study, we fixed L to 0.5.

Classes Extremely Very salty soil Non salty soil

salty soil

Regions Coastal Bare Dry Agriculture Agriculture

soil grass area area

EC mean values (dS/m) 9.06 2.54 2.49 2.21 0.51

Samples number 12 16 11 12 10

TAB.3 - Salinity classes.

2.5 Statistical analysis to predict electrical conductivity

Partial Least Square regression for a single y-variable (PLSR1) was used for EC
prediction. This method is widely used in chemometrics to establish relationships between
soil properties and spectral data. It allows resolving the collinearity between variables (Lee
W.S. 2003). To build a PLS model, 2/3 of the samples are randomly selected as a calibration
set. The remaining part 1/3 is used to validate the model. The choice of the best calibration
model depends on the coefficient of determination (R²), the root mean squared error of cross
validation (RMSEC) and the bias (Berthier L., 2008). The models were generated using
Unscrumble 9.7 software.

3 Discussion
3.1 Spectral indices
As mentioned above, we use the seven spectral bands of Landsat 8 data as indices. In
order to evaluate the performances of the potential of the spectral indices in identifying soil
salinity, a Pearson correlation between electrical conductivity (EC) values and the Landsat 8
bands was computed. The results in figure 2 show the highest correlations correspond to
Identification of soil salinity using spectral salinity indices

band 5 (SWIR1) and band 6 (SWIR2) (respectively -0.75 and -0.56). This is in agreement
with Bannari A. et al. (2008) findings.
Among the six computed spectral salinity indices (figure 3), the SI3 and SI indices offer
the highest correlation coefficient: -48% and -47% respectively.

FIG.2-Correlation between Landsat bands FIG.3-Correlation between salinity indices

and EC. and EC.

The correlation between intensity indices and EC is low with a correlation value equal to
42 % (figure 4). This is in agreement with the findings of Bouaziz et al. (2011). Moreover,
vegetation indices present a weak correlation essentially for the NDVI (Figure 5). Yousef
(2011) highlighted that low NDVI values for vegetation areas (olives, figs, almonds) is either
due to recent young plantation (sample 58) or low density and large distance between trees
(about 25 m for olives trees).

FIG.4-Correlation between intensity indices and FIG.5-Correlation between vegetation

EC. indices and EC.
 Triki et al.

3.2 Mapping salinity

The soil salinity of the study area was determined at laboratory using the 1:5 soil- water
extract method. Three classes were obtained: extremely salty soil (EC> 4 dS/m), very salty
soil (2 dS/m< EC < 4 dS/m) and none salty soil (EC< 0.6 dS/m). Table 3 presents the EC
mean values for each class. The extremely salty soil is restricted to the coastal region.
However, the agriculture area (olives, almonds, fig trees) belongs at the same time to very
salty and none salty soils. In spite of vegetation tolerance to salinity in the investigation area,
the salinization enforces several negative impacts on agriculture sector by reducing crop
productivity and affecting soil fertility.
As reported previously, the spectral SWIR1 band (1610 nm) offers the best correlation
coefficient (-0.57 %) to predict saline soil. A combination between saline soil classes
determined from the ground- truth measurements (table 3) and the SWIR1 data was used to
perform an image classification.
The soil salinity map (figure 7) reveals that the highest salinity is assigned to the coastal
area. The vegetation class (which is marked mainly by date palms) ranges between extremely
and very salty soils. These findings are similar to results revealed by Yousef Y. Aldakheel
(2011). They announced the high salinity tolerance of date palms. The very salty soil extends
widely comparing with that none salty.
In order to assess the classification, a confusion matrix was applied. The overall accuracy
is 73%. In details, the results show that none salty soil class is underestimated. This can be
attributed to a confusing reflectance between none salty and very salty soils. This result is
revealed by the findings of Furby et al. (1995) who found that non- salty soils were confused
with bare, extremely saline areas.

FIG.7 - Soil salinity map applied on the SWIR1 of landsat 8 image.

Identification of soil salinity using spectral salinity indices

3.3 Electrical Conductivity modeling

PLSR1 was applied to predict electrical conductivity (as a dependent variable) from
salinity indices (as an independent variables). The best generated model offers a coefficient
of determination of 33%, a RMSE equal to 4.28 dS/m (figure 6) and a bias about 0. The
validation results of the prediction model are summarized in figure 6. The moderate accuracy
of our calibration model for EC is in agreements with Bouaziz et al (2011), who obtained a
coefficient of determination (R²) of 40% using MODIS Terra data.

FIG.6 – Relationship between measured and predicted electrical conductivity (EC) values.

4 Conclusion
The use of spectral salinity indices with ground-truth measurements shows high
performances to identify saline soil over the investigation area. The results reveal that among
seventeen indices, the SWIR1 band offers the highest correlation -0.57%. Three salinity
classes have been selected to classify saline soils in the study region: (i.e., extremely salty,
very salty and non- salty soils).
To compute the accuracy of the classification, a confusion matrix was applied. The
overall accuracy is 73 %, which indicate good classification results. Nevertheless, remotely
sensing data can present some limitations, essentially caused by confusing reflectance
between classes; it presents high potential to characterize soil properties.
A Partial Least Square Regression (PLSR) was performed to predict soil salinity. The
calibration model gives a moderate coefficient of determination (R² = 33%). Future research
by means of non-linear methods and by increasing the number of soil samples should
improve the prediction.
 Triki et al.

References
Abbas A. and Khan S. (2007). Remote Sensing Based Modelling Applications in Land and
Water Management: Using remote sensing for appraisal of irrigated soil salinity.
MODSIM 2007 International Congress on Modelling and Simulation Society of Australia
and New Zelan.
Allbed Amal , Kumar Lalit (2013). Soil Salinity Mapping and Monitoring in Arid and Semi-
Arid Regions Using Remote Sensing Technology: A Review. Advances in Remote
Sensing, 2: 373-385.
Bannari A. Guedon A. M. El-Harti A. Cherkaoui F.Z and El-Ghmari A. (2008).
Characterization of Slightly and Moderately Saline and Sodic Soils in Irrigated
Agriculture Land Using Simulated Data of Advanced Land Imaging (E0-1) Sensor.
Communications in soil Science and Plant Analysis, 39: 2795-2811.
Bastiaanssen W.G.M., Molden D.J., Makin I.W. (2000). Remote sensing for irrigated
agriculture: examples from research and possible applications. Agricultural Water
Management, 46: 137–155.
Benchallal A., Oukil A. and Belhadj-Aissa A. (2009). Identification et détection, par
imagerie, de la degradation des sols par la salinité dans la cuvette de Ouargla, sud de
l’Algérie. Journées d’Animation scientifique (JAS09) de l’AUF Alger.
Berthier L., Pitres J. C., Vaudour E. (2008). Prediction spatiale des teneurs en carbone
organique des sols par spectroscopie de terrain visible-proche infrarouge et imagerie
satellitale SPOT. Etude et Gestion des Sols, 15 (4): 213-224.
Bouaziz Moncef, Matschullat Jӧrg , Gloaguen Richard (2011). Improved remote sensing
detection of soil salinity from a semi-arid climate in Northeast Brazil. Comptes Rendus
Geoscience, 343: 795-803.
DING Jian-li, WU Man-chun and Tashpolat Tiyip (2011). Study on Soil Salinization
Information in Arid Region Using Remote Sensing Technique. Agricultural Sciences in
China, 10(3): 404-411.
Durand J.H. (1983). Les sols irrigables. Agence de Copération Culturelle et Technique/PUF.
Paris: 339.
FAO (2007). Extent and Causes of Salt-affected Soils in Participating Countries. AGL:
Global Network on Integrated Soil Management for Sustainable use of Salt- affected
Soils.
Farifteh J., Van der Meer F., Carranza E. J. M. (2007). Similarity measures for spectral
discrimination of salt-affected soils. International Journal of Remote Sensing. Vol. 28,
No. 23, 10: 5273-5293.
Ferchichi Ali. Etude Climatique en Tunisie PreSaharienne. N°3/96.
Fraser, D., and S. Joseph. (1998). Mapping soil salinity in the Murray Valley (NSW) using
satellite imagery. Proceedings of the 9th Australasian Remote Sensing and
Photogrammetry Conference, 1, paper no.127, Sydney, Australia.
Identification of soil salinity using spectral salinity indices

Furby S. et al., (1995) Detecting and Monitoring Salt-Affected Land: A report from the
LWRRDC Project Detecting and Monitoring Changes in Land Condition through Time
Using Remotely Sensed Data, CSIRO, Division of Mathematics and statistics.
Hachicha Mohamed (2007). Les sols salés et leurs mises en valeur en Tunisie. Secheresse:
18 (1): 45-50.
Hute A. R (1988). A Soil–Adjusted Vegetation Index (SAVI). Remote Sensing of
Environment, 25 (3): 295-309.
IDNP. Indo-Dutch Network Project (2002): A methodology for identification of waterlogging
and soil salinity conditions using remote sensing. Karnal, India: Central Soil Salinity
Research Intitute.
Kaabi Mourad (2013). Etude d’impact sur l’environnement pour le développement de la
concession Nawara Project de construction de l’usine de traitement des gaz à Gabès.
STGP-TESCO-PMT-0805-HS-REP-0002 Edition.
Lee W. S. , Sanchez J. F. , Mylavapu R. S., Choe J. S.. Estimating chemical properties of
Florida soils using spectral reflectance. American Society of AgricultureEngineers ISSN
0001-2351. Transaction of the ASAE, 46 (5): 1443-1453.
Mathieu C et Pieltain F. (2003). Analyse chimique des sols. Ed TEC et doc. Lavoisier.
Paris : 292.
Metternicht, G. I. and Zinck J. A. (2003). Remote sensing of soil salinity: Potentials and
constraints. Remote Sensing of the Environment, 85:1–20.
UNEP (1991), United Nations Environment Program. Status of Desertification and
Implementation of the United Nations Plans of Action to Combat Desertification. UNEP,
Nairobi.
Yousef Y. Aldakheel (2011). Assessing NDVI Spatial Pattern as Related to Irrigation and
Soil Salinity Management in Al-Hassa Oasis. J Indian Soc Remote Sens. 39(2): 171-180.
Zribi M., Baghdadi N., Nolin M. (2011). Remote sensing of soil. Applied and Environmental
Soil Science. Article ID 904561.

Summary
La dégradation des sols par salinité est l’un des principaux problèmes qui menace
l’humanité. Auparavant, le diagnostique de la salinité des sols au laboratoire parait un moyen
lent et couteux. Récemment, la télédétection est utilisée comme une nouvelle démarche plus
rapide, moins chère et qui couvre de larges zones.
La zone d’étude est située au sud est tunisien et caractérisée par un climat semi-aride. Les
objectifs de cette étude sont : identifier les classes de salinité, explorer le potentiel des
données spectrales Landsat 8 et prédire la salinité des sols. Les corrélations établies entre les
indices spectraux et la conductivité électrique, mesurée au laboratoire, montrent que la bande
SWIR (1610 nm) offre la meilleure corrélation avec -0.57%. La classification de l’image
dévoile trois classes de salinité avec une précision de 73%. Le modèle de calibration de
salinité présente un coefficient de détermination modéré avec R² =33%.
Effects of water salinity on milk production and several blood
constituents of Barbarine sheep in a semi arid climate
Wiem Mehdi elGHarbi ; Sourour Abidi *
Hichem Ben Salem **
*
Institut National de la Recherche Agronomique de Tunisie / Laboratoire des Productions
Animales et Fourragères
Wiem_mehdi2000@yahoo.com ; Sourour.abidi@yahoo.fr
http://www.iresa.agrinet.tn
**
Centre International de la Recherche Agronomique des Régions Arides
h.bensalem@cgiar.org
http://www.cgiar.org

Abstract. Seventy lactating sheep were allotted into two groups (n = 35). One
group was offered potable water (0.5 g of salt per 1 l of water) and another
group was offered saline water containing 10 g of salt per 1 l of water. Sheep
were used to evaluate the influence of high drink salty water on milk yield,
chemical and physical characteristics and metabolites blood concentrations.
Milk yield, milk composition of fat and lactose and serum concentrations of
glucose, total protein, uric acid, creatinine and γ-GT were not significantly
affected by water salinity (P>0.05). However, sheep receiving saline water
produced on the 30 days of lactation milk with high level of protein, urea
nitrogen (P<0.05) and low level of mean somatic cells, pH, salinity and
conductivity (P<0.001). Moreover, consuming saline water decreased serum
triglyceride and cholesterol concentrations during the first month of lactation
(P<0.05) and serum urea concentration during the second month (P<0.01).

Keywords : salinity, sheep, milk, blood

1. Introduction
The importance of water quality has long been emphasized for cows, sows and sheep.
One factor that influences water consumption is the salt. Water containing ≤ 13% of NaCl
has been considered satisfactory for sheep (Norman et al., 2002). Arjomandfar et al., (2010)
showed that the saline water resulted in decreased milk production of the cows under heat
stress. As well as, Jaster et al., (1978) noted a depression in the milk yield and a decline in
the production persistency of the cows consuming tap water plus 2500 mg NaCl per L.
However, the available findings on the effect of water salinity on milk production of
lactating sheep are limited and to some extent contradictory (Thomas et al., 2006).
We investigated the effect of salinity water desalination on the milk yield, composition
and physical characteristics and several blood constituents.
Water salinity in lactating Barbarine sheep

2. Materials and Methods

The experiment was carried out on an experimental center of INRA-Tunisia 180 km

southeast of Tunisia. Seventy lactating sheep, 5 years old with a mean body weight of 39.0
±1.3 kg and a body condition score of 3.2 ± 0.5 were randomly allotted to two groups to
receive water containing either 0.5 (potable water; C) or 10 g per l of water (saline water; S).
The mineral content of the water is shown in Table 1.

Element Content
Dry residue (mg/l) 0.45
pH 7.22
Sodium (mg/l) 70.15
Potassium (mg/l) 1.64
Calcium (mg/l) 61.77
Magnesium (mg/l) 19.58
Chlorure (mg/l) 153.02
Sulfate (mg/l) 35.65
Nitrate (mg/l) 8.22
Carbonate (mg/l) 0.01
Bicarbonate (mg/l) 66.34
TAB.1 - Ionic Balance of potable water.
From the pregnancy to 120 days of lactation, all experimental animals received the
different quality of water. On day 10, 30, 45, 60, 90 and 120th of lactation, milk and blood
sampling were performed. Milk samples were obtained after injection of 1.5 ml of oxytocine
in the auricular vein. At the time of milking, we noted the pH, conductivity and salinity. Milk
fat, protein, lactose, urea nitrogen and mean somatic cells were analyzed by infrared
spectrophotometer (Foss 4000 Milkscan; Foss Electric, Chemicals Analysis Laboratory,
OEP, Tunisia).
Blood samples were obtained from the jugular vein. Serum was separated, after
centrifugation of blood samples at 2000 rpm for 15 min, to determine the serum levels of
triglyceride, cholesterol, glucose, total protein, uric acid, urea, creatinine and γ-GT using a
commercial kits (BioSystem Costa Brava, 30 (Barcelone, Spain).
Milk yield, milk composition and physical characteristics and several blood constituents’
data were analyzed by Proc Mixed of the SAS, using repeated measure ANOVA (SAS,
2004). The data are reported as mean ± SE.

3. Results

Increasing of salt level of the drinking did not significantly affect the milk production and
composition in the present experiment (P>0.05), although the concentration of protein and
urea nitrogen and the mean count cell on the 30 days of lactation were higher for S-sheep
(P<0.05).the salinity, conductivity and pH of milk were high significantly affected by the
water salinity used in the present experiment (P<0.01; Table 4). Although physical
characteristics of milk were depleted following drinking saline water.
 W.G. Wiem et al.

C- S- SE P C- S- SE P C- S- SE P
Day of sheep sheep sheep sheep sheep sheep
lactation Milk yield (ml) Fat (%) Proteine (%)
0 84.43 76.68 0.31 NS 12.74 13.33 0.07 NS 15.31 19.25 1.22 NS
10 42.79 41.87 1.71 NS 4.29 4.18 0.03 NS 4.58 4.71 0.54 NS
30 33.90 29.75 1.24 NS 3.56 2.83 1.71 NS 4.10 4.61 0.18 *
45 29.60 27.4 2.07 NS 2.80 3.15 0.09 NS 2.36 2.22 0.01 NS
60 22.17 18.52 0.45 NS 3.10 3.18 0.01 NS 2.15 2.39 0.07 NS
90 16.82 14.27 0.29 NS 2.75 2.98 0.01 NS 1.95 2.11 0.21 NS
Lactose (%) Urea Nitrogen (mg/dl) Mean Somatic Cells
0 3.11 3.15 0.012 NS 11.40 9.24 0.72 NS 22.66 28.33 1.89 NS
10 2.96 2.66 0.03 NS 15.35 16.09 0.22 NS 32.85 35.68 0.94 NS
30 2.85 2.77 0.05 NS 17.32 20.42 1.02 *** 48.38 49.55 0.39 ***
45 2.73 2.66 0.02 NS 16.72 16.97 0.17 NS 56.72 56.55 0.05 NS
60 2.47 2.67 0.06 NS 12.51 13.22 0.12 NS 72.76 74.80 0.67 NS
90 2.35 2.48 0.05 NS 11.85 12.98 0.35 NS 82.60 78.80 0.88 NS
Conductivity (mS/cm) Salinity pH
0 4.05 3.01 0.12 *** 2.50 2.16 0.73 *** 7.05 6.94 0.34 ***
10 4.54 3.40 0.23 ** 2.57 2.35 0.48 *** 7.08 6.86 0.95 ***
30 4.67 3.59 0.08 ** 2.72 2.45 0.28 *** 7.01 6.94 0.37 *
45 4.19 3.17 0.60 * 2.47 1.92 0.66 * 7.02 7.03 0.08 NS
60 3.88 4.08 0.05 NS 2.41 2.62 0.105 NS 7.01 6.99 0.05 NS
90 3.64 3.68 0.01 NS 2.45 2.42 0.01 NS 6.74 6.80 0.15 NS
SE: standard error of means; NS: P > 0.05; *: P < 0.05; **: P < 0.01; ***: P<0.001

TAB 2 - Effects of water salinity on milk production chemical and physical characteristics of
Barbarine sheep in a semi arid climate
Serum concentrations of glucose, total protein, uric acid, creatinine and γ-GT were not
influenced by the water salinity (P>0.05) but there was a significant (P<0.05) effect of water
salinity on the serum triglyceride and cholesterol on day 10 and 30 of lactation. From day 45
to 90, serum urea levels tended (P<0.05) to be lower in lactating sheep on saline water
(Figure 1).

4. Discussion

Water salinity to 10 g of salt per l of water had no significant effect on most of the
parameters studied, although the triglyceride, cholesterol and urea concentrations in the
blood serum were significantly decreased. Homeostatic mechanisms control the level of
minerals in body fluids; therefore, the concentrations of metabolites tend to stabilize after a
period of saline water intake (NRC, 2001).Increased serum metabolites concentration in the
sheep offered water containing a higher salt level may become detrimental to homeostasis in
the long term. The inconsistencies observed on the effect of salt level on lactating sheep
could partly be due to experimental protocols, such as the number of sheep, source of water,
the level of salt used, the duration of the treatment, and the presence of minerals that may
affect the performance but are not measured in such studies; usually, those minerals that are
important in contributing to salt levels are measured (Solomon et al., 1995).
Water salinity in lactating Barbarine sheep

FIG. 1 - Effects of water salinity on several blood constituents of Barbarine sheep in a semi
arid climate
Saline water tended to increase the plasma levels of minerals and thyroid hormones (Bahman
et al. 1993). Milk yield and composition were not affected by Treatment (Table 2). Our
results agree with Valtorta et al., (2008), where no treatment effects of water salinity on milk
production and composition of lactating grazing Holstein cows were detected. Jaster et al.
(1978) reported a depression in the daily milk yield of about 2 kg for cows on salt water, and
stated that although the difference was small, it reflected a trend which, if extended over the
entire lactation, could be dramatic. Solomon et al. (1995) found increases in water intake,
milk production, and milk composition (lactose, protein, fat), although dry matter intake was
not influenced by the water type. According to Bahman et al., (1993), the quality of the
water did not significantly affect the milk production and composition of cows. Sánchez et
al., (1992) examined interrelationships of sodium, potassium, chloride, magnesium, calcium
and phosphorus and concluded that optimal concentrations of macromineral elements for
maximum DM intake or milk yield depend on one another. The indifferences in the milk
yield in these experiments may reflect the indifferences in water consumption (Arjomandfar
et al., 2010) or the indifference in mineral concentration in milk yield (Jaster et al., 1978).
But, these two factors were not measured in our study. Under non-grazing conditions,
Sánchez et al., (1994) also found that feeding high amounts of sodium does not reduce milk
 W.G. Wiem et al.

production or lactation performance. Milk protein and urea nitrogen presented high
concentrations in S-sheep (P<0.05). Those results disagree with Revelli et al., (2005). This
response could indicate somewhat high effective fiber content in the ingested forage,
possibly affected by pasture intake behavior, since grazing animals select leaves and tender
stems (Valtorta et al., 2008).

References
Arjomandfar, M., Zamiri, M. J., Rowghani, E.,Khorvash, M. and G.H. Ghorbani (2010).
Effects of water desalination on milk production and several blood constituents of
Holstein cows in a hot arid climate. Iranian J. Vet. Res. 11:32-46.
Bahman, A.M., Rooke, J.A. and J.H. Topps (1993). The performance of dairy cows offered
drinking water of low or high salinity in a hot arid climate. Ani. Prod J. 57: 23-28.
Jaster, E.H., Schuh, J.D. and T.N. Wegner (1978). Physiological effects of saline drinking
water on high producing dairy cows. J. Dairy Sci.61: 66-71.
Norman, H.C., Dynes, R.A. and D.G. Masters (2002). Nutritive Value of Plants Growing on
Saline Land: Proceedings of the 8th National Conference and Workshop on the
Productive Use and Rehabilitation of Saline Lands (PUR $L), 16–20 September,
Fremantle, Western Australia, pp. 59–69.
NRC (2001). Nutrient requirements of dairy cattle. 7th Rev. Edn., Washington, D.C.,
National Academy of Sciences. PP: 1-408.
Park, Y.W., Ju´arez, M., Ramos, M. and G.F.W. Haenlein (2007). Physico-chemical
characteristics of goat and sheep milk. Small Rumin. Res. 68: 88–113.
Revelli, G.R., Sbodio, O.A., Tercero, E.J. and M. Uberti (2002). Impacto de la calidad de
agua para bebida animal en relación a parámetros productivos, composicionales y
reproductivos. Revista FAVE (Sección Ciencias Veterinarias). 1: 55–67.
Sánchez, W.K., McGuire, M.A. and D.K. Beede (1994). Macromineral nutrition by heat
stress interactions in dairy cattle: review and original research. J. Dairy Sci. 77: 2051–
2079.
SAS (2004). NC. USA. SAS Online Doc. (R) 9.1.3.
Solomon, R., Miron, J., Ben-Ghedalia, D. and Z. Zomberg (1995). Performance of high
producing dairy cows offered drinking water of high and low salinity in the Arava Desert.
J.Dairy Sci. 78: 620-624.
Thomas, D.T., Rintoul, A.J., Masters, D.G., 2006. Sheep select combinations of high and
low sodium chloride, energy and crude protein feed that improve their diet. Appl. Anim.
Behav. Sci. 105: 140–153.
Valtorta, S.E., Gallardo, M.R., Sbodio, O.A., Revelli, G.R. Arakaki, C.; Leva, P.E. Gaggiotti,
M. and E.J. Tercero (2008). Water salinity effects on performance and rumen parameters
of lactating grazing Holstein cows. Int. J. Biometeorol. 52: 239-247.

Summary
These results indicate that consideration of salt alone would be not enough to characterize
drinking water quality. More studies should be pointed out that, given the ability of lactating
sheep to excrete high amounts of minerals waters that lead to elevated mineral excretion
could induce environmental contamination problems.
Etude de l’inhibiteur de la corrosion de l’acier en milieu acide
à différente concentrations et à température ambiante de
N-mésitylimidazole.
Lazhar BECHKI *,**, A.LOUNAS *,
S.KADDOURI * , M.K.BECHKI *,
M.KADRI*.
* Univ Ouargla / Laboratoire de Valorisation et Promotion des Ressources Sahariennes Univ
Ouargla route de Ghardaïa BP 511./ Alger
** Univ Rennes 1 / UMR 6226 CNRS-Université´ de Rennes 1 ‘Sciences Chimiques de
Rennes’, Equipe ‘Catalyse et Organométalliques’, Campus de Beaulieu, Bat 10C, Avenue du
Général Leclerc, 35042 Rennes Cedex / France
E-mail: lbechki1@gmail.com.
E-mail: belalunas@yahoo.fr.

Résumé. Dans ce travail, nous étudions l'efficacité de l'inhibition de corrosion

2T 2T

de l'acier carboné X70 dans le milieu acide HCl (1M) à différente

1T 1T

concentrations et à température ambiant en utilisant composé préparé au de

laboratoire de france ce composé sont : N-mésitylimidazole. Cette étude a été
réalisée au niveau de laboratoire de chimie analytique et le pouvoir inhibiteur
de ce composé. A été déterminé. En utilisant deux méthodes: méthode
1T

classique de perte de poids et la méthode électrochimique de courbes de

polarisation, spectroscopie d'impédance. Les résultats obtenus par la méthode
1T 1T

de perte de poids ont prouvé que l'efficacité inhibitrice de ce composé est

1T 1T

supérieure à 96%, tandis qu’elle est de l’ordre de 65% pour la méthode

électrochimique. Grâce aux courbes d'adsorption de langmir, et Timken, nous
constatons qu’il ya eu une adsorption de ce composé sur la surface du métal.

Summary. In this paper, we study the effectiveness of corrosion inhibition of

X70 carbon steel in the acidic medium HCl (1M) at different concentrations
and at ambient temperature using the compound prepared in laboratory France
this compound are: N -mésitylimidazole. This study was performed at
analytical laboratory and the inhibitory potency of this compound. A
determined. By using two methods: conventional method of weight loss and
the method of electrochemical polarization curves, impedance spectroscopy.
The results obtained by the method of weight loss have shown that the
inhibitory effectiveness of this compound is greater than 96%, while it is
around 65% for the electrochemical method. Through adsorption curves
langmir and Timken, we find that there was adsorption of this compound on
the metal surface.

Les mots clés: Corrosion, Acier Xc70, Inhibition, Isothermes d'adsorption, Acide (HCl 1M).
 1 Introduction générale
La corrosion résulte d’une action chimique ou électrochimique d’un environnement sur
les métaux et les alliages. Les conséquences sont importantes dans divers domaines et en
particulier dans l’industrie: arrêt de production, remplacement des pièces corrodées,
accidents et risques de pollutions sont des événements fréquents avec parfois de lourdes
incidences économiques.
Les installations et équipements industriels susceptibles de se corroder peuvent être
conçus et réalisés en tenant compte des traitements anticorrosion disponibles. Différents
traitements sont déjà connus et applicables à des installations existantes. Cependant,
l’utilisation de plusieurs métaux différents (ferreux et non ferreux) et L’interdiction
d’inhibiteurs toxiques (chromate, nitrite, etc.) compliquent la mise en œuvre de traitements
anticorrosion efficaces et justifient donc la recherche de moyens de protection.
Les inhibiteurs de corrosion constituent un moyen à part entière de protection contre la
corrosion métallique. Ils présentent l'originalité d'être le seul moyen d'intervention à partir du
milieu corrosif, ce qui en fait une méthode de contrôle de la corrosion facile à mettre en
œuvre et peu onéreuse, pour peu que le ou les produits utilisés soient d'un coût modéré. Les
nombreuses études consacrées, depuis une cinquantaine d'années, à ces composés, ont abouti
à proposer des produits ou des mélanges de produits précis correspondant à des systèmes de
corrosion (couples métal milieu corrosif) donnés. Chaque cas de corrosion reste cependant
un cas particulier, et il est nécessaire de connaître les données de base de fonctionnement de
ces inhibiteurs, leurs limites d'utilisation [1]. Les données thermodynamiques et cinétiques
permettent d’explique le Phénomène d’adsorption des inhibiteurs à la surface d’un métal. [2].
En utilisant deux méthodes, la méthode perte de poids et la méthode électrochimiques. a
étudié le mécanisme et l’efficacité de l’inhibition et il a montré que si le décalage du
potentiel de corrosion inhibiteur de corrosion [1]
Notre projet de recherche s’inscrit dans le cadre de ces travaux. Nous avons choisi de
réparer un nouveau inhibiteur a base hétérocyclique, afin de pouvoir combiner leur propriété
inhibitrice.

2. Résultats et Discussion :
On a étudié l’influence de la concentration de l’acide chlorhydrique sur la corrosion du
métal, pour cela on a testé les concentrations suivantes : 2,65774 10- 5 M au 26,58 10-5 M. La
vitesse de corrosion est déterminée après 30 min d’immersion, à une température ambiant.
Selon les résultats obtenus nous avons montré que la vitesse de corrosion augmente
lorsque la concentration de l’acide HCl (1M) augmente. La susceptibilité du matériau à la
corrosion est fonction du nombre de protons de l’électrolyte. Une forte concentration en
protons dans la solution, augmente l’agressivité du milieu.
Parmi les facteurs qui ont un effet sur la vitesse de corrosion de l’acier, nous citons
le facteur du temps d’immersion, donc pour cela nous avons testé différents temps
d’immersion de l’acier à savoir 05 min à 50 min en milieu HCl (1.M).
L’analyse des résultats dans le tableau (1), montre clairement que la vitesse de corrosion
de l’acier dans HCl (1M), diminue avec l’augmentation du temps d’immersion. Cette
diminution provient de la formation spontanée de la couche protectrice adsorbée à la surface
du métal diminue la dissolution du ce dernier.
 L’effet de l’inhibiteur N-mésitylimidazole sur la corrosion de l’acier en milieu acide.
Pour cela nous avons étudié l’influence de la concentration sur la corrosion de l’acier.
Les conditions expérimentales utilisées sont :
1. Concentration de l’acide HCl 1M
2. La température de la solution température ambiant
La gamme de concentration de composé testé varie entre 2,65774 10- 5 M au 26,58 10-5 M.
L’efficacité inhibitrice est déterminée après 30 min d’immersion, à une température
ambiante, le tableau (2) donne les valeurs de la vitesse de corrosion (V) et le pourcentage de
l’efficacité inhibitrice (R%) calculée par gravimétrie pour différentes concentrations de
l’inhibiteur en milieu HCl (1M).
A partir des résultats obtenus dans le tableau (2) nous pouvons faire les remarques
suivantes :
- L’addition de ce composé au milieu corrosif a une influence sur la vitesse de
corrosion de l’acier. Cette diminution de vitesse (V) est probablement due à
l’adsorption de ce composé à la surface métallique [3].
- La vitesse de corrosion diminue tandis que l’efficacité inhibitrice croît avec la
concentration de l’inhibiteur. Ce comportement pourrait être attribué à la forte
interaction de l’inhibiteur avec la surface du métal, il résulte de l’adsorption des
molécules sur la surface du métal [4].
- L’adsorption de ce composé sur la surface métallique peut être attribuée aux atomes
d’azote, leur paire électronique au métal en présence des site actif à la surface
métallique et faire des liaisons entre eux l’efficacité inhibitrice de ce composé varie
d’un composé à un autre, avec une meilleure efficacité inhibitrice de (96.45%)
21,26 10- 5 M.

3. Etude électrochimique :
Les Figures (4, 5) représentent les courbes de polarisation cathodiques et anodiques de
l’acier, en milieu HCl (1M). sans et avec addition des inhibiteurs à différentes
concentrations. Les paramètres électrochimiques tirés de ces courbes sont donnés dans le
tableau (3).
A partir de ces résultats nous pouvons faire les remarques suivantes :
- Les courbes de polarisation cathodique se présentent sous forme de droites
indiquant que la réaction de réduction de l’hydrogène à la surface de l’acier se fait
selon un mécanisme d’activation pure.
- L’action de inhibiteur se traduit par une diminution des courants anodique et
cathodique. C’est résultat montre que l’addition de inhibiteur réduit la dissolution
anodique du fer et retarde l’évolution de la décharge des ions H+.
- L’ajout de l’inhibiteur fait varier légèrement les valeurs de la pente cathodique bc.
Ce résultat suggère que le mécanisme de réduction du proton n’est pratiquement pas
affecté par l’addition de l’inhibiteur.
- Le potentiel de corrosion varie très peu avec l’augmentation de la concentration de
l’inhibiteur, confirmant ainsi le caractère mixte de l’inhibiteur avec toute fois une
légèrement dance anodique. La meilleure concentration qui diminue la vitesse de
corrosion est de 40 ppm.
 - le déplacement cathodique des courbes montre que N-mesityimidazol est placé sur
les sites cathodiques de la surface de métal.
Les valeurs de taux de recouvrement (θ) pour différentes concentrations des
inhibiteurs obtenues à partir des mesures de perte de poids dans le domaine de
température étudiée, ont été utilisées pour déterminer l’isotherme correspondante au
processus d’adsorption de l’inhibiteur. Ainsi différente isotherme comprenant Langmuir
ont été testées afin de trouver l’isotherme d’adsorption convenable. Ces isothermes
d’adsorption ont été utilisées pour d’autre inhibiteur [3]. Selon ces isothermes, θ est relié à
la concentration de l’inhibiteur (C inh ).
La courbe C inh / ϴ en fonction de la concentration est linéaire pour le N-mésitylimidazole
(figure 6), cela montre que l’adsorption du N-mésitylimidazole sur la surface de l’acier en
milieu HCl (1M) obéit à l’isotherme d’adsorption de Langmuir R2=0.841.
La spectroscopie d’impédance électrochimique (SIE) bien établie est un outil puissant à
l’étude de la corrosion, les propriétés de surface, la cinétique de l’électrode et l’information
sur le mécanisme peut être obtenue à partir des diagrammes d’impédance.
La Figure (7) présente les diagrammes de Nyquist de l’interface acier solution, obtenus au
potentiel d'abandon dans HCl 1M. L’électrode d'acier étant préalablement modifiée ou non
par un film de N-mésitylimidazole, obtenu après immersion de l'électrode pendant 30 min,
dans une solution de l'inhibiteur à différentes concentrations. Ces graphes sont constitués
d’une boucle capacitive principale sous forme de demi-cercle dont le centre est situé au
dessous de l’axe des réels. Ce type de diagramme indique généralement que la réaction de
corrosion est contrôlée par un processus de transfert de charges sur une électrode solide de
surface hétérogène et irrégulière [5].
Nous observons de plus que le diamètre de la boucle capacitive qui représente, rappelons,
la résistance de transfert de charges (t R), est plus important dans le cas de l'électrode N-
mésitylimidazole préalablement modifiée, que dans le cas du témoin (acier non modifié). Un
film protecteur de s'est donc bien auto-assemblé spontanément à la surface du métal après la
simple immersion de ce dernier dans la solution contenant les molécules dissoutes de
l'inhibiteur. Ainsi formée protège efficacement l'acier grâce à son effet de blocage du
transfert d'électrons de la surface du métal vers la solution corrosive.
La taille du spectre d’impédance augmente également avec la concentration de
l'inhibiteur et la valeur de t R, déterminée à partir de la différence entre la limite basse
fréquence et la limite haute fréquence de la partie réelle de l'impédance totale, atteint son
maximum à la concentration de 13.29 10-5 M. Ce résultat, validé ci-après par modélisation
à l'aide de différents circuits électriques équivalents (CEE), traduit l'influence du film de N-
mésitylimidazole sur les processus se déroulant à l'interface acier milieu acide. Ce film
devenant en effet plus efficace lorsque la concentration de l'inhibiteur augmente.

4. Partie Expérimental :
Les spectres RMN 1H et 13C ont été enregistrés sur des spectromètres BRUKER
AVANCE DPX 200 et AM300WB équipés d’une sonde QNP multi-noyaux. Le déplacement
chimique des signaux (δ) est exprimé en ppm et corrélés aux signaux de CDCl 3 (1H: 7.26
ppm, 13C: 77.00 ppm (pic central)).
Le spectre de produit synthétisé ont été réalisé à une température ambiante (≈ 22 °C salle
climatisée), le produit et analysé dans du CDCl 3 .
 Les caractéristiques RMN 1H sont présentées de la manière suivante : δ (ppm)
(multiplicité m, intensité I, constante de couplage J (Hz), attribution).
L’avancement des réactions a été généralement contrôlé par chromatographie sur couche
mince. Les plaques utilisées sont de type Merck Silicagel 60 F254. La révélation des plaques
est effectuée par UV (254 nm), exposition à l’iode, ou à une solution acide de KMnO 4 . Le
produit ont été purifié sur colonne de gel de silice (SDS 60 - 0.040-0.063 mm, 230-400
mesh).
La verrerie est stockée dans une étuve à 100 °C. Dès leur sortie, les tubes de schlenk sont
bouchés et placés sous vide à l’aide d’une rampe composés d’une ligne sous vide et d’une
ligne sous argon. Le vide des rampes s’échelonne de 0.01 à 0.05 mm Hg.

4.1 Le Protocole.
Les essais de perte de poids sont effectués en fixant un échantillon sur une file
support en polymère dans un bêcher contenant 40 ml de l’électrolyte. Un bain marie a été
utilisé pour permettre le maintien de l’électrolyte à la température ambiante. Les échantillons
utilisés sont rectangulaires et présentent une surface totale 14.30 cm2 (deux faces + les côtés)
P P

.les échantillons subissent un rinçage à l’eau distillée, un dégraissage à un rinçage à l’eau

distillée, enfin un séchage. Les échantillons sont pesés après et avant chaque essai En fin on
prend une photo microscopique d’une surface de la pièce avant et après de la tremper, par
l’augumentif 10× a la diamètre est 2.5 donc l’augumentif sera 250 micro.

5. Conclusion générale
Au cours de ce travail nous avons suivi l’action inhibitrice de composé N-mésitylimidazol
utilisée comme inhibiteur sur la corrosion de l’acier carboné XC70.
L’étude à été réalisée dans les milieux: HCl (1M). Les mesure ont été réalisée par la
méthode, perte de masse et méthode électrochimique tel que Les courbes de polarisation et
spectroscopie d’impédance électrochimique.
Tout d’abord nous avons étudié le comportement de l’acier dans le milieu HCl (1M) seul,
ainsi que les facteurs qui affectent la vitesse de corrosion de l’acier la concentration de
l’acide et le temps d’immersion. Pour réaliser cette étude nous avons utilisé la méthode perte
de poids. Les résultats obtenus montrent que la vitesse de corrosion augmente avec
l’augmentation de la concentration du milieu. Pour cela nous avons constaté que le composé
étudié est très efficace.
Les courbes de Nyquist montré que les paramètres d’impédance d’un électrode XC70
dans une solution HCl (1M) en absence et en présence d’inhibiteur N-mésitylimidazol
indiquant que ce sont essentiellement un processus de transfert de charge.

6.Tableaux et Figures
t (min) S (cm2)
P P

Δm(g ) Vg/(cm2.min*10-3)
P P P P

05 14.28 0,009 3,1512605

10 14.28 0,01 7,00280112
15 14.29 0,0115 11,6515045
 20 14.27 0,0118 16,538192
25 14.26 0,0322 56,4516129
30 13.10 0,037 84,7328244
35 13.99 0,033 82,5589707
40 14.20 0,027 76,056338
45 14.24 0,02 63,2022472
50 14.27 0,017 59,5655221

TAB. 1 : vitesse de corrosion et temps d’immersion de l’acier dans HCl (1M) à

température ambiante.

FIG. 1 .Evolution de la vitesse de la corrosion en fonction du temps HCl (1M)

à température ambiante.

C(PPm) S Δm (g) V g/(cm2. P P

V (mm/an % R
(cm2)
P P

Min) *10-3)
P P

00 13.20 0,0391 0,08886364 59,8804196 0000

05 14.30 0,0052 0,01090909 7,35104895 87,7237852
10 14.33 0,0059 0,01235171 8,32315207 86,1003778
15 14.28 0,0038 0,00798319 5,37944408 91,0163554
20 14.27 0,0048 0,0100911 6,79984906 88,6442862
25 14.28 0,0032 0,00673212 4,53641169 2,4242152
30 14.27 0,004 0,00840925 5,66654089 90,5369052
35 14.28 0,0028 0,00588235 3,9638009 93,3804724
40 14.28 0,0015 0,00315126 2,12346477 96,4538245
45 14.28 0,002 0,00420168 2,83128636 95,271766
50 14.27 0,0051 0,01072179 7,22483963 87,9345541

TAB. 2 : Vitesse de corrosion et efficacité inhibitrice de la corrosion dans

HCl 1M avec addition des inhibiteurs à température ambiante,
FIG. 2. Evolution de la vitesse de la corrosion en fonction de la concentration de l’inhibiteur.

FIG. 3. Evolution de l'efficacité inhibitrice en fonction de la concentration de l’inhibiteur.

FIG. 4. La courbe de polarisation de l’acier XC70 dans une solution de HCl 1M.

En étudiant l’effet de l’inhibiteur (N-mésitylimidazole) où les concentrations changer de

5 à 50 ppm et on a obtenue les courbes suivant :
 1,5
HCL
1,0 5PPM
10PPM
0,5
15PPM
20PPM
0,0
25PPM
-0,5
30PPM
i (mA/cm2)

35PPM
-1,0 40PPM
45PPM
-1,5 50PPM

-2,0

-2,5

-3,0
-650 -600 -550 -500 -450 -400 -350 -300
E(mV)

FIG. 5. Courbes de polarisation de l’acier dans HCl 1M sans et avec addition de différentes
concentration de N-mesityimidazol.
C (M) *10-5 -E (mv) Icorr(mA .cm-2) ba(mv) bc(mv) Vcorr mm/an R%
00 471.2 1.5053 138.5 -165.5 17.60 /////

2,65774 471.4 1.2865 140.6 -166.1 15.04 14,5454545

5,31547 471.6 1.0575 133.6 -150.2 12.36 29,7727273
7,97321 476.4 0.5643 88.8 -112.2 6.599 62,5056818
10,63 475.6 0.9484 123.3 -146.7 11.09 36,9886364
13,29 473.8 0.7694 133.7 -150.9 8.999 48,8693182
15,95 476.4 0.6861 94.6 -123.0 8.024 54,4090909
18,6 475.8 0.6496 89.1 -110.4 7.598 56,8295455
21,26 481.1 0.5214 100.3 -123.8 6.098 65,3522727
23,92 483.8 0.5308 93.9 -123.2 6.208 64,7272727
26,58 483.9 0.6532 90.2 -120.2 7.806 55,6477273

TAB. 3- Les valeurs électrochimiques les plus importantes de N-mesityimidazol dans la

solution HCl (1M).
 FIG. 6. Isotherme d’adsorption de Langmuir de l’acier dans HCl (1M).

ZR max Zi max
C (M) *10-5 RCT*103 (ohm) Fmax*102 (Hz)
(ohm.cm2) (ohm.cm2) C*10-5 (μF)
P P P P P

P P P P P P

00 45.66 3.98296 1.47729 15.8230 6.80870

2,65774 13.65017 4.228 1.2260 12.333 7.6589
5,31547 15.6882929 4.19067 4.468 4 9.02895
7,97321 40.71892023 4.50959 3.64528 4 1.0915
10,63 33,68273558 4.40141 4.1364 3.55 9.6236
13,29 43.04524368 5.58828 5.6498 2.5 1.12694
15,95 52,19756989 3.89963 2.71536 6.32910 9.26085
18,6 25.08986242 3.51276 2.73658 6.3291 9.18904
21,26 25.32234182 3.55756 2.7754 6.3291 9.06026
23,92 25.64534046 1.4568 5.717 2.5 0.11133
26,58 52.93074911 8.41629 9.42303 2.5 6.75600

TAB. 4. Les paramètres d’impédance d’une électrode XC70 dans une solution HCl (1 M) en
absence et présence de 05-50 ppm de N-mésitylimidazole

RCT : La résistance de la solution (ohm) , ZR max : L’impédance real,

Zi max : L’impédance imaginaire, Fmax : La fréquence, C : la capacité
 Figure (7) : Courbes de Nyquist d’une électrode XC70 dans une solution HCl (1 M) en
absence et en présence de 05-50 ppm de N-mésitylimidazole

Références :
[1]. E. E. Oguzie, Portugaliae (2008). Corrosion Inhibitive Effect and Adsorption Behaviour
of Hibiscus Sabdariffa Extract on Mild Steel in Acidic Media. Portugaliae Electrochimica
Acta 26 303-314.
[2]. E. M. Sherif, S. M. Park, (2006). Effects of 2-amino-5-ethylthio-1,3,4-thiadiazole on
copper corrosion as a corrosion inhibitor in aerated acidic pickling solutions. Electrochimica
Acta 51 6556–6562.
[3]. K.F.Khaled and N. S. Abdel-Shafi, (2013). Chemical and Electrochemical Investigations
of L- Arginine as Corrosion Inhibitor for Steel in Hydrochloric Acid Solutions. Int. J.
Electrochem. Sci., 8 1409 – 1421.
[4]. Shylesha B.S., Venkatesha T.V. and Praveen B.M. (2011). Corrosion Inhibition Studies
of Mild Steel by New Inhibitor in Different Corrosive Medium. Research Journal of
Chemical Sciences, Vol. 1(7), 46-50.
[5]. Chandrabhan Verma, M.A. Quraishi, E.E. Ebenso, (2013). Green Ultrasound Assisted
Synthesis of N2,N4,N6-tris ((Pyridin-2-ylamino) methyl)-1, 3,5-triazine-2,4,6-Triamine as
Effective Corrosion Inhibitor for Mild Steel in 1 M Hydrochloric Acid Medium. Int. J.
Electrochem. Sci., 8 10864 – 10877.

Summary. In this paper, we study the effectiveness of corrosion inhibition of X70 carbon
steel in the acidic medium HCl (1M) at different concentrations and at ambient temperature
using the compound prepared in laboratory France this compound are: N -mésitylimidazole.
This study was performed at analytical laboratory and the inhibitory potency of this
compound. A determined. By using two methods: conventional method of weight loss and
the method of electrochemical polarization curves, impedance spectroscopy. The results
obtained by the method of weight loss have shown that the inhibitory effectiveness of this
compound is greater than 96%, while it is around 65% for the electrochemical method.
Through adsorption curves langmir and Timken, we find that there was adsorption of this
compound on the metal surface.
 Evaluation des risques sanitaires de la pollution hydrique
au fluor dans le bassin minier au sud tunisien :
Cas de la région de Berka (Gafsa-sud)

Fatma Omrane1, Amina Ben Sâad2, Younes Hamed1,3, Moncef Khadhraoui1,

Boubaker Elleuch1, Imed Gargouri1,4
1
: Laboratoire 3E « Eau, Energie et Environnement », ENIS, Université de Sfax – Tunisie
E-mail : Imed.Gargouri@fmsf.rnu.tn
2
: Centre Régionale de Transfusion Sanguine de Gafsa, Ministère de la santé - Tunisie
3
: Département de Géologie, Faculté de Sciences, Université de Gabes - Tunisie
4
: Département de Médecine du Travail, Faculté de Médecine, Université de Sfax - Tunisie

Résumé :
Aujourd'hui, la relation de causalité entre un agent environnemental et
un effet sanitaire est très difficile a affirmé avec certitude. Dans ce contexte
d’incertitudes, il a été nécessaire de développer des outils d’aide à la décision
dans l’évaluation de risques sanitaires. Dans ce cadre, nous nous sommes inté-
ressés à l’impact sanitaire de la consommation d’eau polluée au fluor dans la
région de Berka du bassin minier de Gafsa.
L’objectif principal a été d’évaluer et hiérarchiser les risques sani-
taires de la pollution hydrique selon la méthode de Kinney. L’objectif secon-
daire est de proposer un plan d’action correctif.
A l’issue de cette démarche d’évaluation du risque sanitaire de la pol-
lution hydrique au fluore, plus que 50% de la population présentait une fluo-
rose dentaire et 11% présentait un score de risque très important. Ceci nous in-
cite à promouvoir le dosage de fluor hydrique et la mise à jour des normes
tunisiennes.

Mots clés : Pollution hydrique, Fluor, Evaluation de risque, Méthode de Kinney,

Prévention
ERS de la pollution hydrique au fluor dans le bassin minier

1 Introduction
Ces dernières décennies, la santé environnementale et les interrogations qu'elle soulève
ont suscité de plus en plus des préoccupations de la part de la société civile, des pouvoirs
publics, des décideurs et des lanceurs d'alertes (Observatoire Régional de la Santé Rhône-
Alpes, 2007).
Hamed dans ces travaux en hydrogéologie (Hamed, 2009) a mis en évidence des taux de
fluor qui dépassent les normes de potabilité de l’eau (OMS, 2006) au niveau de la région de
Berka du bassin minier de Gafsa.
L’absorption fréquente du fluor peut causer de l'ostéoporose et des carries. Le fluore peut
endommager les reins, les os, les nerfs et les muscles (SPF© Emploi, Travail et Concertation
sociale, 2009). A cet effet, nous avons envisagé dans cette étude d’évaluer les risques sani-
taires de la consommation d’eau polluée au fluor dans la zone de Berka.
Après présentation du lieu et de la population d’étude, nous exposons la méthodologie
adoptée qui est l’une des méthodes de Ranking permettant de classer les risques selon leur
degré de gravité la méthode de Kinney (Kinney et Wiruth, 1976) et pour ceux nous avons :
(1) dressé un questionnaire à travers lequel nous avons collecté les données ; (2) hiérarchisé
les risques potentiels sur la santé liés à une exposition au fluor ; (3) évalué les risques sani-
taires liés à l’exposition au fluor présent dans l’eau de boisson.

2 Matériel et méthodes
2.1 Lieu de l’étude
La zone d’étude est située au sud ouest tunisien, appartenant au bassin minier de Gafsa
sud (bassin de Moularès-Redayef) de superficie environ 300 Km2. Devant une demande
croissante en eau, causée par l’installation du complexe industriel de la compagnie de phos-
phates de Gafsa (CPG), la croissance rapide de la population et le développement de
l’agriculture (plusieurs périmètres irrigués), le recours aux eaux souterraines devient très
important. Une partie de ce bassin (80 Km2 environ : zone de Berka) est contaminée par les
rejets des laveries de la ville minière de Moularès et aussi de la 2éme ville minière de Redayef
ainsi que les rejets de l’ONAS (Hamed, 2009).
L’hydrogéologie de ce bassin minier est largement influencée par les rejets des laveries.
Dans la région de Berka (Hamed, 2009), l’eau souterraine est exploitée par des puits de sur-
face de profondeur inférieur à 6 m. Sachant que la nature lithologique du terrain est essentiel-
lement sableuse (porosité importante qui dépasse 35 %) (Besbes, 1978), ce qui a favorisé
l’infiltration des ces rejets vers la nappe. De plus la région est géographiquement localisée
dans une région sismiquement active (Ahmadi, 2006). Les gens de la région exploitent l’eau
souterraine essentiellement de la nappe superficielle pour l’alimentation en eau potable et
dans le secteur agricole.
 I. Gargouri et al.

2.2 Population d’étude

Moularès comptait, au recensement de 2004, 24 487 habitants. La région de Berka, zone
rurale, comptait 250 habitants. Une école primaire est située au cœur du village accueillant
de jeunes enfants, constituant une population vulnérable vis-à-vis d’une exposition au fluore.
Elle dispose également d’un dispensaire type I situé à 8 km de la délégation de Moularès.
Afin d’évaluer les risques sanitaires de la pollution hydrique au fluor (ERS-PHF) à la région
de Berka, nous avons envisagé de prendre un échantillon de la population dont la taille est
100 repartie selon la tranche d’âge comme suit : (1) Enfant non scolarisé (inférieur à 6 ans) ;
(2) Enfant scolarisé (6 à 15 ans) ; (3) Jeune (15 à 30 ans) ; (4) Adulte (30 à 50 ans) ; (5) Agé
(supérieur à 50 ans). Chez cet échantillon de la population de Berka, nous avons administré
un questionnaire préétabli afin de recueillir les données nécessaire pour l’ERS-PHF.

2.3 Méthodologie
L’approche que nous avons adopté dans l’ERS-PHF, a consisté à rechercher auprès de la
population concernée les dangers identifiés, les analysés, mettre au point une stratégie et
fixée des priorités. Cette approche, la méthode de « Kinney » (Kinney et Wiruth, 1976), est
l’une des méthodes de Ranking qui permet de classer les risques selon leur degré de gravité;
Du nom de son inventeur, un chercheur américain, cette méthode datant de 1976 est pro-
bablement une des plus connues (SPF© Emploi, Travail et Concertation sociale, 2009). Elle
se base sur des tableaux donnant des valeurs selon la probabilité (P) (TAB. 1.1), la fréquence
d’exposition (F) (TAB. 1.2) et l'effet (E) (TAB. 1.3) et évaluer le risque (R) par la formule :
R = P x F x E (TAB. 2).

TAB. 1.1 – La probabilité TAB. 1.2 – La fréquence d’exposition

0,1 à peine concevable 0,5 Très rare (moins d’1 fois/an)

0,2 Pratiquement impossible 1 Rare (annuel)
0,5 Concevable mais peu probable 2 Parfois (mensuel)
1 Peu probable mais possible 3 Occasionnel (hebdomadaire)
3 Peu courant 6 Régulier (journalier)
6 Tout à fait possible 10 Continu (permanant)
10 prévisible

TAB. 1.3 – Les effets sanitaires

1 Petit : fluorose dentaire bénigne

3 Important : goitre
7 Sérieux : atteinte rénale
15 Très sérieux : fractures osseuses (ostéomalacie, ostéoporose)
ERS de la pollution hydrique au fluor dans le bassin minier

40 Grave : Fluorose invalidante

100 Très grave : Dommage neurologique

TAB. 2 – Les indices et les score de risque et mesures préventives éventuelles

Indice Score Mesures préventives

Risque
de risque de risque à prendre

R ≤ 20 Très limité 1 Acceptable

20 < R ≤ 70 Possible 2 Attention requise

70 < R ≤ 200 Substantiel 3 Mesures requises

200 < R ≤ 400 Important 4 Amélioration immédiate requise

R > 400 Très important 5 Cesser l’exposition

3 Résultats
3.1 Description de la population d’étude
Nous avons prévu de prendre au hasard un échantillon de la population dont la taille est
de 100 individus. Au cours de la première sortie dans la région de Berka, nous avons pu
interroger 60 sujets. Toutefois, les circonstances sécuritaires nous ont empêchés d’interroger
les 40 sujets restants (TAB. 3).

TAB. 3 – Population d’étude réelle « Echantillon retenu »

Age N (%)
Enfant non scolarisé (< 6 ans) 8 13
Enfant scolarisé (6 à 15 ans) 12 20
Jeune (15 à 30 ans) 16 27
Adulte (30 à 50 ans) 14 23
Agé (> 50 ans) 10 17

Cinquante trois sujets de la population d’étude réside de façon permanente dans la région
de Berka (soit 88%) dont 34 sont de sexe masculin (soit 56 %) ; et 26 sont de sexe féminin
(soit 44%). L’état de santé des individus ayant participé à cette étude a été qualifié de très
bon à très mauvais tout dépend du participant.
 I. Gargouri et al.

Avant son raccordement au réseau public de distribution d'eau potable (SONEDE), la po-
pulation de Berka consommait les eaux des puits locaux. Actuellement, certains consomment
encore les eaux de puits vu la difficulté d’accès au réseau public de distribution d'eau po-
table. Cinquante et un pourcent (51%) de notre population d’étude consomme principalement
les eaux de puits. Le reste consomme l’eau du robinet depuis 2005.

3.2 Evaluation des risques

Si le goitre avait touché 71,6%, son indice de risque est de 1,24 ; alors qu’aucun de
l’échantillon n’est atteint d’une fragilité osseuse (ostéomalacie et ostéoporose) ou un dom-
mage neurologique, mais leurs indices de risque respectifs sont 64,1 et 74,3 (TAB. 4). La
moyenne des indices de risque par tanche d'âge quelque soit l'effet augmente de façon pro-
portionnelle à l'âge (TAB. 5). Le goitre présente le score de risque le plus faible (S R =1). Le
score de risque de la fragilité osseuse varie de 1 à 5, alors que la fluorose osseuse et le dom-
mage neurologique ont un score de risque de 2 (TAB. 6).

TAB. 4 – Les pathologies secondaires aux expositions au fluore

Total Homme Femme Indice de risque
Pathologie
N % N % N % Min-Max Moyenne
Goitre 43 71,6 28 46,6 15 25,0 0,2-1,8 1,2
Atteinte rénale 18 30,0 9 15,0 9 15,0 0,4-42 7,9
Fluorose osseuse 8 13,3 7 11,6 1 1,6 2-40 16,5
Fluorose dentaire 3 5,0 2 3,3 1 1,6 0,1-100 32,6
Fragilité osseuse* 0 0,0 0 0,0 0 0,0 0,8-900 64,1
Dommage neurologique 0 0,0 0 0,0 0 0,0 5-1000 74,3
* : ostéomalacie et ostéoporose

TAB. 5 – Les indices de risques selon l’âge

Tranche Risques
d’âge Fluorose Atteinte Fragilité F. osseuse Dommage
(ans) Goitre
dentaire rénale osseuse invalidante neurologique
< 6 ans 4,7 0,8 1,8 3,8 10,3 25,6
(0,0-36) (0,2-1,8) (0,4-4,2) (0,8-9) (2-24) (5-60)

6 à 15 20,7 1,4 3,4 7,2 19,2 47,9

(0,1-60) (0,2-1,8) (0,2-4,2) (0,8-9) (2-24) (5-60)

15 à 30 46,3 1,4 10,4 17,2 18,8 46,9

(0,1-60) (0,3-1,8) (0,7- 42) (1,5-90) (4 - 24) (10 - 60)

30 à 50 40,7 1,3 10,8 39,9 16,9 42,1

(10-60) (0,3-1,8) (0,7-42) (1,5-90) (4-24) (10-60)
ERS de la pollution hydrique au fluor dans le bassin minier

> 50 ans 32,8 1,1 10,1 289,2 14,4 234

(10-100) (0,3-1,8) (0,7-42) (1,5-900) (4-40) (10-1000)

TAB. 6 – Les scores de risque en fonction des effets

Effectif pour chaque effet

Fluorose Atteinte Fragilité Fluorose Dommage R* S R**

Goitre
Dentaire rénale osseuse osseuse neurologique

0 0 0 4 0 3 R>400 5

0 0 0 2 0 0 200<R<400 4

1 0 0 10 0 0 70<R<200 3

16 0 8 2 33 42 20<R<70 2

43 60 52 42 27 15 R<200 1
* Risque ** Score de risque

4 Commentaires et Discussion
Nos résultats rejoignent ceux de la littérature en terme des effets secondaire au fluor noté
chez notre population d’étude en particuliers la fluorose dentaire, l’atteinte osseuse ainsi que
l’atteinte neurologique (Malchaire et koob, 2006) (Fluoride action network) (Connett, 2004)
(Committee on Fluoride in Drinking Water et National Research Council, 2006).
Le score de risque été très important chez 7cas soit 11% de notre population d’étude. Un
chiffre important pour une population d’étude à 60 personnes. Ceci sous dit qu’une attention
particulière doit être accordée à ce sujet.
Le NRC recommande maintenant à l'EPA d'abaisser la limite permise en raison d'un
vaste faisceau de preuves qui lient l'ingestion de fluorure à des taux accrus de fracture des os,
douleurs aux articulations (arthrite) et dommages aux dents (fluorose dentaire). À cet effet,
un point important soulevé dans le rapport du NRC explicite que, puisque la fonction de
l'émail consiste à protéger l'intérieur de la dent des attaques extérieures, la fluorose dentaire
ne peut plus être considérée comme un problème purement esthétique. Le bon sens nous
indique que puisque la fluorose dentaire touche plus de 50% de notre population d’étude une
action corrective doit être entreprise le plus tôt possible.
Une eau est dite potable quand elle satisfait à un certain nombre de caractéristiques la
rendant propre à la consommation humaine. Les standards de référence dans ce domaine
diffèrent selon les époques et les pays et selon l'autorité en charge de cette définition dans
certains pays (Montestrucq L. et Guye O, 2007). Le concept de « potabilité » varie à travers
le monde, fruit d'un contexte historique, scientifique et culturel local. Il détermine la question
de l'accès à l'eau, puisque une eau de bonne qualité est essentielle au développement écono-
mique et humain.
 I. Gargouri et al.

Un plan d’action a été proposé afin de prévenir tout éventuel impact pouvant résulter du
risque de la pollution hydrique au fluor : (1) Sur le plan collectif : parvenir l’eau aux citoyens
ayant des difficultés d’accès au réseau publique de distribution de l’eau potable (SONEDE) ;
et sensibiliser la population de Berka aux effets néfastes de la consommation des eaux pol-
luées (eau de puits) sur leur santé. (2) Sur le plan individuel : Prendre en charge des sujets
ayant un score de risque très important ; et évaluer quantitativement des risques par les do-
sages urinaires du fluor pourra être pratiquée.

5 Conclusion
L’ERS-PHF, au niveau de la région de Berka, a été conduite selon la méthode de Kinney.
Cette dernière, nous a permis d’objectiver l’ER en hiérarchisant les risques sanitaires puis
en évaluant les risques en tenant compte du score de risque calculé à partir du produit des
indices de probabilité de survenue d'une conséquence délétère, de la fréquence d'exposition
et de la gravité de cette conséquence ou effet. Ainsi, cela nous a permis d’identifier les prio-
rités des actions préventives à mettre en place.
A l’issue de cette démarche d’ERS-PHF, un plan d’action a été mis en place afin préve-
nir tout éventuel impact pouvant résulter du risque de la pollution hydrique au fluor.

Références
Ahmadi, R. (2006). Utilisation des marqueurs morphologiques, sédimentologiques et micros-
tructuraux pour la validation des modèles cinématiques de plissement. Application à
l’Atlas méridional tunisien. Thèse de doctorat, Fac.Sc et Téch. Nantes (France).
Besbes, M. (1978). Etude hydrogéologique du bassin de Moularès-Redayef (Modèle mathé-
matique). Master de recherche, Ecole des Mines (France).
Committee on Fluoride in Drinking Water et National Research Council (2006). Fluoride in
Drinking Water: A Scientific Review of EPA’s Standards. Washington, DC: National
Academies Press. NRC. [En ligne] :
http://books.nap.edu/openbook.php?record_id=11571 (Consulté le 07/04/2012)
Connett, P. 50 Reasons to Oppose Fluoridation (updated April 12, 2004). Medical Veritas.
1:70–80. [Enligne] http://www.ariane-
services.com/vivredurable/IMG/pdf/Fluor_sante.pdf (Consulté le 07/04/2012)
Fawell, J., Bailey K., Chilton J., Dahi E., Fewtrell L., Magara Y. (2006). Fluoride in Drink-
ing-water. Rapport OMS Genève. [Enligne]:
http://www.who.int/water_sanitation_health/publications/fluoride_drinking_water_full.p
df (consulté le 07/04/2012)
Fluoride action network. 10 Facts about Fluoride. [En ligne] :
http://www.fluoridealert.org/fluoride-facts.htm (Consulté le 07/04/2012)
Hamed, Y. (2009). Caractérisation Hydrogéologique, Hydrochimique et Isotopique des Sys-
tèmes Aquifères du Synclinal de Moulares-Tamerza (Sud Ouest Tunisien). Thèse de
doctorat. Faculté de Science de Sfax.
Kinney, G. F and Wiruth, A. D (1976). Wiruth.Practical Risk Analysis for Safety Manage-
ment, NWC technical publication 5865, Naval Weapons Center; China Lake, CA. [En
ligne] : http://www.dtic.mil/dtic/tr/fulltext/u2/a027189.pdf (Consulté le
26/02/2012)
ERS de la pollution hydrique au fluor dans le bassin minier

SPF© Emploi, Travail et Concertation sociale (2009). L'analyse des risques. [En ligne] :
http://www.emploi.belgique.be (consulté le 26/02/2012)
Malchaire, J. et Koob, J. P (2006). Fiabilités de la méthode kinney d’analyse des risques.
Medcine du travail & ergonomie. 43: (1), 3-8 [En-
ligne]:http://www.deparisnet.be/sobane/fr/articles/art_malchaire_koop_fiabilite_de_la_m
ethode_kinney_10-10-11.pdf
Montestrucq L. et Guye O (2007). Observatoire Régional de la Santé Rhône-Alpes.
L’évaluation quantitative des risques sanitaires (EQRS) ; principe et méthodes dossiers
santé-environnement de l’ors. [En ligne] : http://www.ors-rhone-
alpes.org/environnement/pdf/dossier1.pdf (Consulté le 26/02/2012)
Normes Françaises de qualité des eaux destinées à la consommation humaine. Arrêté du
11/01/2007 relatif aux limites et références de qualité des eaux brutes et des eaux desti-
nées à la consommation humaine mentionnées aux articles R. 1321-2, R. 1321-3, R.
1321-7 et R. 1321-38 du code de la santé publique. [En ligne] : http://ile-de-
france.sante.gouv.fr/santenv/eau/regle/a070111_l_r.pdf. (Consulté le 26/02/2012)
Organisation mondiale de la santé (OMS). Normes de l'OMS sur l'eau potable. Water
treatment solutions. lenntech. Mises à jour en 2006. [En ligne] :
http://www.lenntech.fr/applications/potable/normes/normes-oms-eau-potable.htm
(Consulté le 26/02/2012)

Summary
Today, the causal relationship between an environmental agent and a health effect is
very difficult to be affirmed with certainty. In this context of uncertainty, it was necessary to
develop tools for decision support to evaluate health risks. As part of risk assessment we
looked at the health impact of consuming polluted water with fluoride in an exposed popula-
tion in the region of Berka in the mining area of Gafsa.
The main objective of this study was to evaluate and prioritize the health risks of
water pollution with fluoride by the method of Kinney. The secondary objective is to propose
a corrective action plan.
Following this process of evaluation of health risks of water pollution with fluoride,
we have been able to show that over 50% of the population had presented dental fluorosis
and 11% of our population had a very high score of risk. This encourages us to promote the
dosage of fluoride in water and the updating of Tunisian standards for drinking waters.

Keywords: Water pollution, Fluoride, Risk assessments, Method Kinney, Prevention.

 The assessment of degree of contamination associated with
sediments geochemistry of Meboudja wadi, Annaba district,
NE Algeria
Bougherira Nabil * Hani Azzedine *
Djabri Larbi* Chaffai Hicham* Sâaidia Bachir* Bouâbsa Lakhdar** Sayad Lamine***
Haied Nadjib* Jack Mudry****
* Badji Mokhtar-Annaba University P.O. Box 12, 23000 Annaba, Algeria / Laboratory of
Water resources and sustainable development.
** Badji Mokhtar-Annaba University P.O. Box 12, 23000 Annaba, Algeria / Laboratory of
Geodynamics and Natural Resources
*** Laboratory of soil and Hydraulics, faculty of Engineer Sciences, Badji Mokhtar
University, Annaba-Algeria
****Department of Geosciences, Faculty of Science and Technology, 16 Gray Road, 25000
Besançon, France

nabilbough@gmail.com

Abstract. Algeria has established a dense industrial network, concentrating

pollutants and major water and energy consuming sectors. This industrial base
was established near water sources (Mediterranean Sea), or rivers that have
become dumping grounds for uncontrolled liquid discharges. The Meboudja is
one of the most rivers anthropized in the plain of el Hajar: it has one of the
highest densities industrial, agricultural and urban.
In this study, we mainly measured marker of the heavy metals (oxide) content
in sediments, However, Fe and Mn concentrations were significantly higher in
the additional samples of water than in those from the area of Annaba.
In most of this work all possible species in the water solution are described as
to their concentrations leads us to another part of the results is the incorpora-
tion of ETM in sediments.
DRX Analysis is necessary to highlight the main changes of the effects of in-
dustrial discharges, agricultural, and domestic water.

Keywords: water sources, the Meboudja, concentrations, sediment analysis.

The assessment of degree of contamination associated with sediments geochemistry of
Meboudja wadi, Annaba district, NE Algeria

1 Introduction
Increase of waste production is correlated with economical and demographical develop-
ment. While life improvement is expected, such development also leads to negative effects
on the environment and economy of many countries. The demographical development and
the intensification of the economical activities in Algeria are accompanied by an increase of
solid waste production.
The studied zone, that is expected to be the third industrial node of Algeria, has experi-
enced an intensification of the demography (higher than 800000 inhabitants) and economy
(higher than 150 industrial units). Environmental problems such as air and water pollution
could seriously set back this economical and urban development. Indeed, several hundreds of
tons/day of solid and liquid wastes are dumped in the environment without any treatment.
This uncontrolled dumping has negative effects that are clearly identified such as nauseous
smells, smoke generation, pollution of the water table and the soil. The objective of this work
is to compare the results of tow methods 1) XRD (X-ray diffraction) and 2) XSP (X ray
photoelectron spectroscopy) and the extraction of ETM established independently by the
above approaches. The sampling points are distributed in the bed of the Meboudja wadi.

2 Relationship between soil parameters and MTE concentrations

Within the study site, the majority soil types were “technosols” (soils that have been
deeply modified by human activities), “fluvisols” in the Seybouse plain, and “arenosols” in
the Edough massif. Technosols exhibit alkaline pH, high values of sand, and low CEC. Flu-
visols have alkaline pH and high values of clay and CEC. Arenosols are characterized by
acidic to neutral pH, high values of sand and low CEC, Maas, S., et al. (2010). The sampling
area shows a northto- south gradient for clay content, as shown by the representation of the
soil texture triangle (Fig. 1 A)

Mer Mediterranée

4070070 N
W E
S

ANNABA

4070020

4069970

MO39
MO25
MO17 s e
4069920 MO16 ud
ja us
MO18
o
bo
Me yb
Ou
ed Se
383940 383990 384040

FIG. 1 (A) – Soil type map and representation of the samples according to USDA texture
classes (Maas, S., 2010). (B) – Map of sampling points sediments
 N. Bougherira et al.

2.1 Materials and methods

Two sets of sampling were conducted in the month of January 2009 and March 2009 In
keeping with our ai sample must account of a recent pollution; sedimentological metals bind
preferentially on the fine fraction of less than 63μm.
The x-ray diffractometry is a technique for determining the nature of the minerals con-
tained in the whole rock. This method, which is essential in the identification of complex
clay assemblages (i.e. where natural assemblages in soils and sediments)
The X-ray diffraction is to apply radiation of the wavelength of X-rays (0.1 <λ <10 nm)
monochromatic; the condition for radiation is in phase is expressed by Bragg's law:

2.1.1 X-ray diffraction :

Analysis by X-ray diffraction samples taking in Meboudja wadi, gave us

the following results:
After calculating the value of "d" and the intensity of each peak are observed that the ma-
jority of peaks represent the percentage of quartz with a 93.28%, exempt sample 18, it repre-
sent calcite – quartz (Fig.2)

FIG. 2 – XRD diffractogram of the samples MO16 -MO17

XRD results
sample 16 Quartz - Calcite
sample 17 Quartz - Calcite - Muscovite -
Montmorillonite - Smectite
sample 18 Calcite - Quartz
sample 25 Quartz - Mica
sample 39 Quartz

TAB. 1 – Results of analysis by the method of XRD.

2.1.2 X-ray photoelectron spectroscopy (XPS)

X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic

technique that measures the elemental composition at the parts per thousand range, empirical
formula, chemical state and electronic state of the elements that exist within a material. XPS
spectra are obtained by irradiating a material with a beam of X-rays while simultaneously
measuring the kinetic energy and number of electrons that escape from the top 0 to 10 nm of
The assessment of degree of contamination associated with sediments geochemistry of
Meboudja wadi, Annaba district, NE Algeria

the material being analyzed. XPS requires high vacuum (P ~ 10-8 millibar) or ultra-high
vacuum (UHV; P < 10-9 millibar) conditions, although a current area of development is
ambient-pressure XPS, in which samples are analyzed at pressures of a few tens of millibar.
The atomic weight percent, In each type of sediment is represented in Tab.2

Element Wt% Wt% Wt% Wt% Wt%

(MO16) (MO17) (MO18) (MO25) (MO39)
CK 03.44 - 6.58 05.49 08.31
OK 10.86 20.99 20.89 19.08 13.96
MnL 01.02 00.00 0.00 00.00 00.00
CoL 00.43 01.00 0.00 00.14 00.37
NiL 00.00 00.00 0.00 00.00 00.00
CuL 00.04 00.00 - 00.06 00.00
AlK 08.23 11.96 7.87 06.61 11.32
SiK 25.93 27.42 30.66 31.47 23.90
PbM 01.18 00.50 0.88 01.03 02.40
CdL 00.37 00.41 0.34 00.00 00.58
KK 02.01 - 2.05 02.95 03.74
CaK 22.10 10.29 9.60 09.33 05.16
FeK 24.40 22.11 20.38 21.66 28.79
ZnL - 00.00 - - -
NaK - 00.36 - - -
MgK - 01.13 0.68 01.50 00.84
MoL - 01.00 - - -
KK - 02.82 - - -
HgM - - 0.08 00.00 00.18
AgL - - - 00.24 -
ZnL - - - 00.44 00.44

TAB. 2 – Results of analysis by MEB.

In each type of sediment, it is recorded the existence of the metal elements and low levels
of Co-Fe-Ni-Ag-Cd. The distribution of particles in each sample shows that there is a contri-
bution, the origin of the contribution of trace metals dissemination feels more or less easily
depending on whether isolated or releases if they come from sludge (Fig.3&4). For simplici-
ty, the heavy metals in the sludge are those referred, at least for a bound time.
 N. Bougherira et al.

FIG. 3 – XPS analysis of the samples MO16 -MO25

The analyzes carried on surface water (Fig.4 ) , shows high concentration levels (180 mg
/ l) Na2+, K+ (30 mg / l), Ca2+,Mg2+ (88 to 100 mg / l) and values of Iron (3.89 mg / l)
.We observe, from sediment analysis , a joint lower levels of Na+ , Mg2+ and we also note a
sharp drop in values of ETM. In contrast, the concentrations of iron, indicates more trapping
conditions than on all points.
18 200
16 180
160
14
140
Concent {mg/l]

12
120
XPS At%

10
100
8
80
6 60
4 40
2 20
0 0
Fe Mn Cu Zn Pb Na+ K+ Ca++ Mg++ Fe Mn Cu Zn Pb Na+ K+ Ca Mg++

MO16 MO25 MO37 MO16 MO25 MO37

FIG. 4 – concentration of elements in sediments and waters of the samples MO16 -MO25-
MO37

3 Conclusion
The chemical composition of sediments collected must be defined and located in terms of
relative contribution to the geochemical background, but also in relation to existing about the
application of materials likely to contain heavy metals regulations.
Environmental conditions likely to be dissolved elements may be toxic by their nature
and concentration, if the metal is soluble, it will pass into the groundwater and / or the plant;
if insoluble, it will remain in the soil. It must be analyzed using experiments to minimize
risk.
The assessment of degree of contamination associated with sediments geochemistry of
Meboudja wadi, Annaba district, NE Algeria

References
Boughriet, A., B. Ouddane, M. Wartel, C. Lalou, C. Cordier, L. Gengembre, and J.P.
Sanchez (1996). Con the oxidation of Mn and Fe in pollymetallic oxyde /oxyhydroxide
crusts from Atlantic Ocean. Deep-Sea research I, Vol.43, N°3.pp321-343,1996. Elsevier
Science Ltd.
Maas , S., R. Scheifler , M. Benslama, N. Crini , E. Lucot , Z. Brahmia , S. Benyacoub , and
P. Giraudoux (2010). Spatial distribution of heavy metal concentrations in urban, subur-
ban and agricultural soils in a Mediterranean city of Algeria. Environmental Pollution
Journal , Elsevier Science Ltd.
Ouddane, B., E. Martin, A. Boughriet, J.C. Ficher, and M. Wartel (1997). Speciation of dis-
solved and particulate manganese in the Seine river estuary. Marine chemistry. Elsevier.

Summary
Résumé. L'Algérie a mis en place un réseau industriel dense, concentrant les
secteurs gros consommateurs de l'eau et d'énergie. Ce tissu industriel a été im-
planté à proximité des sources d’eau (mer Méditerranée), ou des fleuves qui
sont devenus des décharges pour des rejets liquides non contrôlés. La Me-
boudja est un des fleuves les plus anthropisé de la plaine d’el Hadjar : elle
abrite une des plus fortes densités industrielles, agricoles et urbaines
Dans cette étude, nous avons surtout mesuré la teneur des métaux lourds
(oxydes) dans les sédiments, toutefois, les concentrations de Fe et Mn étaient
significativement plus élevés dans les échantillons d'eau supplémentaires par
rapport à ceux de la région d’Annaba. Dans une majeure partie de ce travail
toutes les espèces possibles dans la solution d'eau sont décrites, quant à leurs
concentrations nous amène à une autre partie des résultats est l'incorporation
des ETM dans les sédiments.
L’Analyse par la DRX est nécessaire de mettre en évidence les principales
modifications des effets des rejets industriels, agricoles et de l'eau domestique.

Mots-clés: sources d'eau, la Meboudja, concentrations , l'analyse des sédiments

 Changes in soil macronutrients after a long- term application
of olive mill wastewater

Leïla Chaari*, Nada Elloumi **, Salma mseddi*, Kamel Gargouri***, Béchir Ben
Rouina***,Taher Mechichi****, Monem Kallel *

*University of Sfax, Laboratory of Water, Energy and Environment, National School of

Engineers of Sfax (ENIS)E-mail : leila-chaari@hotmail.fr; monemkallel@gmail.com
** University of Sfax, Laboratory of Water, Energy and Environment, High Institute of
Biotechnology of Sfax (ISBS), E-mail : nadaelloumi@yahoo.fr
*** Laboratory of Improvement of Olive and Fruit Trees Productivity, Olive Tree Institute
of Sfax, E-mail : kamel.gargouri@iresa.agrinet.tn, E-mail : rouina.bechir@iresa.agrinet.tn

****Laboratory of Enzyme Engineering and Microbiology, National School of Engineers of

Sfax (ENIS), E-mail : tahar.mechichi@enis.rnu.tn

Abstract. The land spreading of olive wastewater (OMW) derived from olive
oil production can represent a suitable option to enrich and maintain
agriculture soils under south Mediterranean climates. Therefore, OMW
spreading field may represent a low cost contribution to crop fertilization and
soil amendment. The main objective of this study was to investigate the long-
term effects of raw OMW application on soil macronutrients and phenolic
compounds dynamics. The results showed that regular application of three
doses: 50, 100 and 200 m3.ha-1 of OMW for nine successive years increase the
soil electrical conductivity significantly with the increasing of OMW rates at
the depth 0- 20 cm. the pH variations were not detected after ten month after
the spreading date. Furthermore, soil sodium adsorption ratio and
exchangeable sodium percentage values were substantially affected by OMW
salinity. The soil organic matter increased from 0.068 % observed at the
control to 0.2 %, 0.34 % and 0.48 %, respectively, with the increasing of
OMW rate in the top layer (0-20 cm). The potassium, phosphorus and nitrogen
increased gradually with the OMW application dose. The Ca2+ contents on soil
decreased with the spreading of OMW rate, referred to control. In addition, the
phenolic compounds variations were not proportional to doses applied and
remained high as compared to the control essentially on top layers (0- 40 cm).
Changes in soil macronutrients after long-term application of olive wastewater

1 Introduction
Mediterranean countries are the major world producers of olive oil with 2.205.300 t
produced by EU member states in 2011 (IOC, 2012). The extraction process of olive oil
requires a high amounts of water and, correspondingly, a large amounts ( more than 30
million m3) of a waste known as olive oil mill wastewater (OMW) is generated ( Mechri et
al., 2007; Sallami et al., 2008). This wastewater is produced over a short lasting period
during the winter time, from November to February (Moraetis, 2011), creating a major
environmental problem. This volume of OMW produced is strongly influenced by the
milling method (Sierra et al., 2001; Kappellakis et al. 2008).
This waste is recalcitrant effluent, with an acidic pH (4- 5.5), a very complex redox
system (conductivity: 6- 16 mS), a high buffer capacity, tension activity and stability
(Ouzounidou et al., 2010). More importantly, OMW presents high values for BOD 5 (40-95
g.L-1), COD (50- 180 g.L-1), LD 50 toxicity for fish 8.7 %. In addition, OMW contains large
amounts of suspended solids and high concentrations of polyaromatic compounds e.g. simple
phenols and flavonoids, or polyphenols from 0.5 to 24 g.L-1 ( Ramos- Cormenzana, 1986;
Paredes et al., 1987; Rouvalis et al., 2004; Roig et al., 2006) while it cannot be directly
disposed into domestic wastewater treatment. Furthermore, this effluent has a high potassium
level and notable concentrations of sodium, phosphorus, calcium and magnesium (Sellami et
al., 2008).
To reduce its environmental impact, different remediation methods have been developed
to dispose of OMW such as evaporation in storage ponds, thermal concentration, physic-
chemical and biological treatments (kapellakis et al., 2008; Roig et al., 2006). These include
its application in agriculture soils as fertilizer. The high content of organic matter and plants
nutrients makes OMW a low-coast fertilizer, as well as a convenient source of irrigation
water in Mediterranean countries suffering of water scarcity (Caputo et al., 2013). Di Bene et
al. (2013) show that a long-term repeated OMW spreading has no residual effects or
negative trends in soil chemical and biochemical changes, even the short-term effects do not
persist and should be considered negligible after a suitable period. The effect of annual
application of three OMW doses (50, 100 and 200 m3 ha-1); at different successive layers on
sandy soil and investigating the soil sodium adsorption ratio (SAR) and exchangeable
 L. Chaari et al.

sodium percentage (ESP); would be interesting for later work. A yearly cumulative OMW
supply amended in agriculture land for a long-term would be interesting to consider.
The main objective of the study was to investigate the long-term effects of OMW
application on several physic-chemical soil properties and phenolic compounds dynamics at
different soil layers of designated olive tree test-sites.

2 Materiel and methods

2.1 Sampling and handling of OMW and soil
The soil was sampled from an agriculture area located in «Chaâl» experimental station.
The olive-trees field for experimental purposes was divided into four plots (T0, T50, T100
and T200). The latter three were regularly spread with the same annual dose of raw OMW
on each January for nine successive years. The experimental plots T50, T100 and T200 have
been respectively irrigated with 50, 100, and 200 m3 ha-1 of untreated OMW (Mekki et al.
2007). The plot non-irrigated with OMW (T0) served as control.
Ten months after every OMW amendment, soil samples were collected at different layers 0-
20, 20-40, 40-60 and 60-80 cm for each plot. The field-moist soil samples were sieved (<2
mm), delivered and then stored at 4 °C prior to analysis.
OMW was taken from evaporation ponds at the extraction factory plant in Chaâl, stored
at -20°C and then characterised accordingly before application.
2.2. Physico-chemical analyses of OMW and soil
The OMW characteristics depend on the olive variety, climate and the oil extraction
method (Kallel et al., 2009). The chemical oxygen demand and Biochemical oxygen demand
were determined according to AFNOR T 90-101, respectively. Total phosphorus P was
measured calorimetrically (Olsen et Sommers, 1982) and total nitrogen was determined by
the Kjeldhal method. The organic matter was measured after the incineration of samples at
550°C for 4 h and K+, Na+, Ca2+ and Mg2+ by atomic absorption spectrophotometry
(HITACHI Model Z-6100). Total phenolic compounds value was determined by using the
Folin–Ciocalteau method (Box, 1983). The physico-chemical characteristics of OMW are
summarized in TAB.1.
Changes in soil macronutrients after long-term application of olive wastewater

Characteristics Average value

pH 4.63± 0.48
EC (dS cm-1) 14.53± 0.20
TOC(g L-1) 24± 0.93
COD (g L-1) 87±1.09
Minerals matters (g L-1) 13.2± 0.28
Nitrogen (g L-1) 0.34± 0.25
Carbon/Nitrogen 117
P (g L-1) 0.19±0,049
Na+ (ppm) 1400± 0.05
K+ (ppm) 4300± 0.05
2+
Ca (ppm) 380± 0.05
2+
Mg (ppm) 320± 0.05
SO42- (ppm) 1.58± 0.05
Cl- (ppm) 3± 0.05
Total phenols (ppm) 4200± 0,49

TAB.1–Characterization of OMW used in spreading

The soil pH and EC were measured on mixture of soil water (1:2.5 and 1:5, respectively).
Walkley-Black method was used for the soil organic matter analysis (Nelson and Sommers,
1996); total nitrogen by the Kjeldahl method; P by Olsen and Sommers methods (1982);
exchangeable bases (Na, K, Ca, Mg) by atomic absorption spectrophotometry (HITACHI
Model Z-6100). The exchangeable Na+ percentage (ESP) was calculated from exchangeable
cations (1) and SAR was determined from Na+, Ca2+ plus Mg2+ (2) in the soil solution
(Sumner et al.1998). The calcium/magnesium (Ca/Mg) ratio was found by dividing the
quantity of calcium (cmol.Kg-1) by the quantity of magnesium (cmol.Kg-1).
ESP=100*([Na+]/CEC) (1);
SAR= [Na+]/ (([Ca2+] + [Mg2+)/2]0.5 (2).
Polyphenolic compounds from the soil samples were extracted with ethyl-acetate. For the
determination of total polyphenol contents, the Folin–Ciocalteau colorimetric method using
gallic acid as a standard (Box, 1983).
2.3. Field experimental soil characterization
On the toplayer (0-20 cm), the soils textures are a sandy (sand 94.3 %, clay 4.7 %, silt 1.3
%) with CaCO 3 content about 4.3 % accordingly a moderately alkaline pH (7.88), low
contents of organic matter (0.068 %) and cation exchange capacity about 4.69 ppm (TAB.
2). The layer 20-80 cm is characterized with an alkaline pH (8.22), EC value about 437
µS.cm-1 and high a content of calcium carbonate (8.3 %). Table 2 shows an increase of
calcium carbonate content and decrease of EC with depth. Naturally, the soil is poor in
organic matter therefore appear to be suitable to applied OMW on soil.
 L. Chaari et al.

Properties Soil layer (cm)

0-20 20-80
Sand (%) 94.3 95.4
Silt (%) 1.3 3.5
Clay (%) 4.7 1.1
Ca CO3 (%) 4.3 8.3
CEC (ppm) 6236 5979.4
MO (%) 0.068 0.068
pH 7.88 8.12
EC (µS.cm-1) 595 437

TAB. 2 –Characterization of Chaal soil sample

2.4. Statistical analysis

Statistical analysis was performed by using the SPSS 16.0. The treatments means were
compared by using the Spearman’s test at 5% significance level. In order to establish the
correlation of the different parameters after OMW amendment, principal component analysis
(PCA) was adopted. This analysis concerned on ten variables per treatment. For all
parameters the Spearman value inferior to 0.05 (p<0.05) corresponded to correlation
coefficient.

3 Results and discussions

3.1. Effect of raw OMW application on soil chemical properties
As a vital component of soil fertility, the soil chemical property reflects its potential
ability to provide nutrients for plants (Arshad et Martin, 2002). In experimental site, a long-
lasting repeated OMW spreading determined the impact of long-term on soil chemical
parameters such as: pH, EC, SOM, Na+, K+, Ca2+, Mg2+ and polyphenols contents in
comparison with the control.
3.1.1 EC and pH progress
As a consequence of irrigation with OMW, soil pH (TAB. 3) indicated no significant
difference with the application of increasing OMW doses. Yet, the pH variation for treated
soil showed no difference if compared to the control soil. Despite of the OMW acidic pH
mainly caused by the presence of organic acids, it did not influenced soil pH. A small pH
variations were temporary (Piotrowska et al., 2011) and were not detected after a few weeks,
even for a high OMW application rate (420 m3 ha-1) that was repeated over several years
(Chartzoulakis et al., 2010).
Table 3 also showed the evolution of EC after the spreading of OMW, OMW EC was
about 14.53 mS cm-1 therefore the increase in soil EC was related to the high salts
concentration in the OMW. The treated soil EC value unregistered in the top layer (0-20 cm)
Changes in soil macronutrients after long-term application of olive wastewater

was high if compared to control but it was still below the EC threshold value for salinity (4
mS.cm-1). In addition, EC values decreased with depth due to the infiltration by precipitation
that induced a transfer of ions to the groundwater (Sierra et al., 2007). Furthermore, the soil
EC increase seemed irreversible especially in the treated upper soil layer for the dose 200
m3ha-1.
Layers (cm) Doses (m3 . ha-1.year-1)
0 50 100 200
pH 0-20 7.88 7.76 7.88 7.83
20-40 8.05 8.12 8.12 8.13
40-60 8.13 8.13 8.13 8.16
60-80 8.16 8.16 8.19 8.17
EC (µS/cm) 0-20 595 2560 3220 5610
20-40 472 601 736 1654
40-60 422 515 651 1560
60-80 416 445 506 1211

TAB.3 –Effect of a raw OMW on pH and EC soil changes

3.1.2. SOM, P and N evolution

As consequence of long-term repeated OMW doses, the soil organic matter on top layer
(SOM) increased from 0.068 % in the control to 0.2 %, 0.35 % and 0.5 % with OMW
gradual doses application 50, 100 and 200 m3 ha-1, respectively. The analysis of SOM in the
various layers (FIG. 1) showed an increase of SOM rate proportionally to the increasing
OMW doses application. Furthermore, Mahmoud et al. (2010) observed that the SOM
increased after spreading OMW over the soil for 5 and 15 years in the top soil. The highest
level was recorded at plot T100 and T200 on layer 0-20 cm, with a slight migration towards
the lower layers compared to the control. It was expected that SOM will increase
significantly with depth for longer term OMW spreading especially for plots T100 and T200.
In addition to being a direct source of essential plant nutrient, SOM was not only supplied of
carbon but also for phosphorus and nitrogen and it was not solely affected by concentration
but also by composition, according to Haug (1993).
The soil P on toplayer increased slightly from 52.5 ppm to 64.5, 69 and 77 ppm with the
application of gradual doses 50, 100 and 200 m3 ha-1, respectively (FIG. 1). The spreading of
OMW on soil involved the enrichment of the high soil layers by P with a small quantity
which migrated towards the lower layers even with a higher dose (200 m3 ha-1).Carreira et al.
(2006) indicated that pedogenic CaCO 3 is the primary geochemical agent in arid ecosystems
capable of reducing leaching losses of P, through secondary precipitation of Ca–P minerals
 L. Chaari et al.

and/or strong sorption reaction of P with CaCO 3 , which has broadened ecosystem
implications for the retention of P, within both the soil profile and the landscape.
The evolution of nitrogen on soil after long-term repeated OMW spreading doses showed
an increase in the top layer (0-40 cm) with increasing a gradual dose (FIG. 1). N content in
the top layers at T50, T100 and T200 plots (210, 273 and 343 ppm) was relatively higher
than the values recorded in the respective control site T0 (161ppm). In the other hands, the
low nitrogen content of raw OMW increase the soil C/N ratio to 117. This high ratio causes a
slow mineralization due to bacteria needs (Mekki et al., 2009)..
Layers (cm)
T200
60-80
T100 40-60
Plots

20-40
T50 0-20

T0

0 0,2 SOM (%) 0,4 0,6

T200 Layers (cm)

T100
Plots

60-80
T50 40-60
20-40
T0
0-20
0 20 40 60 80 100
P (ppm)

T200
Layers (cm)
T100
Plots

40-80
T50
T0 0-40

0 100 200 300 400

N (ppm)

FIG. 1 –Effect of OMW amendment on SOM, P and N at four soil layers (0-20, 20-40, 40-60
and 60-80 cm). Error bars represent ± one standard deviation from the mean, n=3.
3.1.3. Mineral elements progress
Altough K+ is not considered as polluant, it is present in OMW with a high concentration
about 4300 ppm FIG. 2 displays the evolution of K+ after OMW spreading on the soil. K+
level increased on layer (0-20cm) for plot T50, T100 and T200, referred to control. Whereas,
the highest level of potassium (850 ppm) was unregistered on top layer at plot T200. This
level was almost 8 times higher than that in the control, whereas K+ rate recorded no
Changes in soil macronutrients after long-term application of olive wastewater

difference between treated plots and the control from layer 20-40 to 60-80 cm. Potassium is
an essential element for development, plant growth and many plant functions (Mäser et al.
2002; Zhang et al. 2010). Potassium availability in soil has a major role in estimating
fertilisation requirements.
+
Hence, Na showed the same change recorded for K+ (FIG. 2). Na+ rate in the soil
amended with 50 and 100 m3 ha-1 unregistered no difference from layer 0-20 to 60-80 cm.
Notably, the raise of Na+ levels in deeper layers of T200 is related to leachining by
infiltration. In addition, the Na+ excess on soil solution was neutralised by CaCO 3 or CaSO 4 ,
both naturally present in the soil (Gupta and Abrol, 1990). The neutralisation caused a
decrease of Ca2+, and since the soil particles tend to repel each other causing clay dispersy
and the collapse of the soil structure.
T0 T50 T100 T200
Na+ (ppm)

190
140
90
40
0-20 20-40 40-60 60-80

Layers (cm)

1200 T0 T50 T100 T200

1000
800
K+ (ppm)

600
400
200
0
0-20 20-40 40-60 60-80
Layers (cm)

FIG. 2 –Soil Na+ and K+ evolution as a function of amended OMW.

As the resultant of long-term repeated OMW application, the ESP value was under 2.1 %
in each layer and for every dose applied (FIG. 3). As expected the highest ESP values was
recorded at the upper layer (0-20 cm) of soil treated with 200 m3 ha-1 if compared to the
control. These results are below the limit of ESP and it prevents soil from clay dispersy
which can lead to serious physical problems (Qadir et al., 2007). The effect of OMW applied
on the soil lead to an accumulation of Na+ in the soil, for that reason, SAR result was
primordial for our investigation (FIG. 3). SAR values recorded the same progress as ESP
values. Eventually, SAR values were far below the limit (> 15), established to define saline
sodic soil soils (US Salinity Laboratory Staff 1954). Moreover, sodium adsorption should be
 L. Chaari et al.

very low due to the sandy material which is mainly composed of gypsum and has a low
cation exchange capacity (Marlet et al. 2009).
SAR
ESP (%)
0,26
2,0
0,24

0,22 1,8

0,20
1,6
0,18

ESP (%)
SAR

0,16 1,4

0,14
1,2
0,12
1,0
0,10

0,08 0,8
(4 )

(6 )

0 0)

( )

( )

( )

T1 (0 )

T1 (20 )
0)

( )

T2 (0 )

T2 (20 )
0)

(6 )

)
(2 )
0

0 20

0 40

0 60

00 80

00 80

0
80
0
T0 0-4

T0 0-6

T5 0-8

00 -2

00 -4

00 -6

00 -2

00 -4

00 -6
T0 -2

T5 (0-

T5 20-

T5 40-

T1 60-

T2 60-

0-
T1 40

T2 (40
(0

(
T0

FIG. 3 –Effect of long-term OMW application on SAR and ESP progress.

The soil irrigated with OMW for many years may cause accumulative effect of sodium
and displace the calcium and magnesium. FIG. 4 shows Ca2+ level in the different layers of
the control plot as higher than the levels recorded at plot T50, T100 and T200. According to
OMW nitrogen content that affected the pH soil with the realization of ions H+ due to
nitrification (enhanced by the increase in soil microbial populations) inducing Ca2+ loss
through leaching (Chesworth 2008) and Ca2+ set free are adsorbed onto the cation exchange
sites and precipitated as carbonate.
FIG. 4 shows Mg2+ rate high at the plot T0 for each layers, as compared to T50, T100.
The high rate was recorded in the upper layers for plot T200. In fact, Mg was retained and
adsorbed by soil but considerably less strongly than calcium (Foth 1990).
A significant factor affecting plant mineral nutrition is the Ca and Mg ratio (Ca/Mg) in
the soil. A slight variation was found for Ca/Mg ratio (~ 8.2) on different layers at control
plot (FIG. 4). This ratio for plot T100 was about 10.2 and 10.8 on the layer 40-60 and 60-80
cm, respectively. This increase compared to the control was related to the soil Mg level
decrease. On the other hand, the Ca/Mg ratio found at plot T200 decreased on the upper layer
referred to control due to the decrease of Ca. Pal et al. (2006) attest that ESP and Ca/Mg are
an important indicator of soil structure stability. In our investigation, ESP was under 3 and
Ca/Mg was above 6. This value may be far from Tunisian soil dispersion limit.
Changes in soil macronutrients after long-term application of olive wastewater

Ca/Mg
10,8

9,6
Ca/Mg
8,4

7,2

468 Mg (ppm)
Mg2+ (ppm)

416

364

312

5760
Ca (ppm)

5520
Ca2+(ppm)

5280

5040
T0 40- )
(6 60)
T5 0 ( 0)
T5 (20 0)
T5 (4 0)
T1 (60 0)

0 (0 )
0 0 )
00 40- )
T2 (6 0)

0 (0 )
0 20 )
00 0- )
(6 60)

)
T0 20 )
( 40

T1 00 -80
T1 0 (2 -20
T1 0 ( -40

T2 00 -80
T2 0 ( -20
T2 0 (4 -40

80
( 20

-8
0 0-2
0 -4
0 0-6

6
-

0-
T0 (0-

T5 0

0
T0

FIG. 4 – Effect of OMW amendment on Ca2+, Mg2+ and Ca/Mg ratio at four soil layers (0-
20, 20-40, 40-60 and 60-80 cm).

3.2. Phenolic compounds changing

This part of the investigation study was concerned with phenolic compounds level in a
sandy soil (TAB. 4) irrigated by the increasing doses of OMW 50, 100 and 200 m3 ha−1
year−1. It traced the dynamic of the phenolic compounds content in different layers (0-40
and 40-80 cm).
OMW applied (m3 ha-1 )
Layers (cm) 0 50 100 200
0-40 2835 a 4275 b 4362 c 4581 d
40-80 3010 a 3184 b 3446 c 3490 d

TAB. 4– Amount of soil polyphenols (ppm) after OMW spreading of different doses: 50; 100
and 200 m3 ha-1 in the two soil layers (0–40 and 40–80 cm). Means with letters a b c and d
indicate a significant difference at P ≤ 0.05.
Phenolic compounds concentration on soil control varied from 2835 to 3010 ppm with
depth of 0-40 cm and 40-80 cm, respectively. Phenolic compounds level was very high in the
upper layer for each dose amended, and remained high as compared to the control. This
value indicated mobility of phenolic compounds in the sandy soil texture. The investigation
of Sierra et al. (2007) state that phenol are detected in concentration of approximately 200
ppm, even at the depth of 125 cm. The concentration of phenolic compounds decreased
substantially with depth and the value was not proportional to the gradual increase of the
 L. Chaari et al.

OMW doses. The application of raw OMW increased the phenolic compounds in the upper
soil layers to values above the levels unregistered in the deeper layers.
3.3. PCA analysis and relationship between different parameters
In order to test the relationships between macro-nutrient rates on the soil layers and the
gradually applied doses of 50, 100 and 200 m3 ha−1 year−1, a Spearman correlation coefficient
was used to quantify the strength of the relationship (TAB. 5). The pH was a negative
significant correlated with P (r= -0.503*), K+(r= -0.806**), Ca2+(r= -0.638*) and Mg2+(r= -
0.565*), whereas the SOM was a significant positive correlated to P (r= 0.811**), Na+ (r=
0.872**), K+ (r= 0.768**) and SAR (r= 0.872**). K+ was significantly and positively correlated
with Mg2+ (r= 0.542*) and SAR (r= 0.701**) while a significantly negative relationship was
calculated for Mg2+ level and Ca/Mg ratio. CE was significantly (p <0.01) positive correlated
with SOM, P and Na. A significantly (p <0.01) positive correlation was calculated with Na+
and K+ levels.
Parameters pH CE SOM P Na K Ca Mg Ca/Mg SAR
pH 1
CE -0.47 1
SOM -0.319 0.902** 1
P -0.503* 0.735** 0.811** 1
Na -0.427 0.898** 0.872** 0.68** 1
K -0.806** 0.830* 0.768** 0.824** 0.771* 1
Ca -0.638** -0.38 -0.040 0.09 -0.073 0.347 1
Mg -0.565* 0.298 0.298 0.495 0.465 0.542* 0.289 1
Ca/Mg 0.377 -0.371 -0.337 -0.420 -0.556* -0.45 -0.13 -0.923** 1
SAR -0.286 0.885* 0.872** 0.622* 0.964* 0.701** -0.24 0.307 0.307 1
*p <0.05, **p <0.01

TAB. 5 – Spearman Correlation matrix for analytical parameters after nine years OMW
application

This analysis reveals relationships between available nutrients in the soil treated and
untreated plots. Based on the components loading after the varimax rotation (FIG. 5), the
result of PCA showed a component 1 (PC 1) and component 2 (PC 2) 69.72 % and 14.67 %,
respectively. The components were considered significant and errors being included the
variation and various errors in soil sampling and analysis. This analysis displays the presence
of two groups.
Changes in soil macronutrients after long-term application of olive wastewater

The first group, including SOM, P, Na, K, Mg, K, SAR and ESP, showed a positive
correlation, justified the mineralization of organic matter to available nutrient for plant
growth by the microbial activity and confirm the improvement of soil fertility.
The second group including pH and Ca/Mg ratio correlated negatively with group 1 related
tothe mineralisation of carbon and the subsequent production of OH ions by ligand exchange
such as K+, Ca2+ and Mg2+ or to the Na+, brought by this waste which generated NaCO 3 of
more alkaline hydrolysis than the CaCO 3 .

FIG. 5– Plot of the first two principal components for chemical properties

4 Conclusion
The beneficial effects of waste application on the soil depends on the quality of waste, the
soil texture, structure, micro-organism activity and the discrimination by plant root during
uptake. These results may confirm that the applications of OMW on soil properties show an
opposite effect, due to amounts of beneficial and toxic organic compounds present. The
yearly application of OMW for 9 successive years improved the fertility of Tunisian sandy
soil. Therefore, one could consider it as a useful, low-cost soil amendment and an effective
fertilizer. However, for the applied dose 200 m3.ha-1, one should take into account the
cumulative effect of soil salinisation, which would transform the soil into an unproductive
one.

References
Arshad, M. A., et S. Martin (2002). Identifying critical limits for soil quality indicators in
agro-ecosystem. Agriculture Ecosystems Environment, 88: 153–160
Box, J.D., (1983). Investigation of the Folin–Ciocalteau phenol reagent for the determination
of polyphenolic substances in natural waters. Water Research, 17: 511–522.
Caputo, M.C., A. M. De Girolamo et A. Volpe (2013). Soil amendment with olive mill
wastes: Impact on ground water. Journal Environmental Management, 131: 216-221.
 L. Chaari et al.

Carreira, J.A., B. Vinegla et K. Lajtha (2006). Secondary CaCO 3 and precipitation of P–Ca
compounds control the retention of soil P in arid ecosystems. Journal of Arid
Environments, 64: 460–473.
Chartzoulakis, K., G. Psarras, M. Moutsopoulou et E. Stefanoudaki (2010). Application of
olive wastewater to Cretan olive orchard: Effects on soil properties, plant performance
and the environment. Agriculture Ecosystems and Environment, 138: 293-298.
Chowdhury, A.K.Md, C.S. Akratos, D.V. Vayenas et S. Paulou (2013). Olive mill waste
composting: A review. Internatinal Biodeterioration and Biodegradation, 85: 108-119.
Di Bene, C., E. Pellegrino, M. Debolini, N. Silvestri et E. Bonari (2013). Short- and long-
term effects of olive mill wastewater land spreading on soil chemical and biological
properties. Soil Biology and Biochemistry, 56: 21-33.
Foth, H.D. (1990). Fundamental of soil science. Chapter 12: Plant soil macronutrient
relations. John Wiley and Sons.
Gupta, R.K. et I.P. Abrol (1990). Salt-affected soils: their reclamation and management for
crop production. Advances in Soil Scence., 11: 223–289.
Haug, R.T. (1993). The practical handbook of compost engineering. Lewis Publishers.
Florida.
IOC, International Olive Council (2012). The world market in figures. Olivae 117: 28-34.
Kallel M., C. Belaid, R. Boussahel, M. Ksibi, A. Montiel, B. Elleuch (2009). Olive mill
wastewater degradation by Fenton oxidation with zero-valent iron and hydrogen
peroxide. Journal Hazardous Materials, 163: 550-554.
Kappekalis, I.E., K.P. Tsagarakis et J.C. Crowth (2008). Olive oil history, production by
product management. Reviews in Environmental Science and Biotechnology, 7: 1-62.
Mahmoud, M., M. Janssen, N. Haboub, A. Nassour et B. Lennartz (2010). The impact of
olive mill wastewater application on flow and transport properties in soils. Soil and
Tillage Research, 107: 36-41.
Marlet, S., F. Bouksila et A. Bahri (2009). Water and salt balance at irrigation schema scale:
A comprehensive approach for salinity assessment in Saharan oasis. Agricultural Water
Management, 96: 1131-1322.
Mäser, P., M. Gierth et J. I. Schroeder (2002). Molecular Mechanisms of Potassium and
Sodium Uptake in Plants. Plant and Soil, 247(1): 43-54.
Mechri, B., A. Echbili, M. Issaoui, M. Braham, S.B. Elhadij et M. Hammami (2007). Short-
term effects in soil microbial community following agronomic application of olive mill
wastewater. Applied Soil Ecology, 36: 216-223.
Mekki, A., A. Dhouib et S. Sayadi (2007). Polyphenols dynamics and phytotoxicity in a soil
amended by olive mill wastewaters. Journal Environmental Management, 84: 134–140.
Mekki, A., A. Dhouib et S. Sayadi (2009). Evolution of several soil properties following
amendment with olive mill wastewater. Progress in Natural Science, 19: 1515-1521.
Changes in soil macronutrients after long-term application of olive wastewater

Moraetis, D., F.E. Stamati, N.P. Nikolaidis et N. Kalogerakis (2011). Olive mill wastewater
irrigation of maize: impacts on soil and groundwater. Agricultural Water Management,
98: 1125-1132.
Nelson, D.W. and L.E. Sommers (1996). Methods of soil analysis, part 3. Chemical methods
p 961-1010. Madison.
Olsen, S.R. and L.E. Sommers. (1982). Phosphorus p. 403–430. In: Page A.L., R.H. Milller
and D.R. Keeny.editors. Methods of soil analysis, part 2. Madison: American Society of
Agronomy.
Ouzounidou, G., G.I. Zervakis et F. Gaitis (2010). Raw and microbiologically detoxified
olive mill waste and their impact on plant growth. Terrestrial and Aquatic Environmental
Toxicology, 4: 21-38.
Pal, D.K., T. Bhattacharyya, S.K. Ray, P. Chandran, P. Srivastava, SL. Durge et S.R. Bhuse
(2006). Significance of soil modifiers (Ca-zeolites and gypsum) in naturally degraded
Vertisols of the Peninsular India in redefining the sodic soils. Geoderma, 136: 210–228.
Paredes, M.J., E. Moreno, A. Ramos-Cormenzana et J. Martinez (1987). Characteristics of
soil after pollution with wastewaters from olive oil extraction plants. Chemosphere, 16:
1557–1564.
Piotrowska, A., G. Iamarino, M.A. Rao, L. Gianfreda (2006). Short-term effects of olive mill
waste water (OMW) on chemical and biochemical properties of a semiarid Mediterranean
soil. Soil Biology and Biochemistry,38: 600–610.
Piotrowska, A., M.A. Rao, R. Scotti et L.Gianfreda (2011). Changes in soil chemical and
biochemical properties following amendment with crude and dephenolized olive mill
waste water (OMW). Geoderma, 16: 8-17.
Qadir M., Oster J.D., Schubert S., Noble A. D. and Sahrawat K. L. 2007. Phytoremediation
of sodic and saline-sodic soils. Advances in Agronomy, 96: 197-247.
Ramos- Cormanzana, A. (1986). Physicals chemical, microbiological and biochemical
characters of vegetation water. International symposium on valorization of olive by
products, 19-40, FAO, la Caja de Ahorros, Madrid. ISBN 84-505-4814-4.
Roig, A., M.L. Cayuela et M.A. Sanchez-Monedero (2006). An overview on olive mill
wastes and their valorization methods. Waste Management, 26: 960-969.
Rouvalis, A., J. Iliopoulou- Georgudaki et G. Lyberatos (2004). Application of two
microbiotests for acute toxicity evaluation of olive mill wastewaters. Fresenius
Environmental Bulletin, 13: 458-464.
Saadi, I., Y. Laor, M. Raviv et S. Medina (2007). Land spreading of olive mill wastewater:
effects on soil microbial activity and potential phytotoxicity. Chemosphere, 66: 75–83.
Sellami, F., R. Jarboui, S. Hachicha, K. Medhioub et E .Ammar (2008). Co-composting of
oil exhausted olive-cake, poultry manure and industrial residues of agro-food activity for
soil amendment. Bioresource Technology, 99: 1177-1188.
Sierra, J., E. Marti, M. Garau et A. Cruanas (2007). Effects of the agronomic use of olive oil
mill wastewater: field experiment. Science Total Environment, 378: 90-94.
 L. Chaari et al.

Sierra, J., E. Marti, G. Monserrat, R. Cruanas et M.A. Garou (2001). Characterisation and
evolution of a soil affected by olive mill wastewater disposal. Science Total
Environment, 279: 207-214.
US Salinity Laboratory Staff (1954). Diagnosis and improvement of saline and alkali soils,
agriculture handbook no. 60. US Department of Agriculture, Washington DC, USA.
Zhang, F., J. Niu, W. Zhang, X. Chen, C. Li, L. Yuan et J. Xie (2010). Potassium Nutrition
of Crops under Varied Re- gimes of Nitrogen Supply. Plant Soil, 335(1-2): 21-34.

Summary
L’épandage des margines dans le sol ; déchets liquides de l’industrie oléicole ; présente une solution
convenable pour enrichir et conserver les sols agricoles sous les conditions climatiques sud –
méditerranéennes. En effet, la margine est un fertilisant liquide à faible coût économique, qui garantit
l’apport approprié en macroéléments pour le sol ainsi que la plante. Les résultats ont montré que la
conductivité électrique a augmenté en fonction de la dose de margine appliquée au niveau de l’horizon
0- 20 cm. Les variations de pH gardent la même évolution que celle du témoin, dix mois après le
traitement du sol au niveau des différents horizons. Le rapport d’adsorption du sodium (SAR) et le
pourcentage de sodium échangeable (ESP) ont été clairement influencé par la salinité de la margine
appliquée. Ainsi que, la teneur de la matière organique au niveau de l’horizon 0- 20 cm a augmenté
nettement, elle a passé de 0,068 % à 0,2 %, 0,34 % et 0,48 % en recevant les doses respectives de 50,
100 et 200 m3 ha-1. L’application successive à long-terme de la margine a mené à l’augmentation des
concentrations en potassium, azote et phosphore au niveau du sol. Les teneurs en Ca2+ a diminué en
comparent aux teneurs enregistrés au niveau du témoin. Quant, aux concentrations en composés
phénoliques au niveau des sols traités ont enregistrés des teneurs élevés non proportionnel à la dose
appliqués au niveau de l’horizon 0- 40 cm par rapport à celles du témoin.
 Energy efficiency through integrated environmental
management
Souad Benromdhane, Ph.D.
Physical Scientist/Environmental Engineer

Office of Air Quality Planning and Standards

US Environmental Protection Agency
benromdhane.souad@epa.gov

Abstract. Integrated Environmental Management has become an economic necessity after

industrial development has proven to be unsustainable without accounting for direct and
indirect impacts on the environment. Energy dependency, and the link between emissions
and climate change, are major challenges facing both developed and developing countries.
Several programs exist in different parts of the world to implement environmental protection
policies while fostering sustainable development. A new global market structure emerged
and changed the way we do trade. As a result, scientists, policy makers, as well as environ-
mental activists agreed on the need to focus on strategic conservation of natural resources,
and more specifically optimization of energy use. Energy prices and dependency are the
main forces driving the current search for alternatives to petroleum. However, environmental
concerns will remain unaddressed if we continue to consume as much energy as we currently
do. Greenhouse gas emissions will continue to rise with economic growth.
In this paper I will talk about programs like Environmental Labelling of manufactured
products that have a lesser impact on the environment. I will address energy efficiency
through optimization as well as integration of increasingly higher percentages of alternative
energy sources and the use of best available technologies. Energy criteria for Environmental
Labelling certification developed by such programs will be presented. The intent is to en-
courage manufacturers and service providers to supply consumers with less polluting and
less energy-consuming goods and services, inform consumers of the environmental and en-
ergy impacts, and thereby instil a more sustainable and responsible consumption. As many of
these programs were initiated in Europe and other developed countries, Environmental La-
belling requirements are a barrier to many exports manufactured in developing countries,
affecting current world trade and putting more pressure on those countries to meet these
requirements. Defining an institutional and legal framework of Environmental Labelling is a
key challenge in implementing such a program for key economic sectors such as tourism,
textiles and food production where energy needs are the most important aspect to control. A
case study of Tunisia and its experience with eco-labelling is discussed.
________________________________________________________________________
Key words: Energy optimization; Tourism, Textiles, Food Industry; and Environ-
mental Management.
Disclaimer: The views and opinions expressed in this article are those of the author and do
not reflect the official policy or position of any agency of the U.S. government.
Energy efficiency through integrated environmental management

1 Introduction
Rapid economic growth in the Seventies resulted in adverse effects on the environment
that led experts to seek urgent actions to preserve the future quality of life on earth. Against
this background, the concept of sustainable development was born. As defined at the time by
the Prime Minister of Norway, who chaired the World Commission on Environment and
Development, sustainable development is: “A development that meets the needs of the pre-
sent generations without compromising the ability of future generations to meet theirs.”
Sustainable development is a concept based on three principals and closely linked pillars: the
society, the economy, and the environment (Brundtland, 1987). It is essential to insure a
balance between economic growth and the different ecosystems as well as social justice. This
will allow developing countries to position themselves fairly in an international and global
economy and have improved access to health and education. The Brundtland Report also
promoted a controlled consumption of energy among other natural resources.
The attitude change, especially in developed countries, was captured by the marketing
business sector and applied to translate environmental worries to a commercial benefit. A
number of environmental declarations in product advertising emerged. Among others, labels
such as: “recyclable” or “this product uses less energy” or “this product contains recycled
matter” are now commonly seen on many market products. This attracted the attention of
consumers who were already looking for ways to lessen their impact on the environment
through the selection of greener products in their purchases. Given the risk of confusion on
the consumer side, governmental concern led to the creation of national and regional pro-
grams of Eco-Labelling. Government programs responded to the absence of standards to
ensure that such claims by businesses are credible and verifiable. This also aimed to protect
the consumer while preserving the environment.

2 Environmental Labelling and its Role in Energy Saving

Environmental programs are developed with each country's specific environmental goals
and needs in mind. It indicates for manufacturers that produce and market products are rela-
tively less harmful to the environment and encourages consumers to purchase products la-
belled as environmentally preferable. It is all done with the hope to encourage other produ-
cers to change their manufacturing procedures and reduce environmental harm (EPA, 1998).
Environmental Labels are intended to generate environmental benefits through their posi-
tive influence on consumers` purchasing decisions. They are a great instrument to create a
synergy between the different stakeholders in the society. While the consumer recognizes a
label or a logo as a selection aid to make greener purchases, the manufacturer uses the desig-
nation to communicate good environmental production practices. Nevertheless, this practice
should be accompanied by institutional and regulatory policies to prevent misuse and false
claims. This also will differentiate serious environmental claims from fraudulent marketing
slogans.
The implementation of such programs will also encourage the use of cleaner production
technologies to respond to a more demanding and competitive market while also informing
consumers. Furthermore, Environmental Labelling is seen by many producers and manufac-
turers as an opportunity to seek value-based distinction over a cost-based one.
 I. Benromdhane

The high cost of energy and the increased dependency on foreign supplies, has driven
most businesses to analyse their energy bills more closely. With prices doubling and tripling
in the last few years, businesses are struggling to stay competitive, and trying to find new
ways to improve their bottom line. For many years energy intensive industries were explor-
ing new manufacturing technologies along with alternative energy sources.
Industries are not always open to change, especially when those changes require addi-
tional investment spending. It is, however believed that Environmental Labelling programs
may foster the use of innovative available technologies offering cleaner and more sustainable
production. In fact, these programs calling for compliance with environmental regulations
are indirectly implying conservation or more specifically optimisation of natural resources
use. Energy and water availability, cost, and end use impact are often key concerns for any
business, and their conservation will not only improve the bottom line and competitiveness,
but will also lower emissions and reduce pollution. The environmental benefit is a net im-
provement that will, in the long run, preclude incurring remediation costs.

3 Energy Criteria in Environmental Programs

In recent years several programs, as shown in Table 1, emerged to respond to pressing
environmental issues. Even though the primary objective of Environmental Labelling is to
improve global environmental welfare, the driving force was to protect both consumers and
industries from false claims. In fact Environmental Labelling went from self-claimed infor-
mation by some manufacturers, to a third party certification by an accredited organization
and a board of Eco-Labelling in an Eco-Labelling program by ISO 14024 Directives.
TerraChoice in Canada is one example of labelling intended to reduce stress on the envi-
ronment. Another common goal is to educate consumers and increase environmental awa-
reness. It is believed that visible labels will educate consumers, and disseminate information
about environmentally sound products. Japan's EcoMark and Singapore's GreenLabel, speci-
fically stress green consumerism and environmental awareness.

Designation EU, Flower German, Japan, Canadian, USA,

Blue Angel Eco Mark TerraChoice Green Seal

Year of Creation 1992 1977 1989 1988 1992

Logo

TAB. 1 – Selected International Eco-labelling Programs

Energy efficiency through integrated environmental management

The Blue Angel has led the international effort in Eco-Labels. It was initiated in the Se-
venties by the German Agency of Environmental Protection. This agency succeeded in edu-
cating consumers about their “Right to Know”, and their role in protecting the environment.
Many Eco-Labelling programmes in other countries followed, but rarely with such success
(Loewe, 2004). This is likely due to the lack of financial and human resources allocated to
the programs in some cases, and a lack of authority to enforce regulatory environmental
policy in others.
In the midst of several Eco-Labels, the need for standardization emerged and we are cur-
rently witnessing a harmonization trend aimed at understanding/unifying international trade
issues. A great example is the European Union Eco-Label to bring harmony in different Eco-
Labelling programs to a unified program called the European Flower. The Flower is playing
an information dissemination-leading role in formulating a consensus standard across the EU
markets (EPA, 1998).
Eco-Labelling programs covered several areas of the industry, but took into consideration
market trends to make sure the message resonates with a large enough number of consumers
in order to create a meaningful market demand. In fact textiles, and tourism industries fit
well in these programs given the wide exposure that consumers have with their products and
services. In many countries these sectors are the heart of the economy and do have major
environmental impacts. Such sectors were also high energy consuming and depend largely
on foreign resources. A clear link between pollution prevention and energy efficiency is then
established. Energy Efficiency has become the number one criterion developed in all Eco-
Labelling programs.
Energy Criteria are different from one program to another and depend on available tech-
nologies and the opportunity to acquire them. These criteria are flexible and take into ac-
count improvements observed from one year to another. Table 2 illustrates indirect savings
observed as a result of the EU program within and outside the EU. It is however essential to
state that Energy Efficiency minimum requirements are set up to be met at the time of Eco-
Labelling Certification.

Designation Average Savings per Year

Within EU Outside EU
Units
Money 763 -- Million Euros
Energy 43 2.9 TeraWatt-hour
CO 2 27 1.9 Million Tonnes
Reduced Air Pollution 49 3.5 Thousand Tonnes

TAB. 2 – European Union Flower Indirect Benefits (2006)

3.1 Energy Criteria for the Tourism Sector

In many parts of the world, sustainability of the tourism sector is threatened. Energy con-
sumption patterns of tourist attractions were long studied and are known to consume a con-
siderable amount of any nation’s energy resources. For example, in New Zealand, tourism
 I. Benromdhane

was found to contribute considerably to the country’s energy bill, particularly when moto-
rised travel is used to overcome physical barriers such as scenic flights or jet boating which
consumption varies from (344 MJ/flight) to (255 MJ/ride), on a per capita basis. It is quite
high when compared to tourist attractions, such as museums (10 MJ/visit) (Becken, et al.,
2002).
In less developed areas of the world, increased tourist activities can easily increase na-
tional energy expenses. The lack of integrated environmental management in the design of
the buildings, the choice of equipment, and appliances can result in increased demand in
electricity given the increased flow of tourists for these relatively cheaper destinations.
Environmental Auditing has become an important tool to assess environmental perfor-
mance in many businesses, and tourism is no exception (Goodall, 1995). In established ho-
tels, it has become standard practice to find different ways to save on the energy bill and
improve the bottom line given the stiff competition.
In Canada for example, hotel energy efficiency measures were provided to cut costs
by 20 percent. Major expenditures were evident in lighting for guest rooms and common
areas, heating and ventilation as well as air conditioning and motorized equipment such as
elevators (ORHMA, 2006). This is also in line with the United States, where the average
energy consumption for water heating and lighting is about 41%, and space heating is about
18% of the total cost (Figure 1, EIA, 1995). The Alliance to Save Energy website lists a
number of measures that can assist hotels and resorts in improving their overall energy man-
agement, identify source energy-efficiency technologies and service providers, and bench-
mark energy use data in several countries.
These programs focus on improving energy consumption in several areas. For example,
controlling costs by avoiding wasteful consumption, and uses of alternative energy sources in
particular local renewable ones such as solar or wind power. Many of these programs pay
close attention to energy audits and advise the contender to seek energy efficiency measures
to make sure the systems are optimised.

Refregiration Office
Ventillation 2% equipement Cooking
1% 3% 5%

Cooling
6%
Water
Heating Others
41% 6%

Space
Heating
18%
Lighting
18%
Energy Information Administration, 1995

FIG. 1 – Average Distribution of Hospitality Energy Use in USA

Energy efficiency through integrated environmental management

3.2 Energy Criteria for the Textiles Sector

The textiles industry has witnessed drastic changes in energy consumption handling.
With stiff competition worldwide and low labour costs, manufacturers are driven to research
different ways of cutting costs and maximize profits. Energy is one critical area where tre-
mendous improvements have been made and record savings were reached in the last decade.
Several programs were implemented. For example in Canada, the textile industry enhanced
its energy intensity by 44.0 percent and cut its actual energy use by 39.7 percent between
1995 and 2002 (Office of Energy Efficiency- Annual Report 2002-2003).
The Textiles Sector Task Force in Canada remained committed to an energy intensity re-
duction target of 1 percent per year through 2010 to meet Kyoto Protocol goals. The chal-
lenge however is to involve more companies in the program, as well as Industrial Energy
Innovators. To make further advances in energy efficiency, companies must adopt bench-
marking and best-practices approaches to energy management as a part of their ongoing
business management strategies (Office of Energy Efficiency- Annual Report 2002-2003).
Another very important area of interest is technological advances. Companies should be
more open to new and cleaner ways of production. For example, Nansulate High Heat insula-
tive coating is demonstrating its ability to conserve energy when applied to high surface
temperature equipment in textile plants where Nansulate High Heat applied to heat exchan-
gers caused a 25% decrease in the amount of time necessary to heat water to 110 degrees
Celsius for one of the company’s customers (Bilgin, 2006).
Many textiles manufacturing operations use wet processing techniques. These techniques
involve using an aqueous solution or bath to apply chemicals to a textile substrate, fixing the
chemicals to the fibre, scouring or washing to remove loose chemicals and drying to produce
a finished fabric or garment. Heating and later evaporating water make these wet processes
very energy intensive. Industry experts estimate that wet processes use approximately 60%
of the energy consumed in the textile industry. This gives a great margin to work with to
save on energy consumption.

3.3 Energy Criteria for the Food Processing Industry

Health and safety issues are the main driver in food production control and many labels
have been created to stress the origin and ingredients in food products. Very little has been
done about the food production process itself as long as costs can be translated into the con-
sumer price. Potential energy savings in the food processing industry are found in almost
every facet of operations. Processes used to manufacture, package, and process food are key
areas where energy could be saved. Emerging technologies in efficiency and productivity
design are available and could be commercially found in newer or recently upgraded food
industry facilities. However, lack of incentives discouraged manufacturers from seeking
these technologies despite proven reliability and capability through research, and prototype
testing. Potential benefits were also proven from distributed generation of energy onsite
instead of energy transmission lines. Combined heat and power, solar and wind power are
among several technologies that could be used in food processing.
On the other hand, producers looking to market their products may find that what appears
on the outside of the package is as critical as what they put inside. Hence they discovered
early enough in this industry what does “Eco-Label” tell about their product? (Lockeretz,
2005). In a Nutrition Today article on Eco-Labels, William Lockeretz, and Kathleen Merri-
 I. Benromdhane

gan, at the Friedman School of Nutrition Science and Policy at Tufts University, note that the
“organic sector has been growing at an annual rate of 20% for the past decade… [and] Eco-
Labels could soon move into the mainstream.”
An Eco-Label is used to indicate that a food has been produced in a way that is consi-
dered environmentally friendly. There is a broad range of labels that fall under the Eco-Label
category, including “various fair trade claims.” Farm animal welfare, decent treatment of
farm workers, and authenticity of a product are among those claims according to Lockeretz
and Merrigan. But which Eco-Labels are to be believed? For example EuropGap has gained
interest all over the world in the business field. But very little has been done at the consumer
level. In contrast, “Organic” labels are increasingly growing at a steady pace. Nevertheless,
they both lack the rationale behind Eco-Labelling Life Cycle Approach. It is therefore essen-
tial to demonstrate how well Eco-Labelled products can help small farms and small food
companies to compete in today’s food retailing environment, which favours larger suppliers
who can better afford to pay incurring fees. Nevertheless, the effort of implementing these
programmes faces various international trade issues (Dawkins, 1996).
This returns us to the main purpose of this paper, namely, addressing how an ECO-
LABELLING program that aims at raising the awareness of the consumer, and at the same
time fostering the interest of the industry to use integrated environmental management sys-
tems, could help a developing country compete in the current global market. This program is
helping policy makers to enforce environmental protection programs that encourage the use
of new energy efficient technologies for manufacturing as well as pollution prevention.

4 Tunisia: Case Study - An Eco-Labelling Experience

4.1 Project Initiative
Access of Tunisian products to European markets is highly dependent on compliance
with stringent European environmental directives and requirements. Environmental Label-
ling of Tunisian products is an initiative taken by the International Center of Environmental
Technologies of Tunisia (CITET) to encourage manufacturers and service providers to
supply consumers with less polluting goods and services, and instil a more sustainable and
responsible consumption. The project of Eco-Labelling included technical studies and con-
tribution from national and international experts. The objective was to evaluate social,
economic, and environmental conditions to set up the legal, regulatory, and institutional
framework as well as develop criteria for certification.

4.2 Regulatory Framework and Incentives

Tunisia has been well aware of the potential energy problem. Conscious of its fragile si-
tuation, it committed itself to undertake action and build a culture of energy conservation,
and in 1985, it created a national agency for renewable energies to play that role and several
actions were gathered in its Summary Report of twenty years of activities (ANME, 2006).
One very important move on energy efficiency was made, jointly by the Ministry of Trade
and the Ministry of Industry and Energy, on mandatory labelling of equipment and electric
appliances (Law N# 2004-72, August 2004 and its Decree N# 2004-2145 of Application,
September 2004).
Energy efficiency through integrated environmental management

A government initiative was set up to allow competition for rational use of energy and
promotion of renewable energies (Decree N# 2006-1394, May 2006). The immediate impact
of such a program was the promulgation of the legal documents that introduce the availabil-
ity of the Eco-Labelling program and its credibility. It is also the incentive for manufacturers
involved in this program to have an integrated environmental management system where all
aspects from energy to water to raw materials are taken into consideration as an integral part
of daily business management. The reinforced capacity of these companies is critical to the
access of Tunisia’s manufactured products in the European free exchange market in 2008
and its readiness to compete in a global market.

5 Recommendations
Regardless of what lies behind Eco-Labels use, a well-implemented program will ensure
that the basic requirements in getting certified are met. Therefore, a proper legal framework
is a key element to the enforcement of such practices. Eco-Labelling has addressed the area
of energy efficiency as an essential requirement given its potential to realise not only envi-
ronmental protection but also cost benefits, which got the attention of manufacturers in diffe-
rent industries. It is however essential to recognise that the most successful programmes are
the ones initiated by governmental authorities given the human and financial resources in-
volved as well as their capacity in enforcing their application through legal actions and fi-
nancial incentives. Moreover, from a policy maker perspective, it is recommended to help
establish environmental policy that promotes cleaner production and the transfer of innova-
tive technologies.
An energy audit or analysis is the first step toward a comprehensive energy management
plan. It provides information and insight into how the business uses energy. This is one
common criterion in all Eco-Labelling programs and applies to all industries. However, Eco-
Labelling goes beyond energy and resources handling. It addresses the lifecycle of the prod-
uct from its raw materials and the way they are handled to the waste generated at the end of
its use and its possible valorisation.

6 Conclusions
Eco-Labels are ideal tools to reach integrated environmental management as one way to
improve the image of how business is run. And, with their rapid growth have come several
important questions: How credible are they? How can one distinguish those motivated by
real environmental concern from those that use Eco-Labelling just as a marketing tactic? Do
consumers understand what they do and do not mean, or are they just “information over-
load”? Some economists as well as green critics challenged the idea that improving energy
efficiency will lower energy prices, (Greening et al, 2000). They insist rather on switching
to alternative replacements to fossil fuels, such as renewable energies and more energy con-
servation (Herring, 2000). Nevertheless, an Eco-Labelling program must be practiced in a
profitable economical environment for businesses. It should be in accordance with market
dynamics and must be able to adjust quickly and promptly to technological changes as well
as those of the global market. Thus, it must carry out periodic examinations to update the
criteria of certification and take into account technological advances and newly approved
standards.
 I. Benromdhane

References
ANME (2006). Twenty Years of Achievement and New Challenges. National Agency for
Energy Conservation. Tunisian Ministry of Industry and Small and Medium Enterprises,
annual report.

Becken S. and D. G. Simmons (2002). Understanding Energy Consumption Patterns of Tou-

rist Attractions and Activities in New Zealand. Tourism Management, Volume 23, Issue
4, Pages 343-354. New Zealand.

Bilgin V. Industrial Nanotech, Inc. (Press Release, April 6, 2006) (PRIMEZONE) Industrial
Nanotech's Nansulate Coating Demonstrates Ability to Increase Energy Efficiency for
Textile Industry. Naples, Fla.

Brundltland Bericht Report (1987). Report of the World Commission on Environment and
Development. UN General Assembly.

Dawkins, K. (1996). Eco-Labelling: Consumers’ Right to Know or Restrictive Business

Practice? GETS paper #95-3, Institute for Agriculture and Trade Policy, Minneapolis,
MN, 80 pp.

Goodall, B. (1995) Environmental Auditing: A Tool for Assessing the Environmental Per-
formance of Tourism Firms. The Geographical Journal, Vol. 161.

Greening, L. A., D. L. Greene, and C. Difiglio (2000). Energy Efficiency and Consumption -
The Rebound Effect -A Survey. Energy Policy, Volume 28, Issues 6-7, Pages 389-401.

Herring, H. (2000). “Is Energy Efficiency Environmentally Friendly? Energy and Environ-
mental, Volume 11, Number 3, pp.313-325 (13), Multi-Science Publishing Co Ltd.

Lockeretz, W., and K. Merrigan (2005). Selling to the Eco-Conscious Food Shopper. Nutri-
tion Today, 40:1.

Loewe, C., and M. Lichtl (2004). Overcoming the Communication Gap. Public-Private
Partnerships Towards Sustainable Lifestyles. ESOMAR, ISBN: 92 831 1357 8, Germa-
ny.

Office of Energy Efficiency (2003). - Annual Report 2002-2003. Textiles Improvements in

Day-to-Day Operations Drive Company Reductions in Energy Use.

Ontario Restaurant and Hotel & Motel Association, ORHMA, News, “Saving Energy Dol-
lars”, http://www.orhma.com/NEWS/saving_energy_dollars.asp, 2006.

Tunisian Decree n° 2006-1394 of may 22nd 2006, establishing a Presidential price to en-
courage the rational use of energy and promotion of renewable energies for the year
2005.
Energy efficiency through integrated environmental management

US Environmental Protection Agency. (1998). Environmental Labelling Issues, Policies, and

Practices Worldwide. Office of Prevention, Pesticides, and Toxic Substances, United
States Environmental Protection Agency.

Summary (French)
La gestion intégrée de l'environnement est devenue une nécessité économique à la suite du
développement industriel qui s'est avéré insoutenable sans tenir compte des effets directs et
indirects sur l'environnement. Les besoins énergétiques et la dépendance des sources étran-
gères en plus des problèmes liés aux changements climatiques dus à la pollution sont les
défis principaux auxquels sont confrontés les pays développés et les pays en développement.
Plusieurs programmes ont étés créés pour mettre en œuvre des politiques de protection de
l'environnement au profit d’un développement durable. Un nouveau marché mondial a émer-
gé et a changé la façon dont nous faisons les échanges commerciaux. En conséquence, les
scientifiques, décideurs, ainsi que les écologistes ont convenu de la nécessité de mettre en
place des stratégies pour la conservation des ressources naturelles et plus spécifiquement
l'optimisation de l'utilisation de l'énergie. Les prix de l'énergie ainsi que la dépendance des
sources étrangères sont actuellement les principales forces à l'origine de la recherche de
solutions alternatives au pétrole. Toutefois les préoccupations environnementales restent non
résolues si nous continuons à consommer autant d'énergie que nous le faisons actuellement.
Émissions de gaz à effet de serre continueront à augmenter avec la croissance économique et
les problèmes de pollution vont persister.
Dans ce document, je vais parler de programmes de produits labellisés (labels environnemen-
taux) à impact moindre sur l'environnement. Je vais aborder l'efficacité énergétique grâce à
l'optimisation, ainsi que l'intégration de plus en plus de sources d'énergie alternatives et l'uti-
lisation de meilleures technologies disponibles. Les critères de l'énergie pour l'étiquetage
écologique (écolabels) et la certification développée par de tels programmes seront présentés.
L'intention est d’encourager les fabricants et les fournisseurs de services à fournir des biens
et des services qui sont moins polluants et consommant moins d'énergie, et d’informer les
consommateurs des effets de l'énergie sur l'environnement pour aboutir à une consommation
durable et responsable. Comme un bon nombre de ces programmes ont été lancés en Europe
et dans d'autres pays développés, les exigences environnementales en matière d'étiquetage
sont devenues un obstacle à de nombreuses exportations fabriquées dans les pays en déve-
loppement. Ce qui affecte actuellement le commerce international, et met de plus en plus de
pression sur ces pays pour satisfaire à ces exigences. La définition d'un cadre juridique et
institutionnel de labels environnementaux est un défi en lui-même dans la mise en œuvre
d'un tel programme. Les principaux secteurs économiques tels que le tourisme, les textiles,
et la production alimentaire où les besoins énergétiques sont l'aspect le plus important à con-
trôler auront une tendance a bien bénéficié de ces programmes. Une étude de cas en Tunisie
et son expérience avec l'éco-étiquetage est discutée.
----------------------------------------------------------------------------------------------------------------
Mots Clés : Optimisation Énergétique; Ecolabel; Tourisme; Textiles; Industrie alimentaire;
et Gestion de l'Environnement.
 Defluoridation of Tap water by electrodialysis: effect of chloride and sulphate
anions
Soumaya Gmar, Ilhem Ben Salah, Mohamed Tlili, Mohamed Ben Amor
Laboratory of natural water treatment, Water Researches and Technologies Center,
Technopole Borj Cedria, Route touristique de Borj Cedria BP: 273 Soliman 8020, Tunisia

Soumaya.gmar@ymail.com; Ilhem_bensalah@yahoo.fr; Mohamed.tlili@certe.rnrt.tn ;

Mohamed.benamor@certe.rnrt.tn

ABSTRACT:
In Tunisia, the concentration of fluoride in south of Tunisia greatly exceeds the World Health Organization
(WHO) standards. Then, according to physicochemical analysis achieved on samples collected from several tap
water in south of Tunisia, it was shown that waters are contaminated by fluoride. In these waters fluoride
concentration varied between 0.8 and 4mgL-1. In this study, the electrodialysis (ED) technique was applied to
remove fluoride from these waters. Experiments were carried out using a pilot unit as a conventional ED in batch
recirculation mode. It was shown that ED is an efficient technique to remove fluoride and to reduce salinity of
water. Considering the effect of chloride and sulphate on fluoride’s removal through the anion exchange
membrane, the performance of ions exchange membrane (Neosepta) was studied. It was shown that fluoride’s
removal was influenced by chloride but not by sulphate ions.

1 INTRODUCTION:
Located in a semi-arid zone, Tunisia has limited water resources (Burghard (2013)). The scarcity of good water
quality in particular at the south regions requires brackish water desalination to supply these regions with potable
water. In addition to their high salinity, these waters contain high levels of fluoride (Mnif et al (2010). Fluoride
ions are necessary and beneficial for the human health at low concentration in drinking water. However, at high
concentration, water becomes toxic and leads to serious problems such as dental and skeleton fluorosis and
lesions of the endocrine glands, thyroid and liver (Fawel et al (2006), Mohapatra et al (2009). The optimum
fluoride ion level in drinking water is considered to be between 0.5 and 1.0 mg L-1 (Fewetrell et al (2001)).
According to the WHO, the maximum acceptable concentration of fluoride is 1.5 mg L-1 (Fewetrell et al (2008)).

In the literature, many methods have been investigated to remove the excess of fluoride from water, such as
adsorption (Loganathan et al (2013)), ion exchange (Kodama et al (2001)), chemical precipitation (Jiang et al
(2013)), electrochemical techniques (Tezcan et al (2013)) and membranes processes like, nanofiltration
(Chakrabortty et al (2013)), Donnan Dialysis (Boubakri et al (2013)) and electrodialysis (ED) ( Menkouci sahli
et al (2007), Amor et al (2001),Ben sik Ali et al (2010)). Most of them suffer from one of the following
drawbacks: high initial cost, lack of selectivity, low capacity, and complicated or expensive regeneration.
However, ED which is widely used for desalination of brackish water (Walha et al (2007), Banasiak et al (2007))
presents many advantages: it was a simple process which has an average installatalion cost and low chemicals
consumption (Zeni et al (2005)). In this present work ED technique was used for defluoridation of tap water.
Indeed, the interest in using ED processes to remove the excess of fluoride and other contaminants such as
nitrate and borate from drinking water has worldwide increased (Banasiak et al (2009),Tahaikt et al (2006),
Menkouchi sahli et al (2008)). It was demonstrated that ED is an efficient process for removing these
contaminants. On the other hand, it was shown that the presence of co-existing anions in brackish water play an
important role in defluoridation by ED process (Kabay et al(2008),Ergun et al (2008) .

The aim of this work is to remove excess fluoride from tap water using ED technique. In order to confirm that
water is contaminated by fluoride, physicochemical analysis were achieved on samples collected from several
tap water in the south of Tunisia. The effect of chloride and sulphate on fluoride removal was studied using
ions exchange membrane ( Neosepta).

2 MATERIALS AND METHODS

2.1 Chemicals reagents
Analytical grade Sodium Fluoride (NaF), Sodium Chloride (NaCl), Sodium hydrogenocarbonate (NaHCO 3 ),
Sodium sulfate (Na 2 SO 4 ), sodium hydroxide (NaOH) and glacial acetic acid (CH 3 COOH) are used in
experiments to produce solution with known amounts of salts and electrode rinse solution. Each solution was
prepared using distilled water. All chemicals were purchased from Sigma- Aldrich.

2.2 Tap water samples

Natural water samples are tap water collected from south of Tunisia. These waters are underground. The
physicochemical characteristics of these water samples are given in table1.

2.3 Electrodialysis equipment and membranes

The ED setup consists of a power DC, a concentrate reservoir, a dilute reservoir, a rinsing electrode reservoir and
three pumps (Heidolph D-93309) equipped each with a flow-meter (PC Cell GmbH). Figure1 shows a simplified
scheme of ED setup.
 FIG.1- Scheme of the ED installation

The ED cell was a PC Cell ED 64-004 (Germany) used as a conventional ED unit with two compartments: the
dilute and the concentrate compartment. ED cell is made by two polypropylene blocks supporting electrodes.
One electrode is made of Pt /Ir-coated Ti stretched (anode) and the other of Ti stretched metal (cathode). The
membranes and spacers are stacked between the two electrode-end blocks. ED stack is formed by 10 repeating
sections called cell pairs. A cell pair consists of the following:
- cation exchange membrane
- dilute flow spacer (0.5mm)
- anion exchange membrane
- concentrate flow spacer (0.5mm)
Spacers are made in plastic and are placed between the membranes to form the flow paths of the dilute and
concentrate streams. The spacers are designed to minimize boundary layer effects and are arranged in the stack
so that all the dilute and concentrate streams are manifold separately. For each membrane, the active surface area
is 64 cm2. The flow channel width between two membranes is 0.5mm determined by the thickness of
intermembrane spacers. Two types of ions exchange membranes were used: PC Cell membranes (PC-SK and
PC-SA are cation and anion exchange membranes respectively) and Neosepta membranes (CMX and AMX are
cation and anion exchange membranes respectively).The stack is equipped with three separate external
plastic reservoirs: The first serves to concentrate solution, the second to dilute solution and the third to rinse
electrode solution. The fluid circulation is achieved using three pumps equipped with flow-meters. Experiments
are performed in batch recirculation mode at ambient temperature.
2.4 Experimental procedure
During all experiments, the volume of dilute, concentrate and rinsing electrode solutions was 1L each. Rinse
solution was 0.1M Na 2 SO 4 in order to prevent generation of toxic gas. Before the onset of the desalination test,
the same solution was introduced in dilute and concentrate compartments. Flow rate of electrode rinse solution
was fixed at 100L h-1 for all experiments. Although the flow rate of the dilute and concentrate solutions were
fixed at the beginning of experiment.
The experiment starts at time of the potential application. Conductivity was recorded in time. It was measured
using conductivity meter (consort D 292). Dilute and concentrate were circulated through the ED cell until the
desired product conductivity (≈ 0.5mS cm-1) was achieved in the dilute. Samples were taken periodically from
dilute and concentrate compartments for analysis. After every experiment, ED cell was cleaned with circulation
of 0.1M HCl solution during 15min followed by circulation of distilled water in order to remove any deposits.
2. 5 Analytical methods
Fluoride concentration was determined using ion selective electrode (I.S.E 6.0502.150 fluoride ion electrode) in
conjunction with a standard reference electrode connected to a Metrohm 781pH/Ion-meter. To avoid the effect of
ionic strength on the activity of ion, a total ionic strength adjustment buffer (TISAB) solution was used. It
contains 58g of NaCl and 57mL of glacial acetic acid and their pH was regulated at 5.5 value using NaOH. The
fluoride samples and the fluoride standard were diluted by addition of TISAB solution with a molar ratio of 1:1.

Na+ and K+ were analyzed by atomic emission spectroscopy using a “Sherwood 410” spectrophotometer. Ca2+
and Mg2+ amounts were determined using a conventional colorimetric ethylene diamine tetraacetique (EDTA)
titration. HCO 3 - was determined using a conventional colorimetric sulfuric acid (H 2 SO 4 ) titration. Nitrate and
phosphate concentrations were measured by UV- visible spectrophotometric method. Chloride analysis was
measured by potentiometric titration using an automatic titrator (metrohm 809). Sulphate concentration was
determined by gravimetric analysis using BaCl 2 in acidified medium. pH-meter (consort D 291) was used for
measuring pH solutions.

2.6 Removal rate of fluoride ions (R F - %)

To investigate the effect of chloride and sulphate ions on fluoride removal by ED, the R F - (%) was calculated for
all experiments by the following equation:

Ct
RF- (%)=100 �1-( )�
C0

Were C t (mg L-1) is fluoride’s concentration in dilute compartment and C 0 (mg L-1) is the initial concentration of
fluoride in the feed phase.

2.7 Demineralization rate (DR%)

The demineralization rate (DR%) is calculated by the following equation:

St
DR (%)=100 �1-( )�
S0

Were S t (mg L-1) is the salinity in the dilute compartment and S 0 (mg L-1) is the initial salinity in the feed phase.
2.8 Specific power consumption (SPC)
Specific power consumption (SPC) can be described as the energy needed to treat unit volume of solution. SPC
was calculated using the following equation (Kabay et al (2008)):
t
E ∫0 I(t) dt
SPC =
VD
Where E is the applied potential, I the current, V D the dilute stream and t the time.

3 RESULTS AND DISCUSSIONS

3.1 physicochemical analysis of tap water
Tap water distributed for human consumption, in south of Tunisia was collected for physicochemical Analysis.
The salinity of these samples varies between 800 and 2200 mg L-1. The fluoride concentration varies between 0.8
and 4 mg L-1. In this study, only two examples of physicochemical characteristics of brackish waters rich on
sulphate and chloride ions are presented in table 1.

Table 1 shows that fluoride concentration largely exceeds 1.5 mg L-1, the value recommended by the WHO for
the two samples. The recommended value of 400 mg L-1 for sulphate is also exceeded for the two samples. Then,
the recommended value of 45mgL-1 for nitrate is exceeded for the two samples. However, for the chloride, the
recommended value of 250 mg L-1 is exceeded only for the sample 2. According to the salinity water sample 1 is
fresh (Total dissolved salt (TDS) ˂1500mgL-1) but sample 2 is brackish. If for the water sample 1 only fluoride
and nitrate must be reduced to obtain a drinking water with good quality. The sample 2 must be desalted to
reduce the salinity and pollutants.

TAB.1- Physicochemical characteristics of water samples

sample 1 sample 2
-1
Conductivity (mScm ) 1.90 3.16
pH 7.17 7.41
TDS (mg L-1) 1200 2000
- -1
Cl (mg L ) 149 305. 5
- -1
HCO 3 (mg L ) 119.56 111
SO 4 2- (mg L-1) 467 889
- -1
F (mg L ) 2.65 3.94
- -1
NO 3 (mg L ) 54.54 55.5
3- -1
PO 4 (mg L ) 3.63 4
+ -1
K (mg L ) 4.21 7.345
+ -1
Na (mg L ) 136.5 322
2+ -1
Ca (mg L ) 138.5 179.5
2+ -1
Mg (mg L ) 67.50 103.5
3.2 Treatment of tap water samples by ED

Many factors such as applied potential (E) flow rate (Q) and concentration of salt (C) influence the ED
efficiency. These factors were optimized in our research using 23 full factorial designs, for desalination of
brackish water. This method of optimization could satisfy high demineralization rate with low energy
consumption. The best optimal condition for desalination and depollution of brackish water were established at
applied potential 12V, Flow rate (Q) 90 L h-1 and C = 1 g L-1. These conditions will be applied in this work for
desalination and defluoridation of tap water of south of Tunisia. The physicochemical characteristics of treated
water are given in table 2.

TAB. 2- Physicochemical characteristics of treated water at E=12V and Q = 90L h-1 using PCCell membranes

sample 1 sample 2 Recommended values

-1
Conductivity (mS cm ) 0.5 0,5 0.5
pH 6.95 7.17 6.5-8.5
-1
TDS (mg L ) 390 390 500
- -1
Cl (mg L ) 78 81.65 250
- -1
HCO 3 (mg L ) 0 9.76 -
SO 4 2- (mg L-1) 158.5 164.5 400
- -1
F (mg L ) 0.212 0.283 1.5
- -1
NO 3 (mg L ) 0.58 0.55 50
K+ (mg L-1) 2 5 12
+ -1
Na (mg L ) 58.5 74 250
2+ -1
Ca (mg L ) 16.5 7.60 -
Mg2+ (mg L-1) 5.5 5.5 -

Defluoridation of tap water was achieved with fluoride concentration lower than the maximum recommended
by WHO. 92% of removal rate of fluoride was obtained after 21min and 30 min of ED application respectively
for sample 1 and 2. Moreover, the concentration of different species in the treated water is lower than the
amounts recommended by WHO for drinking water. The salinity around 400 mg L-1 was obtained after 21 min
of ED application with SPC= 2.52Wh L-1 for sample 1 and 30 min with 3.48 Wh L-1 for sample 2. This
difference was related to the initial salt concentration of water. The increase of salt concentration enhances an
increase in operation time and SPC. On the other hand, fig 2 shows that DR% depends on initial salt
concentration. A slight decrease is observed in the DR% for water sample 2. An increase of the initial
concentration leads to the decrease of DR%.
 TAB. 3- Variation of salinity, [F-] and SPC for sample1

Time Salinity [F- ] SPC R F

-

(min) (mg L-1) (mg L-1) (Wh L-1) (%)

0 1310 2.65 0 0
5 1034 1.05 0.8 60.37
11 689.78 0.517 1.92 80.49
21 325.78 0.212 252 92

TAB. 4- Variation of salinity, [F-] and SPC for sample 2

Time Salinity [F- ] SPC R F

-

(min) (mg L-1) (mg L-1) (Wh L-1) (%)

0 2179 3.94 0 0
3 1724 1.88 0.4 52.28
7 1379 1.24 0.84 68.52
12 1034 0.55 2.28 86.04
19 689.7 0.4 3 89.84
30 325.78 0.283 3.48 92.81

Desalination process can be stopped after only 5 min for a salinity value about 1000 mg L-1 and a fluoride
concentration of 1 mg L-1 for the sample 1 (Table 3). For the sample 2, ED desalination can be stopped after 12
min for approximately the same salinity and a fluoride concentration of 0.55 mg L-1 for sample 2. Fig 3 shows
that the initial current intensity necessary for ion transfer is more important for water simple 2. In fact, high
initial concentration of salt requires high intensity of current for the ions’ transfer. A significant

reduction in the current intensity was observed for sample2 in comparison with sample 1 which explain the large
reduction of fluoride concentration for water 2.
FIG. 2- Effect of initial salt concentration on DR% FIG.3- Change of current versus time

3.3 Effect of chloride and sulphate ions on Fluoride’s removal by ED

Table1shows that analyzed waters are rich in sulphate and chloride ions. So, the effect of the two types of ions
on fluoride’s removal by ED was studied using Neosepta membranes. Experiments were therefore conducted
with synthetic solutions containing 0.0357mol L-1 of NaHCO 3 doped with 15 mg L-1 of F-. Hydrogenocarbonate
ions was replaced by Chloride or sulphate at different values of molar ratio (R= [Cl-]/[HCO 3 -] and R’ [SO 4 2-
]/[HCO 3 -] = 0; 0.1; 0.25; 0.5; 0.75; 1). The solutions ionic strength was fixed at 0.0357molL-1 and maintained
constant. Current applied and flow rate of dilute and concentrate compartments were fixed at 0.6A and 40 L h-1
respectively for all experiments. Under these conditions, electrodialyser operate under the limiting current.

a- Effect of chloride on fluoride’s removal b- Effect of sulphate on fluoride’s removal

FIG. 4- Effect of chloride and sulphate on fluoride’s removal by ED
Figure 4.a shows that the competition between Chloride and fluoride ions during their electromigration to the
concentrate compartment was certain. The increase of chloride ions on the feed solutions leads to the decrease
of the removal rate of fluoride ions (Fig 5.a). This result could be explained by the decrease of ionic mobility of
fluoride in the presence of chloride ions. Similar result was obtained by Bensik Ali et al (2010), Kabay et al
(2008) and Ergum et al (2008). On the other hand fluoride’s removal by ED was not influenced by sulphate ions
(fig4.b). The transfer of fluoride ions is more rapid than the transfer of divalent ions which are strongly retained
in the membrane material. This is not in accordance with results of Bensik Ali et al (2010) and Ergun et al
(2008) which showed that fluoride removal rate decreases in the presence of sulphate ions. This difference was
related to operating condition, (initial concentration of fluoride, applied current and flow rate). Fig 5.b shows no
change in the removal rate of fluoride in the presence of sulphate ions.

a- Effect of chloride b-Effect of sulphate

FIG. 5- Effect of chloride and sulphate on removal rate of fluoride

CONCLUSION

Tap water of south of Tunisia was contaminated by fluoride and contained high concentrations of sulphate and
chloride ions. The effect of sulphate and chloride on fluoride’s removal by ED was studied. The results show
that there is no competition between fluoride and sulphate ions. However, the competition between fluoride and
chloride is certain. ED technique was applied for desalination and reduces contaminant fluoride from tap water.
It was shown that ED is an effective method for removal of excess fluoride from water. Fluoride ions could be
reduced from 2.650 to 0.212 mg L-1 corresponding to a fluoride removal of 92% for sample 1 and from 3.940 to
0.283 mg L-1 (92.81% removal) for sample 2. The reached concentrations of fluoride are lower than the WHO
standards as well as the concentrations of other ions for drinking water. The most important advantage of this
process is that salinity could be reduced to 1000 mg L-1 with 1 mg L-1 of fluoride ions.

References

Amor,Z. Bariou,B. Mameri,N. Takey,M. Nicolas,S. Elmidaoui,A (2001). Fluoride removal from brackish water
by electrodialysis. Journal of Desalination, 133: 215- 223.

Boubakri,A. Helali,N.Tlili,N.Ben Amor,M (2013).Fluoride removal from diluted solutions by Donnan dialysis
using factorial design. Journal of chemical engineering, 11814: 1- 6.

Ben Sik Ali, M. Hamrouni,B. Dhahbi, M (2010). Electrodialytic Defluoridation of brackish water: Effect of
process parameters and water characteristics. Journal of Clean- Soil, Air, Water 38(7): 623- 629.
Banasiak, L. J. Kruttschitt, T.W. A.I.Schafer, A.I (2007). Desalination using electrodialysis as a function of
voltage and salt concentration. Journal of Desalination, 205:38- 46.

Banasiak, L.J. Schafer, A.I (2009).Removal of boron, fluoride and nitrate by electrodialysis in the presence of
organic matter. Journal of Membrane Science, 334: 101- 109.

Burghard,M (2013). Solar power plant technology and future perspective for water desalination in the Maghreb
region. Conference, the 4th Maghreb conference on desalination and water treatment.

Chakrabortty, S. Roy, M. Pal, P (2013). Removal of fluoride from contaminated groundwater by cross flow
nanofiltration: transport modeling and economic. Journal of Desalination, 313: 115- 124.

Ergun,E. Tor,A. Cengeloglu,Y. Kocak,I (2008). Electrodialytic removal of fluoride from water: Effects of
process parameters and accompanying anions. Journal of Separation and Purification Technology, 64: 147- 153.

Fawell,J, Bailey, K. Chilton, J. Dahi,E. Fewtrell,L. Magara,Y (2006). Fluoride in drinking –water. World
Health Organization, Geneva, Switzerland.
Fewtrell,L.Bartram,J (2001). Water quality: Guidelines, standards and health.
Fewetrell,L. Bartram,J (2008).WHO, Guidelines for Drinking Water quality. Second Addendum to third edition.
Geneva.
Jiang,K. Zhan, K. Yan, Y. Du,H (2013). A pilot – scale study of cryolite precipitation from high fluoride –
containing waste water in a reaction – separation integrated reactor. Journal of Environmental Sciences,
25:1331- 1337.

Kabay,N. Arar,O. Samatya,S. Yuksel,U.Yuksel,M (2008). Separation of fluoride from aqueous solution by
electrodialysis: Effect of process parameters and other ionic species. Journal of Hazardous Materials, 153:107-
113.

Kir,E. Alkan,E (2006). Fluoride removal by Donnan Dialysis with plasma modified and unmodified anion
exchange membranes. Journal of Desalination, 197: 217- 224.

Kodama,H. Kabay,N (2001). Reactivity of inorganic anion exchange BiPbO 2 (NO 3 ) With fluoride ions in
solution. Journal of Solid State Ionics 141/142: 603- 607.

Loganathan,P. Vigneswaran, S. Kandasamy, J. Naidu,R (2013). Defluoridation of drinking water using

adsorption processes. Journal of Hazardous Materials, 248- 249: 1-19.

Menkouchi Sahli,M.A. Annouar,S. Mountadar,M. Soufiane,A. Elmidaoui,A (2008). Nitrate removal of

brackish underground water by chemical adsorption and by electrodialysis. Journal of Desalination, 227: 327-
333.

Menkouchi Sahli, M. A. Annouar, S. TAhaikt,M. Mountadar,M. Soufiane,A. Elmidaoui,A (2007). Fluoride

removal for underground brackish water by adsorption on the natural chitosan and by electrodialysis. Journal of
Desalination, 212: 37- 45.

Mohapatra, M. Anand,S. Mishra, B.K. Giles, E.D. Singh,P (2009). Review of fluoride removal from drinking
water. Journal of environmental Management, 91: 67- 77.
Mnif,A. Ben sik Ali, M. Hamrouni,B (2010). Effect of some physical and chemical parameters on Fluoride
removal by nanofiltration. Journal of Ionics, 16: 254.

Tahaikt,M. Achary,I. Menkouchi Sahli, M.A. Amor,Z. Takay,M. Alami,A. Boughriba,A. Hafsi,M.
Elmidaoui,A (2006). Defluoridation of Moroccan ground water by electrodialysis: continuous operation. Journal
of Desalination, 189: 215- 220.

Tezcan,U. Savas koparal, A. Bakir Ogutvern, U (2013). Fluoride removal from water and waste water with a
bach cylindrical electrode using electrocoagulation. Journal of Chemical Engineering, 223: 110- 115.

Zeni, M. Riveros,R. Melo, K. Primieri,R. Lorenzini,S (2005). Study on fluoride reduction in artesian well- water
from electrodialysis process. Journal of Desalination, 185:241- 244.

SUMMARY
Les techniques d’élimination des ions fluorures sont variées (membranaire, adsorption, électrochimique,
précipitation, coagulation – floculation). Les travaux réalisés dans ce travail avaient l’objectif l’application
d’une technique electromembranaire : l’électrodialyse, pour la défluoruration des eaux dont la teneur en fluorure
est supérieure à la valeur maximale admissible (1.5mg/L) selon l’OMS. L’analyse physico-chimiques des eaux
de robinet de sud Tunisien réveille que ces dernières sont contaminées par les fluorures et présentent des teneurs
élevés en sulfate et chlorure. Nous avons montré que l’élimination des ions fluorures a été influée par la présence
des ions chlorure, alors que les ions sulfate ne présentent pas un effet remarquable sur le transfert de ces
derniers. L’application de cette technique sur les eaux de boissons consommées par les habitants du sud Tunisien
nous a permis un abattement de la salinité et de la teneur des ions fluorures.
Managing urban parks for social and sustainable development
in Rome (Italy)
Stefano Ancilli *

*Università di Roma "La Sapienza"

stefano.ancilli@uniroma1.it

Abstract.. RomaNatura is the public institution that manages all the natural
parks inside the city of Rome, more than 16.000 ha of natural and historical
environment. In the last months the Communication and Education Office tried
a new and different management, based on people involvement. A new project,
called VITA (that can be translated in english as LIFE) started with six differ-
ent goals. The main purpose is to give back natural resources and spaces to cit-
izens, involving them in management and decision making. This paper wants
to present the first results of this project and the future programs to make peo-
ple understand the importance on natural parks in urban context.

1
 I. Stefano Ancilli.

1 Introduction
RomaNatura is the public regional office that manages all the natural protected areas in-
side the city of Rome. Established in 1997 by a Regional Law (number 29), RomaNatura
supervives 16.000 hectares, which is more or less the area covered by the entire city of Bolo-
gna, and about four times the city of Hammamet.
Archaeological finds, historical monuments, villas and castles are only a small part of the
treasures offered by this great heritage: the real treasure is made of a number of ecological
islands providing a natural habitat for over 1.000 different species of plants, 5.000 species of
insects, and 150 species among mammals, birds, amphibians, and reptiles (VV.AA. 2009).
Many of these areas are still used for farming, and the Municipality or Rome is still the
largest agricultural town in Italy.
The Education and Communication Office started, from the beginning, a policy ad-
dressed to environmental education. In particular in 15 years, more than 15.000 pupils were
involved in our events and projects in the entire city of Rome. Many associations contributed
to divulge the mission of RomaNatura, based on protection and safeguard of natural protect-
ed areas in urban context. In 2008 a 1 million euros project started to provide events, confer-
ences, public debates to involve citizens and make them live roman parks, but the results
were satisfying only in education projects with schools.
In 2010, at the end of this first big project, with the simultaneous economic crisis that in-
volved many european countries, RomaNatura decided to change not its mission, but the
means by which to achieve a bigger people's involvement.
In 2013, during my PhD in Communication, I spent six months in San Francisco studying
the city parks system. The main goal was to understand the mistakes we did in the past and
what San Francisco Parks Department's winning strategies can be adapted in the different
social and economic context of Rome.
The end of the research gave us the main idea we want to export from US, based on vol-
unteer programmes. This idea came from a comparison with volunteer projects in San Fran-
cisco, where people were involved from the beginning to the end of the process. In Italy
volunteers are well organized but often the mentality is that volunteers need to be rewarded
for what they do.
If someone is paid for its activity, is not 100% volunteer and if someone decided to spend
time helping in some project, is not often involved from the beginning but only for single
events or one day programme, without understanding the mission or the main goals of the
entire project.
Our new project, called VITA 1 (Volontariato Insieme per il Territorio e l'Ambiente)
wants to try to change this wrong mentality to create a bigger involvement in population who
use and live the park around its own house.
We chose a small area in one of RomaNatura parks and we decided to start the project as
a master plan; in case of success, the model should be applied to other areas inside Rome, to
create a network of volunteers in the entire city.

1
VITA is the italian word for LIFE, the acronym of Volontariato Insieme per il Territorio e l'Ambiente,
that can be translated as Volunteers Together for Territory and Environment.

2
 I. Stefano Ancilli.

2 The area of study

One of the main problems of natural parks in Rome is that most of them are private prop-
erty (around 80%). That is why management seems to be very difficult, first of all because
most of the parks are not accessible.
Therefore, there were few options and the area chosen is a small part of Valle dell'Aniene
Natural Reserve (FIG. 1), called Pratone delle Valli (FIG. 2), a 31 ha area with the river
Aniene on the west and south borders and high density buildings on the north and east bor-
ders.

FIG. 1 – Valle dell'Aniene Natural Reserve. In the black rectangle on the top right, the Re-
serve location inside the city of Rome. In the black circle on the top left, the area of study
(Taken from www.romanatura.roma.it).

3
 I. Stefano Ancilli.

FIG. 2 – In red, the Pratone delle Valli area (Taken from www.romanatura.roma.it).

The reasons for this choice were:

− it is a high density area;
− it is used by different kind of people (seniors, kids and families);
− it could be used with different purposes (sport, nature, relax);
− it is provided with some facilities (a dog area, a jogging track, paths, a multi-
functional building);
− a good transportation system around the area (a new metro station was opened
600 metres from the main entrance);
− many associations already have projects in this park.
The first step of the research was to find some statistics about the area, which were pro-
vided by 2013 population census of Rome.
More than 19.500 people live near the chosen area; about half of them are families with
children (46.5% are married) and 53.5% of population are composed by singles or divorced.
Seniors are a consistent part of the population (23.6%), they are well organized and the
main seniors' association manages part of the multifunctional building inside the park. Peo-
ple under 14 years are 12.5% (TAB. 1).

Population per
class ages (%)
1-4 4.3
5-14 8.2
15-29 13.2
30-49 30.5
50-64 20.2
65 and more 23.6

TAB. 1 – Population per class ages living around the area of study (Comune di Roma 2012).

The area is characterized by a bigger percentage of seniors in comparison with Rome (the
average percentage of senior of the entire city is 21.7%). Besides, many students live near
the area thnaks to the good transportation to the main Universities of Rome.
The idea of foreign citizen involvement seems to be hard to realize because in the area
there is a small percentage of foreigners (8.2%), compared with the higher percentage of
Rome (13.1%).
After a social analysis of the population we started our project based on six different ac-
tivities:
1. connection between the different institutions around the area;
2. volunteer projects for citizens;
3. volunteer projects for groups of citizens and associations;
4. long term projects (civil service);
5. short term projects (university students);
6. sponsorship, donations, and fundraising.

4
 I. Stefano Ancilli.

2.1 Public institutions

Despite Rome has the biggest green area surface per citizen in Europe (more than 131
square metres), in the European Green City Index 2 it is only 14th in the overall ranking and
23rd in Environmental Governance's ranking.
The main reason for such a low ranking is because in Rome there are four different level
of management that often hinder between themselves.
In the same city 3 there are National Parks, managed by the State and the Environment
Ministry, regional parks, managed by RomaNatura, provincial parks, managed by the entire
Province of Rome, and historical villas and gardens, managed by the City of Rome and by
smallest districts (Pratone delle Valli is inside District III).
In the chosen area there are different responsibilities:
− RomaNatura is the general manager;
− the City owns the multifunctional building, and assigned it to the District;
− cleaning is managed by the City;
− there are at least three private associations that manage facilities and ser-
vices in the park.
It is easy to understand that the first step is to make all these subjects communicate each
other. It is important to establish from the beginning everybody's responsibilities and tasks,
especially about the multifunctional building that is the headquarters we would like to use for
our project.
The second step is to understand the level of involvement of any administrations and pri-
vate associations, in order to better plan all the future activities in the area.
At the moment the City of Rome, the District and RomaNatura are discussing about the
building entrusting and, thereby, how to use it.

2.2 Projects for citizens

The second activity is to create specific volunteer projects for citizens. Many people do
not want to be involved with private associations, because it is not always easy to trust in
them or to be accepted as a member.
The goal is to give all these people the occasion to do something for the community they
live in, especially for a park that they use every day and that need to be protected and revital-
ized.
The difference between the existing projects and VITA project is to involve people from
the beginning of the decision making, and not only in single events about which people do
not understand the mission.
Involving people from the beginning and through the entire project means to make them
feel part of something bigger and give them a different and new motivation.

2
The European Green City Index measures the environmental performance of 30 european cities,
taking into account 30 different indicators.
3
Italy has 4 different administration levels: the State, Regions (20), Provinces (110) and Municipalities
(8057). In big cities like Rome there are also small Municipalities called Municipals (15 in Rome) that
are responsible for local activities and development. The population of Rome's Municipals goes from
52.000 to 244.000 people; it means that the most peopled Municipio in Rome has the same citizen of
Venice, the 12th biggest city in Italy.

5
 I. Stefano Ancilli.

Considering the social composition of the area and all the resources inside and around it,
one of the main purposes is to train seniors about the history of the park, from the first envi-
ronmental groups and associations, through its creation in 1997 and the actual management.
The second idea is to train people about urban history of the District, which can be observed
from inside the park, because of the strong urban pressure around the area. Understanding
how the District grew up can make people understand why and how much is important to
preserve such a big green area for all the population.
Training will be done in the multifunctional building by some volunteers (territory's ex-
perts) and by RomaNatura employees. The training will be around 4/6 weeks and at the end
all the volunteers will be able to conduct a guided tour about different aspects of the park.
We want to create something like the "San Francisco City Guide"; they offer free guided
tours in the city and people can give a contribution directly to the guide to lend support to the
project. The guides will not receive any salary but all the money will be used to create new
training opportunities and to improve services in the park. Donations are also tax-deductible,
and RomaNatura will give a receipt for all the funds received; all the donations will be avail-
able on the official website in a quarterly report.

2.3 Projects for groups and associations

The third activity is about projects for groups of citizens or associations. There are three
different associations already operating on the park.
Insieme per l'Aniene is one of the most active environmental associations in Rome; it is
expert in environmental education for schools and recreational activities, and it can give a
good contribution to the general project thanks to its employees' great experience and profes-
sionalism.
Mercatino Conca d'Oro is a small antique and craft market located inside the area. They
can arrange meetings and provide with indoor areas in case of bad meteorological conditions.
The last one is a seniors association that, at the moment, manages part of the multifunc-
tional building.
Despite it is not easy to create a network between different associations and groups,
which have different goals, the attempt is to make them understand the importance of mutual
help. All the activities and events need to be communicated using a common way, as a single
website or newsletter, which can be managed by RomaNatura.
The same people who spend their free time in the market need to be informed that, in the
same days, they can also do a guided tour and they can play a cards tournament with seniors
association.
The second part of this activity is to involve all the other associations that are interested
in doing activities inside the park. The goal is to create a group of people that can coordinate
all the activities having common goals and helping one each other.

2.4 Long term projects

Long and short term projects concern especially students and youth involvement. Long
term projects could be planned only having new and long term staff. Because of the general
economic crisis, at the moment RomaNatura cannot hire new staff but can afford to train
people.

6
 I. Stefano Ancilli.

One of the easiest solutions is to ask for civil service accreditation 4. This is not an easy
process because of the high number of institutions or associations that make request every
year, but RomaNatura, as a public office, could have the precedence.
Having a small group of people for one entire year means, first of all, to give free access
to the multifunctional building every day, for all the planned activities and events.
Civil service workers, after training, could be promoted senior manager being responsible
for single activities like:
− guided tours;
− volunteer programmes;
− specific environmental education projects with school;
− communication.
The second solution is to raise money from sponsors to hire people with specific exper-
tise, but this process seems to be more difficult as well as expensive.

2.5 Short term projects

Short term projects could be planned with university students, to give them the opportuni-
ty to work in a public office to improve their skills and résumé.
The present selection system, called Jobsoul, allows every registered office to offer stag-
es and internship to all the students from every university in Rome.
It is possible to choose position, duration, the specific Department and area of interest to
have students from. Usually a stage or internship is totally free (if the student lives inside the
city) and it is specific for a single programme rather than for a general project.
Students can be selected from different university Departments and fields:
− economics and marketing, for sponsorship and fundraising events;
− communication, to create and manage a website and social networks communi-
cation (Facebook and Twitter profiles, YouTube channel and Instagram);
− pedagogy, to help civil service workers in environmental education projects;
− natural sciences and biology, to support the guides' training.

2.6 Sponsorship, donations and fundraising

Last, but for sure the most important activity, is to manage sponsors, donations and fund-
raising activities.
After detecting all the commercial activities near the park, and some big company in
Rome, the main idea is to have three different actions:
− donations from singles to guarantee the daily activities. Donation can be done
both with money and objects that can be used by volunteers and by staff (i.e. t-
shirts for all the guides);
− donations from small commercial activities around the park (i.e. greenhouses
and plant nurseries can donate plants and seeds for gardening);

4
In Italy the Civil Service gave the opportunity to young people to be involved in a project for one year
(working 30 hours per week), being paid by the State. The institution or association that ask for civil
servants has to guarantee a specific training about the project people are involved in.

7
 I. Stefano Ancilli.

− donations from big private companies interested in linking their name to envi-
ronmental projects.
Donations are tax-deductible and the main idea is to recognize with gratitude what people
could do for the park, giving them visibility in communication campaigns and through social
networks.

3 Conclusions
VITA project, started in April 2014, gave both our Office, both people involved a new
motivation.
In the first 45 days we already involved five associations and we started several meetings
with other institutions. RomaNatura is registered in Jobsoul, the university website for stages
and internships, and we started the process to have civil service accreditation, starting from
October 2014.
To give back to the citizens a green and well organized area is the main goal of this pro-
gramme, considering that green areas in urban context improve the general quality of life, in
different fields, as reported by Garvin (2010):
− natural environment conservation (air and water quality improvement and pollu-
tion reduction);
− individual health, thanks to the activities and physical exercise that can be done
inside a park;
− public health, reducing cardiovascular problems and all the linked diseases, and
therefore public health expenses;
− social interaction, as a park is the perfect place for people to socialize;
− urban sustainability conservation.
The best strategy to reach these goals is to make people understand the importance of
green areas inside a city with huge urban pressure. People are more predisposed to under-
stand it if they are directly involved in parks management. We want to give people back their
territory, and allow them to live it and love it always more.

References
Ancilli, S., A. Lo Re (eds) (2010). Educare per l'ambiente. Percorsi didattici nelle aree
naturali protette urbane. Roma: Carocci.
Ancilli, S. et al. (2009). Ente Regionale RomaNatura. Guide ai servizi delle aree naturali
protette del Lazio. Roma: Ente RomaNatura.
Camagni, R., R. Capello et P. Nijkamp (1998). Towards sustainable city policy: an economy-
environment-technology nexus. Ecological Economics, 24: 103-118.
Chiesura, A., (2004). The role of urban parks for the sustainable city. Landscape and Urban
Planning, 68: 129-138.
Coley, R., F. Kuo et W. Sullivan (1997). Where does community grow? The social context
created by nature in urban public housing. Environment and Behaviour, 29: 468-494.
Comune di Roma (2012). Annuario statistico 2013. Roma: Comune di Roma.

8
 I. Stefano Ancilli.

De Paoli, R.G. (2012). Compatibilità e sostenibilità: il fattore antropico nelle scelte ambien-
tali. Milano: FrancoAngeli.
Garvin, A. (2010). Public Parks: The Key to Livable Communities. New York: W.W. Nor-
ton.
Giuntarelli, P. (2008). Parchi, politiche ambientali e globalizzazione. Milano: FrancoAngeli.
Hartig, T., M. Mang et G. Evans (1991). Restorative effects of natural environment experi-
ences. Environment and Behaviour, 23: 3-26.
Martinico, F., D. La Rosa et R. Privitera (2013). Il ruolo delle aree non urbanizzate nei con-
testi metropolitani: scenari di adattamento ai cambiamenti. Territorio, 66: 92-99.
Thompson, C.W. (2002). Urban open space in the 21th century. Landscape and Urban Plan-
ning, 60: 59-72.
VV. AA. (2009). European Green City Index. Munich: Siemens AG.

Summary
RomaNatura est l'institution publique qui gère tous les parcs naturels à l'intérieur de la
ville de Rome, plus de 16.000 ha de l'environnement naturel et historique. Dans le derniers
mois le Bureau de Communication et de l'Éducation a tenté une nouvelle et différente ges-
tion, basé sur la participation des habitants. Un nouveau projet, appelé VITA (qui peut être
traduit en anglais comme LIFE) a commencé avec six buts différents. L'objectif principal est
de redonner des ressources naturelles et des espaces pour les citoyens, en les impliquant dans
la gestion et la prise de décision. Ce document veut présenter les premiers résultats de ce
projet et les futurs programmes pour faire comprendre l'importance de parcs naturels dans le
contexte urbain.

9
 Application of Seepage Time Series Results to Estimation of Water
Seepage, Case Study: Lar Dam Reservoir

Ali.Aalianvari 1, Mohammad.Salehi 2
P0F P P1F

Abstract
The main objective of this paper is to estimation of water seepage from Lar dam
reservoir with accordance to dye test results. For this purpose, the effective porosity of
limestones has been calculated using by seepage time series method, Results show that
effective porosity of limestones is about 1.5%. Regarding to the dye tests results and
effective porosity, the equivalent permeability of limestones is estimated between
1.1*10-4 m/sec to 2.47*10-4 m/sec. Water seepage from Lar dam reservoir has been
P P P P

calculated using finite element method. According to numerical method results, when
the normal water of dam is about 2485 m.a.s.l, Average of water seepage is around 8.51
m3/sec. Average discharge of springs in downstream of the reservoir has been used to
P P

verify the numerical method, results show the very close relation between estimated
seepage and observed flow .
Keywords:Karst, Dye test, Seepage, Lar Dam

1- Introduction
Leakage from dam reservoirs has been reported in different karst regions of the world.
Water leakage occurs through the karst features directly or indirectly. The estimation of
leakage locations, path(s), and quantity are subject to error due to uncertainties in the
non-homogenous nature of a karst formation, method of study, and limited investigation
due to time and cost factors.
Milanovic´ (1997) reported the maximum leakage from reservoirs in different karst
areas of the world. The main causes of leakage at karst dam sites are the non

1
Department of mining engineering, Faculty of engineering, University of Kashan, Kashan, I. R. Iran,
ali_aalianvari@yahoo.com
2
Member of Engineering Geology Group of Mahab Ghodss, Iran, msalehi146@yahoo.com
homogeneous nature of the karst formations, inadequate data, limited investigation due
to time and cost limitations, and unreliable models.

The Lar dam is located in distance of almost 110 km in northeast of Tehran in Plour
region.One of the major aims for building the Lar Dam was to supply part of Tehran
and its adjoining rural areas drinking water and the production of electric power. This
dam was exploited in 1979 but it became provided due to lack of water preservation &
water seepage in dam basements in water providing, according to former designed
program. However, from the predicted volume of reservoir, only about 100 millionm3 is
recoverable that is very different from the primary purpose of the project. (Fig.1)

Fig1. The location of Lar dam on A)geological map of Iran and B) View of Dam lake
6T

The lar valley in the vicinity of Lar dam is situated mainly in Mesozoic (Jurassic,
Certaceous) carbonate rocks. Tiz Kuh limestones are regional distributed to the Tiz Kuh
mountain, south of the dam amd the Dombak Kuh mountain, west of Delichay river.
Because of joints and fissures TizKuh limestones show a relative high permeability. Tiz
Kuh limestones are underlayn by Lar limestones which are heavy karstified. The lowest
formation is Shemshak shales which represent the impermeable rocks. The geological
map and cross section of dam is show in figure 2.
Fig.2. Geological map of Lar dam and cross section of dam foundation.( A Uromeihy, 2000)

Generally, hydrological properties of rocks are related to lithological conditions,

tectonic conditions and geomorphology of region. Geological investigations of dam
reservoir show that the area is covered by formations with very different hydrological
conditions.

The part of Annual precipitation runoff into the valley and join to the river. The other
part of water penetrated into the porous rock from the discontinuity and karstic cavern
and formed the springs in the area (eg.Haraz, Galugah, etc)

Based on the geological and hydrological investigation of the area, the most important
geological features of area is the karstic cavern and porous rocks.So karstic limestones
are the major paths for water seepage from the dam reservoir.

In this paper attempt to estimate the equivalent permeability of limestones using the dye
test results. For this purpose, effective porosity of limestones has been calculated using
by seepage time series method, and then with attention to the dye test results, equivalent
permeability of rocks has been calculated.

Afterward the water seepage from dam reservoir has been calculated for the different
elevation of the normal water in dam with the Geostudio software. The results verified
by the average discharge of springs that show the good relation between calculated
results and observed flow.

2- Estimation of porosity of limestones with seepage time series method

Whenever the reservoir water level goes up and down quickly, the minimum volume of
caverns that store the groundwater and connect to the reservoir via springs can be
calculate.
In this regard, the outflow of springs when the reservoir water level goes up quickly
compared with the outflow of springs when the reservoir water level goes up gradual
and the variation of the water level in the reservoir and outflow of the springs is plotted
versus time. Reservoir impounding curve is calculated from equation 1.

(Q-Q1)/(H-H1)= (Q2-Q1)/(H2-H1) (1)

Where the Q1 is the Seepage intensity at the beginning the reservoir impounding
(m3/sec), Q2 is the is the Seepage intensity when the reservoir level is constant
(m3/sec), H1 is the minimum level of the reservoir at the beginning the reservoir
impounding (m) and H2 is the maximum level of t he reservoir when the reservoir level
is constant (m).

The volume of the porosity and cavern between the minimum and maximum
groundwater level is equal to area between the measurement and calculated outcome in
curve.

Using this equation, Q values correspond to the experimental values of reservoir water
levels are calculated and the corresponding curve is plotted.

Water filled pore volume of the rock formations with respect to differences between the
measured and calculated curves are obtained. Obviously, this value represents the
minimum size of the holes because the most of them were filled by the water before
reservoir impounding.

Therefore in order to calculate the effective porosity of limestones in Lar dam, water
level fluctuation in BL29, P5 and FP14 holes was monitored by the fluctuation of the
reservoir water level. (table1)
Table.1. water level fluctuation in piezometric holes (BL29, P5 and FP14)

piezometric Reservoir water level Piezometric

hole fluctuation (m) elevation(m)

BL29 17.11 36.11

P5 13.68 17.32

FP14 17.11 34.24

Using these results and equation1, seepage time series were calculated for several
consecutive years (Figures 3, 4, 5)
 Seepage Time Series(1989) Seepage Time Series(1993)

2510
13000 2510 12500
2505
12500

Springs Discharge(lit/sec)
2505 11500 2500
12000 10500 2495
Discharge(lit/sec)
2500

R.W.L(masl)
R.W.L(masl)
11500 9500 2490
Springs

11000 2495 2485

8500
2480
10500 7500
2490 2475
10000 6500
2470
2485
9500 5500 2465
9000 2480 4500 2460
0 10 20 30 40 50 60 0 10 20 30 40 50 60 70 80 90 100 110
Date(day) Date(day)
Spring discharge(lit/Sec) Calculated Outcome(lit/Sec)
Q from Eq1 Head of Water Level(m) Spring Discharge(Lit/Sec) Calculated Outcome(Lit/Sec) Head of Water level(m)

Fig.3. Seepage Time Series for 1989 Fig.4. Seepage Time Series for 1993

Seepage Time Series (2003)

2495
7800
2490
Springs Discharge(lit/sec)

2485
6800
2480
R.W.L(masl)

5800 2475
2470
4800
2465
2460
3800
2455

2800 2450
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Date(day)

Spring discharge(Lit/Sec) Calculated Outcome(Lit/Sec) Head of Water (m)

Fig.5. Seepage Time Series for 2003

Using by the piezometric holes in different years, seepage time series for each year
calculated and the minimum volume of the cavern and porous volume has been
estimated. As described above, this value represents the minimum size of the holes
because the most of them were filled by the water before reservoir impounding so the
estimated porosity is the minimum porosity. For example Seepage time series for the
1989 is calculated from this equation:

Q= 179.61H - 437318.7
The curve in Figure 3 has been obtained from this equation, the amount of porous media
in this curve is equal to area between experimental and estimated discharge. That is
about 3192030m3. The reservoir water level varied in the range from 2486.4 to 2506.9
m.a.s.l that is about 20.5 m.

According to the piezometric level in holes, area of karstic aquifer (12 km length and 1
km width) , the minimum porosity is about 1.5% .

Seepage time series calculation for different years (1989, 2003, and 2010) verify the
results of 1993. So the prosoity was considered about 1.5%

3- Estimation of water seepage from Lar dam reservoir

The SEEP/W software (GEO-SLOPE Company) has been used for modeling and
analyzing the seepage from dam reservoir.
The input data for the software include the equivalent permeability of various geological
formations (such as Lar limestones, Shemshak formation, Lava and alluvium) and
reservoir water level that have been described below

3-1- Permeability
3-1-1- Alluvium
The data about permeability condition of alluvial unit is not sufficient, so the estimation
of equivalent permeability of alluvial unit has been done based on the geological and
lithological description and Terzaghi equition:

K eq=
R R (Terzaghi 1943)

Where Keq is the equivalent permeability, H is the total width of all alluvium, H1, H2,
…Hn are the width of each alluvium layer and K1, K2,…Kn is the permeability of each
layer.
Using this equation and geological description, the estimated permeability of alluvium
unit is about 6.5*10-6 m/sec.

3-1-2- Lava formation

With accordance of geological investigations and description of formation, equivalent
permeability is about 10-6 m/sec

3-1-3- Shemshak formation

Permeability of Shemshak formation is estimated around 1.3*10-6 m/sec.

3-1-4-Lar limestone
Regarding to the geological investigations and field studies, the major part of water
seepage in right abutment has been done in the Lar limestones.
Because the lack of data from drilled holes and with attention to the karstified condition
of area, equivalent permeability of limestones estimated from dye test results and back
analysis of downstream sprig’s discharges.

A) Dye test results

The dye-tracer test is one of the most powerful techniques to determine karst
development, the main objective of tracing test should be:
• To determined the influence of technical assessment on the existing reservoir
leakage.
• To determine the path or to distinguish between different pats of underground water
flow and
• To determine the rate of leakage to springs downstream of Lar and Haraz river

To identify the major path of water flow and estimation of permeability in the area, dye
test has been done in the holes, (Figure6.)
 Fig.6. location of injection point and sampling point in Lar dam reservior

Using the dye test studies and calculated velocity in dye tests, the equivalent
permeability has been calculated by the below equiation:

ne
K =V
I
Where K is the equivalent permeability (m/sec), V is the dye velocity (m/sec), ne is the
effective porosity (estimated by the seepage time series) and I is the hydraulic gradient.

According to the ASTM-D5613, index tortusoity is equal to the 1.47 that is considered
in the calculations.
Based on the different type of dye velocity, minimum, maximum and average
permeability for the limestones has been estimated.(table 2)

Table.2. estimated permeability based on the dye test results

Equivalen permeability(m/sec)
1.1*10-4
minimum P

1.82*10-4
Average P

2.47*10-4
maximum P

b) Estimation of permeability using by back analysis of spring’s discharges

Reservoir water level fluction is directly related to the spring’s discharges.

So using the back analysis of spring outcome and Darcy law, the equivalent
permeability was estimated about 1.9*10-4 m/sec

3-2-Estimation of water seepage from Dam reservoir using by numerical method

(Seep/w Software)
In order to calculate the water seepage from dam reservoir and abutments, a few
geological sections prepare (Figures7, 8)
3.0

8 9
2.9

10
2.8

2.7 Alluvium 11
Elevation(m) (x 1000)

6 12
2.6
16
Lava
2.5
7 Lar Limestone
5
17 15 14
2.4 1 13
2
4
3
2.3

3
2.2

2.1

1 2
2.0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00
Length(m) (x 1000)
Fig.7. Geostudio model with geological units
2.9

2.8

2.7
Elevation(m) (x 1000)

2.6

2.5
2468

2.4

2.3
2462

1.3247e-005
2464
2466

2.2
2460

2458

2456

2448
2450
2454

2.1 2452

2.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0

Length(m) (x 1000)

Fig8. Flow lines and iso potential line

Seepage calculation was been done in different elevation of normal water elevations.
Table 3 shows the results of modeling.

Table.3. results of seep/w modelling

Estimated Seepage(m3/Sec) Normal water elevation(m.a.s.l)

7.3 2470

7.50 2475

7.99 2480

8.51 2485

Statistical investigation show that about 83% of seepage has been done from right
abutment and 17% flow from left abutment.

3-3- verification of results by the downstream spring discharge

The general direction of ground-water flow is mostly toward the local base of erosion, parallel to the
strike. Karst water discharges as springs or flows into the adjacent alluvium aquifer where a direct
connection exists between the alluvium and the karst formation.

The discharges of downstream springs are directly related to the normal

water conditions. Measurement discharges of springs are shown in table 4.

Table.4. Measurement discharges of springs

Spring discharge(m3/Sec) Normal water elevation(m.a.s.l)

6.2 2470

8.2 2475

8.5 2480

8.75 2485

Table 5 shows the spring discharges, calculated seepage and normal water
elevation.

Table.5. comparison between spring discharges, calculated seepage and normal water elevation.
Calculated Seepage(m3/sec) Spring discharges(m3/sec) Normal water elevation(m.a.s.l)

7.3 6.2 2470

7.50 8.2 2475

7.99 8.5 2480

8.51 8.75 2485

4- coclusion
Seepage time series show that estimated effective porosity represents the minimum size
of the holes because the most of them were filled by the water before reservoir
impounding so the estimated porosity is the minimum porosity

Comparison between calculated seepage and discharge of downstream springs show

that equivalent permeability of limestones is about 1.9*10-4 m/sec and the future
prediction such as estimation of water seepage for the normal water of reservoir must be
done based on this permeability.

Geological investigations and field studies show that due to the sinkholes in
higher elevation, the permeability may be increased.
 5- Refrences
A Uromeihy, "The Lar Dam; an example of infrastructural development in a geologically
active karstic region", Journal of Asian Earth Sciences, Volume 18, Issue 1, February 2000,
Pages 25–31
Karimi, H., Raeisi, E., and Zare, M., 2005, Physicochemical time series of karst spring
as a tool to differentiate the source of spring water: Carbonates and Evaporites, v. 20,
no. 2, p. 138–147.
Milanovic´, P.T., 1997, Reservoirs in karst: Common watertightness problems, in Gu¨
ney, G., and Johnson, A.I., eds., Karst Waters and Environmental Impacts, Rotterdam,
A.A. Balkema, p. 397–400.
Milanovic´, P.T., 2000, Geological engineering in karst: Zebra Publishing Ltd, 347 p.
Belgrade, Yugoslavia.
Raeisi, E., and Laumanns, M., 2003, Cave Directory of Iran: Berlin, Berliner
Hohlenkundliche Berichte, 101 p.
Raeisi, E., and Kowsar, N., 1997, Development of Shahpour Cave, southern Iran: Cave
and Karst Science, v. 24, no. 1, p. 27–34.
Z.Mohammadi, E RAEISI, "HYDROGEOLOGICAL UNCERTAINTIES IN
DELINEATION OF LEAKAGE AT KARST DAM SITES, THE ZAGROS REGION,
IRAN", Journal of Cave and Karst Studies, v. 69, no. 3, p. 305–317.
Effect of curing time on behavior of sandy soil treated with
biopolymer

Mohamed Ay-Eldeen* Abdalazim Negm**

Ahmed Tawfik***

Environmental Engineering Department, School of Energy, Environmental and Chemical

and Petrochemical Engineering, Egypt-Japan University of Science and Technology (E-
JUST), Alexandria, Egypt.
http://www.ejust.edu.eg/
*mohamed.ayeldeen@ejust.edu.eg
** negm@ejust.edu.eg
***ahmed.tawfik@ejust.edu.eg

Abstract. This preliminary investigation presents the results of the effect of

time on cohesionless soil treated with biopolymers. Xanthan gum concentra-
tions were varied from 0.25% to 2.00%. The results showed that adding Xan-
than gum solution to the sand soil improved the geotechnical properties.
Moreover, supplementation of the soil with Xanthan gum increased the
strength of the treated sample to 290 kPa at increasing the concentration of
Xanthan gum from 2.00% after 3 week curing time. This was not the case for
the permeability of sand, where it was reduced from 3.40x10-4 m/s to 9.70x10-6
m/s with increasing the biopolymer concentration from 0.00% to 2.00% re-
spectively. However the effect of biopolymer on the hydraulic conductivity
(permeability coefficient) of the soil decreases after a while.
 Effect of curing time on behavior of sandy soil treated with biopolymer

1 Introduction
Improving the mechanical properties of soil becomes a very important issue. Most of the
materials used in soil improvement such as cement or chemical have a negative impact on
the environment. It may change the pH level of the soil or contaminate the soil or the water.
Therefore, it is urgently to find an environmentally and friendly soil treatment method.
Biopolymers is a sustainable, carbon neutral and are always renewable, because they are
made from natural plant materials which can be grown indefinitely such as agricultural non-
food crops. Therefore, using of biopolymers to improve the soil behavior would become a
green solution for improvement of the mechanical behavior of sandy soils.
At the present, biopolymers are related mainly to the applications of plants or vegetative
soil cover for control erosion, slope stability, and to reduce water infiltration into slopes
(Karol, 2003). Although there are many potential applications of biopolymers to geotechnical
engineering, at the present, promising applications are only concentrated in the bioclogging.
The process of bioclogging is mainly reduced the hydraulic conductivity of soil and porous
rocks. It could be used to reduce drain channel erosion, form grout curtains to reduce the
migration of heavy metals and organic pollutants, and prevent piping of earth dams and
dikes(Ivanov & Chu, 2008).
Martin et al. (Martin, Yen, & Karimi, 1996) and Karimi (Karimi, 1998), investigated the
effects of addition of biopolymers namely, xanthan gum and sodium alginate, on permeabil-
ity and the shear strength of a silty soil. They found that there is a reduction of two orders of
magnitude in permeability and a 30% increase in shear strength. In another study, Khacha-
toorian (Khachatoorian, Petrisor, Kwan, & Yen, 2003) showed that the flooded biopolymers
into the matrix of a petroleum reservoir decreased the permeability relative to the fluids situ-
ated in the reservoir. Khatami, and O`Kelly (Khatami & O’Kelly, 2013) studied the mechan-
ical behavior of sand supplemented with agar and six modified starches over a range of con-
centrations (1-4% agar and 0.5-1% starch). Experimental results demonstrated the
compatibility of agar and starch. Depending on the biopolymer concentration, the unconfined
compressive strength of the sand treated with agar and starch biopolymers ranged from 158
to 487 kPa. Triaxial compression tests over a range of confining pressures also indicated that
the biopolymers effectively increased the cohesion intercept and stiffness of the treated sand.
This study comes on the line to contribute in filling the gap of research in the field by inves-
tigating the effect of addition of different concentrations of Xanthan gum on the geotechnical
properties of sandy soil.

2 Materials and methods

2.1 Sand Properties
The sand used in this study was collected from Sand quarry near 6 October city The spe-
cific gravity of the soil particles was determined by the gas jar method. The samples were
tested five times resulting an average value of 2.63. The maximum and minimum dry densi-
ties of the sand were 19.5 and 16.1 kN/m3. This corresponds to void ratios of 0.35 and 0.63
respectively. The particle size distribution of the soil was determined using the dry sieving
 I. Ay-Eldeen et al.

method and illustrated in Fig. 1. The effective diameter (D10); the mean diameter (D50);
uniformity coefficient (Cu); and coefficient of curvature (Cc) were 0.18 mm, 0.50 mm,
3.388, and 0.99 respectively. The selected parameters were chosen to achieve a relative den-
sity of 54.3% (medium dense sand) according to the compaction of the sand with a density of
17.8 kN/m3. Void ratio (e) and porosity (n) for the sand were calculated resulting values of
0.478 and 0.323, respectively.

2.2 Xanthan Gum characteristics

The biopolymer used in the present study is a an anionic polysaccharide namely Xanthan
gum which produced by Xanthomonas campestris(Sutherland, 1994). Xanthan gum consists
of glucose linked with β-1,4 bonds, and every second glucose possesses a mannose-
glucuronic acid-mannose side chain(Hassler & Doherty, 1990). Xanthan gum powder is
commercially available and when mixed with water functions as a colloid to thicken water
based systems to produce gels, which can act as stabilizer and binders (Kamel, 2001).
100
90
80
70
Percent Finer (%)

60
50
40
30
20
10
0
100 10 1 0.1 0.01 0.001 0.0001
Grain Size, D (mm)

FIG. 1- Partical size distribution curve of untreated sand

2.3 Experimental setup

The sand was initially washed several times to get rid of debris and impurities then dried
at 105°C for 24 hour. The biopolymer powder was dissolved in deionized water with differ-
ent concentrations. The concentration of the solutions is defined as the ratio in percentage of
the dry weight of biopolymer to the total weight of the biopolymer solution. The biopolymer
powder was slowly added into water, and stirred for 10 min until a homogeneous solution
was obtained to prevent clumping. Xanthan gum solutions with concentrations of 0.25, 0.5,
1, and 2% were used in this study.
 Effect of curing time on behavior of sandy soil treated with biopolymer

The sand samples were carefully mixed with different concentrations of Xanthan gum (0,
0.25, 0.5, 1, and 2%) with the same water content of 10% solution weight to the soil weight.
The mixture was placed in the four identical containers to ensure the densities are equally
distributed in all samples. All specimens were kept at fixed temperature of 35°C during the
study duration. Each test was performed three or four time to ensure the quality of the re-
sults.

3 Test procedure
3.1 Shear Strength Test
Using a 60 x 60 mm shear box, a series of direct shear tests were performed on the un-
treated sand and on sand that had been treated with biopolymers solutions. The first series of
shear tests were performed immediately after the mixing of the samples to evaluate the effect
of uncured biopolymer solution on the sand behavior. The tests were performed according to
the ASTM D3080-04 standard.

3.2 Permeability Test

The falling head permeability test was used to determine the permeability of the soil ac-
cording to specification ASTM D5084-03. It is a common laboratory testing method used to
determine the permeability of fine grained soils with intermediate and low permeability.
Results and discussions

3.3 Shear strength

Figures 2-a, b, c and d show the relationship between the shear strength and the applied
normal stress for the treated sandy soil specimens for different times ranging from zero to
three weeks and for different biopolymer concentrations ranging from 0 to 2%. The results
presented in Fig. 2a indicated that adding 0.25% biopolymer concentration increases cohe-
sion stress from 0 kPa to 55 kPa after 1 week. Moreover, after the 2nd week the soil strength
became higher, the same as the 3rd week. The cohesion stress increased from 55 kPa in the
first week to 75 kPa in the 3rd week. This behavior repeated again in the other three curves.
However, it is observed that the increase in soil cohesion (Fig. 2d) is accompanying with a
corresponding reduction in the friction angle form 37° in the first week to 34° in the 3rd
week. The improvement in shear strength of the soil can be explained as biopolymers possess
various chemical functional groups, such as hydroxyl, ester, or amines. Their long-chain
structure also provides more sites at which the characteristic chemical reaction of a given
functional group would occur. Chemical bonding corresponds to the adhesive forces whose
function is to hold the soil particle and gel together at their surfaces.
Figure 3 shows the effect addition of different concentrations of biopolymer on the cohe-
sion stress. At a microscopic scale, the effectiveness of the bonding depends mainly on the
type of forces present at the interface of the particle and the gel. The forces operating at such
a phase interface include ionic/electrostatic or covalent bonds (chemisorption), hydrogen
bonding (strong polar attraction), and van der Waals forces (physical absorption). Short-
range ionic/electrostatic and covalent bonds have the highest bond energy in terms of KJ/mol
 I. Ay-Eldeen et al.

and therefore give the strongest bond. Van der Waals forces, which are the interaction be-
tween dipoles within the bulk material, develop the weakest bonds over a long
range(Khatami & O’Kelly, 2013).

(a) (b)

(c) (d)
FIG. 2. - Relationship between shear stress (Kpa) and applied normal stress (Kpa)for
untreated and treated sand samples with (a) 0.25% biopolymer concentration, (b) 0.5%, (c)
1% and (d) 2%, for different time intervales from 0.0 to 3 weeks.

Table 1 summarizes the results of direct shear tests for all concentrations with time. It is
clearly observed that the cohesion stress directly proportional to the concentration of Xan-
than gum. Furthermore, it can be noticed that the friction angle of the soil slightly effected
with the increasing in biopolymer concentration. The friction angle after curing varied from
34° to 37°. It is postulated that the coating effect of the biopolymer on the grain surfaces
smoothened the microscale roughness, thereby reducing the asperity interlocking of the sand
grains leading to slight reduction in the friction angle.
 Effect of curing time on behavior of sandy soil treated with biopolymer

Fig. 3 - Variation of cohesion stress with time for different biopolymer concentrations

Biopolymer Con-
Time for Curing C (kPa) Ø (degree)
centration (%)
Untreated Sand 0.00 0 32
0.25 0 31
Immediately after 0.50 0 30
treatment of the speci- 1.00 0 29
mens 2.00 0 28
0.25 55 34
0.50 134 36
After 1 week
1.00 184 37
2.00 260 37
0.25 62 34
0.50 141 36
After 2 week
1.00 195 35
2.00 283 34
0.25 74 34
0.50 149 35
After 3 week
1.00 213 34
2.00 291 34
TAB. 1 - Shear parameters for untreated sand and sand treated with biopolymers

3.4 Permeability
The results presented in Table.2 showed the effect of Xanthan gum on soil permeability
for both treated and untreated sand. These results showed a strong effect of Xanthan gum on
soil permeability (hydraulic conductivity), where biopolymer concentration of 0.5% reduced
the soil permeability to almost 25% of the initial value. On the other hand, at Xanthan gum
 I. Ay-Eldeen et al.

concentration of 2.0%, the reduction in permeability is only 3% This is attributed to Xanthan

gum absorbs water; therefore, when an amended soil is wetted, the xanthan gum expands,
forming a fibrous network and fills the pores in the soil (Czarnes & Hallett, 2000). Increas-
ing in the permeability was observed in the 2nd and 3rd week. In spite of the previous notice,
P P P P

Xanthan gum still has significant effect on the permeability of the soil until the 3rd week.P P

Permeability (m/s)
Bio. Concentration, %
Time for Curing
0.0 0.25 0.5 1.0 2.0
After 1 week 3.40x10-4
P
1.80x10-4
P

8.50x 10 -5
2.84x 10-5
P P 9.70x 10-6 P

-4 -4
After 2 week 3.40x10 P
2.00x10P
1.02x 10-4 3.40x 10-5
P P 1.15x 10-5 P

After 3 week 3.40x10-4

P 2.15x10P
-4
1.13x 10 -4
4.11x 10-5
P P 1.60x 10-5 P

TAB. 2 - Hydraulic conductivity for untreated and treated sand with biopolymers

4 Conclusions
Within the experimental range of this investigation, the following conclusions can be
drawn:
- Xanthan gum has a remarkable effect on sand stiffness which begins after curing
time. This effect was impacted by the concentration of the biopolymer solution.
- The strength of the soil treated with xanthan gum increased with time. In case of
concentration 0.25 % the cohesion stress increased from 55 kPa in the first week to
74 kPa in the third week and from 260 kPa to 291 kPa for the same period for con-
centration of 2.00%.
- Xanthan gum has significant effect on the permeability of the soil. After one week
the permeability was reduced to about 25% of its original value with biopolymer
concentration of 0.50%, and to about 3% in case of biopolymer concentration of
2.00%.
- After time the effect of biopolymer on the soil permeability reduced. The permeabil-
ity increased from 8.50 x 10-5 m/sec in first week to 1.13 x 10-4 m/sec in 3rd week for
P P P P P P

concentration of 0.50% and from 9.70 x 10-6 m/sec in first week to 1.60 x 10-5 m/sec
P P P P

in 3rd week for concentration of 2.00%.

P P

- As the research project is still undergoing, it is recommended to extend the range of

experiments to cover higher concentrations and long period of treatments to detect
whether the trend will change or not.

5 Acknowledgements
The first author would like to thank Egyptian Ministry of Higher Education (MoHE) for
providing him the financial support (PhD scholarship) for this research as well as the Egypt
Japan University of Science and Technology (E- JUST) for offering the facility and tools
needed to conduct this work.
 Effect of curing time on behavior of sandy soil treated with biopolymer

References
Czarnes, S., & Hallett, P. D. (2000). Root- And Microbial-Derived Mucilages Affect Soil
Structure And Water Transport. European Journal of Soil Science, 51(3), 435–443.
Hassler, R. A., & Doherty, D. H. (1990). Genetic Engineering of Polysaccharide Structure:
Production of Variants of Xanthan Gum in Xanthomonas campestris. Biotechnology
Program, 6(3), 182–187.
Ivanov, V., & Chu, J. (2008). Applications of microorganisms to geotechnical engineering
for bioclogging and biocementation of soil in situ. Reviews in Environmental Science
and Bio/Technology, 7(2), 139–153. doi:10.1007/s11157-007-9126-3
Kamel, R. N. (2001). Geotechnical Applications of Biopolymer Technology. University of
Southern California.
Karimi, S. (1998). A Study of Geotechnical Applications of Biopolymer Treated Soils with an
Emphasis on Silt. University of Southern California, Los Angeles.
Karol, R. (2003). Chemical grouting and soil stabilization. In 3rd M. Dekker.
Khachatoorian, R., Petrisor, I. G., Kwan, C., & Yen, T. F. (2003). Biopolymer plugging
effect: laboratory-pressurized pumping flow studies. Journal of Petroleum Science and
Engineering, 38, 13–21.
Khatami, H., & O’Kelly, B. (2013). Improving Mechanical Properties of Sand Using
Biopolymers. Journal of Geotechnical and …, 139(8), 1402–1406. Retrieved from
http://ascelibrary.org/doi/abs/10.1061/(ASCE)GT.1943-
5606.0000861?mi=3cg7ev&af=R&startPage=0&nh=20
Larson, S. L., Newman, J. K., Griggs, C. S., Beverly, M., & Nestler, C. C. (2012).
Biopolymers as an Alternative to Petroleum- Based Polymers for Soil Modification
Engineer Research and Development Modified Biopolymers as an Alternative to
Petroleum-Based Polymers for Soil Modification. US Army Corps of Engineering,
12(August). Retrieved from http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA566903
Martin, G. R., Yen, T. F., & Karimi, S. (1996). Application of Biopolymer Technology in
Silty Soil Matrices to Form Impervious Barriers. In 7th Australia New Zealand
Conference on Geomechanics: Geomechanics in a Changing World (pp. 814–819).
Barton, ACT, Australia.
Sutherland, I. W. (1994). Structure-Function Relationships in Microbial Exopolysaccharides.
Biotech Advances, 12(2), 393–448.

Résumé
Cette enquête préliminaire présente les résultats de l'effet du temps sur le sol sans cohé-
sion traités avec des biopolymères. Les concentrations de gomme de xanthane ont été modi-
fiées à partir de 0,25% à 2,00%. Les résultats ont montré que l'ajout de la solution de gomme
xanthane dans le sol de sable améliore les propriétés géotechniques. Par ailleurs, la supplé-
mentation du sol avec de la gomme xanthane augmente la résistance de l'échantillon traité à
290 kPa à l'augmentation de la concentration de la gomme de xanthane de 2,00% après 3
semaines de temps de durcissement. Ce n'était pas le cas pour la perméabilité-lité de sable,
où il a été réduit de 3.40x10-4 m / s à 9.70x10-6 m / s avec l'augmentation de la concentration
de biopolymère de 0,00% à 2,00% respectivement. Cependant, l'effet de biopolymère sur la
conductivité hydraulique du sol diminue après un certain temps.
 Framework for Application of Life Cycle Assessment
Approach on Egyptian Residential Building
Case Study: New Assiut City, Egypt

Ahmed AbdelMonteleb M. Ali 1,*, Abdelazim M. Negm 1,**, Mahmoud Farghly

P P P P

Bady 1,***, Mona Gamal El-Din Ibrahim 2,****

P P P P

1
P P Environmental Engineering Department, Egypt-Japan University of Science and Technolo-
gy (E-JUST), Alexandria, Egypt
2
P P Dean of School of Energy, Environment and Chemical & Petrochemical Engineering,
Egypt-Japan University of Science and Technology (E-JUST), Alexandria, Egypt
http://www.ejust.edu.eg/
*
P P Corresponding Author: ahmed.abdelmonteleb@ejust.edu.eg
**
E-mail: negm@ejust.edu.eg
P P

***
P E-mail: mahmoud.bady@ejust.edu.eg
P

****
P E-mail: mona.gamal@ejust.edu.eg
P

Abstract. To the best knowledge of the authors, there are no life cycle assessment (LCA)
studies in Egypt. Therefore, the paper suggests a framework to applying the LCA approach
on all stages from cradle to gate approach of New Assiut City building, Egypt. The applied
method is LCA ruled by the ISO 14040 series. The software SimaPro 8.1 is used for the
calculation of input and output of each system. The existing buildings in New Assiut is taken
as a case study. Eventually, this study represents the first step to apply the LCA approach in
Egyptian building as an Environmental Impact Assessment Tool. The main difficulty of
applying LCA is the shortage of the Egyptian database for the Life Cycle Inventory (LCI).
Therefore, the researchers suggest a mechanism to synthesize the missing parts of Egyptian
LCI Database from the International Database. Moreover, few recommendations are present-
ed for future studies.
Keywords: Life Cycle Assessment; Egyptian Residential Building; New Assiut City
Framework for Application the Life Cycle Assessment Approach on Egyptian Residential Building

1. Introduction
Among the many different procedures and tools used to perform an Environmental Per-
formance Evaluation (EPE) of a material or product are the Environmental Indicator Systems
(EPIs), the Environmental Management Accounting (EMA), the Environmental Management
Systems (EMSs), the Eco-labeling (A.M. Papadopoulos 2007), and the Life Cycle Assess-
ment (LCA) (EN ISO 14044 2006) which is the most complete one. LCA was developed by
industrial ecologists, chemists, and chemical engineers seeking to understand and reduce the
impact of manufacturing and process chemistry. (James Parker, Paul Cropper) Today, LCA
is being promoted as a tool for analyzing the environmental impact of buildings and making
decisions to reduce these impacts. (Guinee 2001)
The concept of building LCA is based on the following key points: the entire life cycle
that includes the extraction and processing of raw materials, production, and use up to recy-
cling or disposal; all environmental impacts connected with the life cycle, such as air, water,
and soil emissions, wastes, raw material consumption, or land use; the aggregation of the
possible impacts of the environmental effects and their evaluation so to give environmentally
oriented support to decisions makers. (Asdrubali et al. 2013)

2. Methodology
According to EN ISO 14040 (EN ISO 14040 2006) and EN ISO 14044 (EN ISO 14044
2006), a Life Cycle Assessment includes four main steps:
1. Goal and scope definition.
2. Life cycle inventory.
3. Life cycle impact analysis.
4. Interpretation of the results.
LCA is a framework for evaluating the environmental impacts of a product, process or
service from cradle to grave and is carried out according to International Standards, ISO
14040 (EN ISO 14040 2006). ISO 14040 defines LCA as the: ‘Compilation and evaluation
of the inputs, outputs and the potential environmental impacts of a product system through-
out its life cycle. (Monahan and Powell 2011)
The initial phase defines the scope of the study, including defining the functional unit,
the system boundary, level of detail and how the environmental burdens will be allocated. It
is dependent upon the subject and the intended use of the study and can vary considerable
depending upon the particular LCA. (AS/NZS ISO 14040 1998) The second phase, the life
cycle inventory (LCI), is the compilation of an inventory of the input/output data with regard
to the system under study. The third phase, the impact assessment (LCIA), evaluates the
significance of potential environmental impacts using the LCI results and provides infor-
mation for the final interpretation phase. Life cycle interpretation is the final phase in the
LCA framework. In LCA-type models, two main methods in describing impacts can be dis-
tinguished: (Blankendaal et al. 2014)
1. At the level of midpoint impacts, e.g., covering issues such as climate change, ozone
layer depletion, human toxicity, acidification, and abiotic resource depletion;
2. At the level of endpoint impacts, covering issues such as; (Asdrubali et al. 2013)
• Those to human health, expressed as the number of years of human life lost or
in suffering from disease.
 Ahmed AbdelMonteleb, et al.

• Those to the quality of ecosystems, expressed as the loss of living species in a

certain area over a certain time.
• Those to resources, expressed as the surplus of energy necessary for further ex-
tracting minerals and fossil fuels.
Results of this method are available in Ecopoints (Pt). It is noted that the eco-indicator
calculations, introduce higher uncertainty than the former. (AS/NZS ISO 14040 1998)

3. LCA related computations

SimaPro V8.1 software was used in the analysis of the Egyptian building as a case study
by using the above inventory databases. SimaPro (PRé Consultants, Amersfoort, the Nether-
lands) is a dedicated LCA software tool for undertaking LCA studies.

4. LCA application to Egyptian residential building case study

The research choses existing buildings, typical of current Egyptian construction tech-
niques and building typologies in New Assiut (NA) City, from cradle to grave LCA analysis.
To study a residential pattern and analyze its models, the area of each pattern had to be
calculated, along with its percentage in the housing of NA City. Analysis for housing pat-
terns in NA City shows that Ibn Baytak ranks first in the city with a 33.15% of the total pat-
terns area. Consequently, this pattern was selected for conducting climate analysis for its
residential models, and studying the impact of different orientation and vertical louvers on
the thermal performance of the buildings. (Ahmed AbdelMonteleb Mohammed Ali 2012)
Ibn Bytak consists of five phases. Figure 1, shows the different phases of Ibn Baytak project
in the city. It is noticed that the first and third phase are located in the second district.
Whereas the fifth stage in the first district, and the second and fourth phases are located in
the future extension area of the city. (Ministry of Housing 1997)

FIG. 1 – Different phases of Ibn Baytak project in New Assiut City ( AbdelMonteleb 2012)
The case study is chosen in the first phase for studying the impact of vertical lou-
vers length on the thermal performance of the model. The selected model comprises three
building types X, Y and Z. Model X is attached from one side and with three free facades.
For Models Y and Z both two are attached from two directions and free from the other two,
i.e. only two facades. Figure 2, shows the distribution of the three models (X, Y, Z) of the
first phase of Ibn Baytak in NA City. Table 1, illustrates the numbers and percentages of the
three models. In this paper analysis is done only on type Z. The total area of the model Z is
Framework for Application the Life Cycle Assessment Approach on Egyptian Residential Building

150 m2 (17.5 · 8.6 m). The model consists of ground and two typical floors with a floor
height of 2.70 m. Figure 3, shows the plans and facades of model (Z).

Model Number Percentage

Model X 206 plots 40,95 %
Model Y 13 plots 2,60 %
Model Z 234 plots 56,45 %

TAB. 1 – Numbers and percentages of the three Ibn Baytak models ( AbdelMonteleb 2012)

FIG. 2 – The distribution of the three models (X, Y, Z) of the first phase of Ibn Baytak in New
Assiut City ( AbdelMonteleb 2012)

FIG. 3 – The plans, and facades for the selected model (Z) – Ibn Baytak project.
(AbdelMonteleb 2012)
4.1. Goal
Setting on the goal is an important step in applying LCA in construction industry. A
possible goal is to evaluate/assess the environmental impact of Egyptian buildings through-
out their entire life and also to assess the impact of some optimization scenarios to reduce the
energy consumption and the environmental impacts. The lifetime of the buildings is assumed
to be 50 years, which is consistent with most of the published case studies.
 Ahmed AbdelMonteleb, et al.

4.2. System boundaries

The system boundaries determine which unit processes are included in LCA study. The
system-building is broken down into process units, encompassing all the elements, materials,
and components that constitute the building and are affected by flows of matter and energy
during their life phases. For classifying the building’ elements, the research choose typical
residential building in New Assiut City which is Ibny Bytac model. In Figure 4, the research
suggests three phases of the LCA which are; construction material (which include; material
production and building construction), operational/use phase and End-of-Life phase. Each
item has many other elements will study it by using life cycle impact analysis.

4.3. Life cycle inventory database

From previous authors literature which published in (Ahmed AbdelMonteleb
Mohammed Ali et al. 2014), Egypt suffered from shortage of life cycle inventory database,
thus, the researcher suggests making framework of how to choose any country in the world
(which has already life cycle inventory database, See Table 2) to be suitable for Egyptian
case study. The criteria of this framework are;
1. World climate zones by using ASHRAE STANDARD (Edition et al. 2011);
ANSI/ASHRAE/IES Standard 90.1-2010 (Supersedes ANSI/ASHRAE/IESNA
Standard 90.1-2007); Energy Standard for Buildings Except Low-Rise Residential
Buildings.
2. The used technology in the construction material plants; transportation system and
End-of-Life phase by using SimaPro database, which shown in Fig. (4).
3. The field visits and surveys in Egyptian plant/factories to collect local data and to
help in defining the optimal database to be selected.
After choosing the country and its database; any missing data will take it from literature
review, international papers and assumption.

LCI Database Name Description

BUWAL250
DK Input Output Database
99
Ecoinvent system and unit
process
ETH-ESU System and unit
Franklin USA 98
IDEMAT 2001
Industry data 2.0
USA Input Output Database
Inventory of packaging materials for the Swiss Packaging
This Danish input output database is based on the Danish
The Swiss center for Life Cycle Inventories has combined
and extended different LCI databases.
Inventory data for Swiss and the Western European.
Inventory data for North American materials.
This database has been developed at Delft University.
This library contains data as collected by European industry
The US input-output database consist of a 500x500 matrix.

TAB. 2 – International life cycle inventory database in SimaPro software

Framework for Application the Life Cycle Assessment Approach on Egyptian Residential Building

FIG. 4 – Current suggested framework of Egyptian building LCA scenarios

4.4. Life cycle impact analysis

Several impact assessment methods have been used in order to provide a broad picture
of environmental consequences. The approach developed at the Dutch Institute for Environ-
mental Sciences (CML) constitutes a basis, complemented with resource indicators like the
cumulative energy demand (Frischknecht et al., 2004) and water consumption, but also
waste-related indicators and damage oriented indicators: the DALY indicator (Disability
adjusted life loss years) for human health and the Potentially Disappeared Fraction of spe-
cies for biodiversity. The environmental issues considered in this study are listed in Figure 5,
example with the corresponding indicators and units. (Oyarzo and Peuportier 2014)
 Ahmed AbdelMonteleb, et al.

FIG. 5 – Typical impact assessment of environmental loading from Life cycle Inventory step
(Oyarzo and Peuportier 2014)

Simapro has many several environmental impact categories, thus, the research suggests
to make comparison between these categories and to make sensitivity analysis to ensure
which category more related to the suggested framework of Egyptian building life cycle
assessment. The example of environmental impact categories considered are listed in Figure
6, which involved in SimaPro software.

FIG. 6 – Typical impact assessment categories in SimaPro software [SimaPro Screenshot]

Several methods, such as the Environmental Priority Strategy and the Ecological Foot-
print Method, view land occupation and transformation from a resource utility perspective
(separate from impacts on biodiversity). This is in contrast to Eco-indicator 99, which uses
the impact category Land use to measure impacts on species diversity. Figure 7, showing the
mapping of the 75 impact category definitions to the 21 overall categories in SimaPro.
(Bengtsson and Howard 2011)
Framework for Application the Life Cycle Assessment Approach on Egyptian Residential Building

FIG. 7 – Mapping of the 75 impact category definitions to the 21 overall categories used in
SimaPro (Bengtsson and Howard 2011)

5. Conclusions
Since the recent survey by the authors indicated that there is no LCA-related studies in
Egypt and in Africa, this studies comes to cover partially this gap. However, due to unavail-
ability or incomplete or missing database of different industries in Egypt including build-
ing/construction industry, the present study suggests a frame work for applying the life cycle
assessment. The developed framework is based on the assumption that any missing data for
the life cycle inventory data will be assumed based on pre-defined criteria using the interna-
tional data base. These synthesis data base for the construction materials can be used for
various related studies in order to open the door for this important tool of environmental
impact assessment to be applied widely in Egypt and in Africa as well.
 Ahmed AbdelMonteleb, et al.

6. Recommendations
Using the above suggested framework, the following studies might be conducted:
1. Synthesis Egyptian Life Cycle Inventory Database from the International Database
through pre-defined suggested criteria.
2. Life Cycle Assessment of Egyptian building material: Towards evaluating the ener-
gy consummation and environmental impacts.
3. Assessing the Environmental Impacts of E-JUTS Complex Building using Life Cy-
cle Assessment Approach.
4. Evaluating the Life Cycle Assessment of Construction Procedures/Processess:
Egyptian Residential Building Case Study.
5. Integration of LCA and GIS for Decision Support for New City Building in Egypt
(Case Study National Housing Program in New Assiut City).
6. LCA Assessment of Operational Use Stage of Egyptian Residential Building..
7. Environmental Impact Assessment of End-of-Life Stage of Egyptian Residential
Building using Life Cycle Assessment
8. Evaluating the Disposal Scenarios of Egyptian Residential Building Using Life Cy-
cle Assessment Approach.
9. Comparative analysis of Life Cycle Assessment of Brick-Cement Building and
Steel Building in Egypt.

Acknowledgment
The first author would like to thank Egyptian Ministry of Higher Education (MoHE) for
providing him the financial support (PhD scholarship) for this research as well as the Egypt
Japan University of Science and Technology (E-JUST) for offering the facility and tools
needed to conduct this work.

References:
Papadopoulos, A.M., E. Giama (2007). Environmental performance evaluation ofthermal
insulation materials and its impact on the building. Building and Environment
42:2178–2187.
AbdelMonteleb, A. (2012). Using simulation for studying the influence of vertical shading
devices on the thermal performance of residential buildings (Case study: New Assiut
City). Ain Shams Engineering Journal 3:163–174. doi: 10.1016/j.asej.2012.02.001
AbdelMonteleb, A., A. Negm, M. Bady, and M.G. Ibrahin (2014). Towards An Integrated
Tool To Estimate Carbon Emissions From Life Cycle Assessment Of Building
Materials In Egypt. IMPACT: International Journal of Research in Engineering &
Technology 2:81–92.
ISO 14040 (1998). Australian/New Zealand Standard, Environmental management – Life
cycle assessment – Principles and framework. Standards Australia, NSW, Australia.
Framework for Application the Life Cycle Assessment Approach on Egyptian Residential Building

Asdrubali, F., C. Baldassarri, V. Fthenakis (2013). Life cycle analysis in the construction
sector: Guiding the optimization of conventional Italian buildings. Energy and
Buildings 64:73–89. doi: 10.1016/j.enbuild.2013.04.018
Bengtsson, J., N. Howard (2011). A Life Cycle Impact Assessment Part 1: Classification and
Characterisation. BPIC Ltd.
Blankendaal, T., P. Schuur, H. Voordijk, (2014). Reducing the environmental impact of
concrete and asphalt: a scenario approach. Journal of Cleaner Production 66:27–36.
doi: 10.1016/j.jclepro.2013.10.012
Schwedler, M.C.A, M.M. Hydeman (2011). ASHRAE STANDARD Energy Standard for
Buildings Except Low-Rise Residential Buildings. 2010:
ISO 14040 (2006). Environmental Management – Life Cycle Assessment – Principlesand
Framework.
ISO 14044 (2006). Environmental Management – Life Cycle Assessment – Require-ments
and Guidelines.
Guinee, J.B. (2001). Life Cycle Assessment - An Operational Guide to the ISO Standards.
Parker, J., P. Cropper (2011). LS Using Building Simulation To Evaluate Low Carbon
Refurbishment Options For Airport Buildings. 12th Conference of International
Building Performance Simulation Association, 14-16 November.
Ministry of Housing (1997). Utilities & Urban Communities, GOPP. General planning of the
new urban community in the Assyuti Valley. 22–5.
Monahan, J., J.C. Powell (2011). An embodied carbon and energy analysis of modern
methods of construction in housing: A case study using a lifecycle assessment
framework. Energy and Buildings 43:179–188. doi: 10.1016/j.enbuild.2010.09.005
Oyarzo, J., B. Peuportier (2014). Life cycle assessment model applied to housing in Chile.
Journal of Cleaner Production 69:109–116. doi: 10.1016/j.jclepro.2014.01.090

Summary:
A la connaissance des auteurs, il n'y a pas d'évaluation du cycle de vie (ECV) des études en
Egypte. Par conséquent, le document propose un cadre pour l'application de l'approche de
l'ACV sur toutes les étapes du berceau à l'approche de la porte du des bâtiments de la Nou-
veau Assiout Ville, Egypte. La méthode appliquée est LCA gouverné par la série ISO 14040.
Le logiciel SimaPro 8.1 est utilisé pour le calcul de l'entrée et la sortie de chaque système.
Les bâtiments existants à Nouveau Assiout est pris comme une étude de cas. Finalement,
cette étude représente la première étape d'appliquer l'approche de l'ACV dans la bâtiment
égyptien comme un outil d'évaluation des incidences sur l'environnement. La principale
difficulté de l'application de l'ACV est la pénurie de la base de données égyptienne pour le
cycle de vie Inventaire (CVI). Par conséquent, les chercheurs suggèrent un mécanisme de
synthétiser les parties manquantes de la base de données CVI égyptienne à partir de de la
base de données internationale. En outre, quelques recommandations sont présentées pour de
futures études.
 Relation Between Vehicles Time Headway and Carbon
Monoxide Emissions from Traffic in Urban Areas: Case
Study : New Borg El-Arab City – Egypt

Ahmed Elkafoury1,* Abdelazim M. Negm1,**

Mahmoud Farghly Bady 1,*** Mohamed Hafez Aly 2,****
1
Environmental Engineering Department, Egypt-Japan University of Science and Technolo-
gy (E-JUST), Alexandria, Egypt.
http://www.ejust.edu.eg/
2
Transportation Engineering Dept., Faculty of Engineering, University of Alex., Alexandria,
Egypt.
www.alexu.edu.eg/
*Corresponding Author: ahmed.elkafoury@ejust.edu.eg
** negm@ejust.edu.eg
*** mahmoud.bady@ejust.edu.eg
****mhafezal@yahoo.com

Abstract. Controlling traffic characteristics is essential for environmentally

oriented traffic management. Among these characteristics, time headway of
vehicles is in focus. This paper reveals the relationship between time headway
and vehicle Carbon monoxide emission. In this work, field measurement of
traffic characteristics have been conducted on two lanes per direction road
network link at the entrance of New Borg El-Arab City-Egypt. The distribution
of time headways for vehicles has been investigated showing that about 80%
and 78% of heavy vehicles and passenger cars respectively flow with time
headway less than 5 (sec/veh). The instantaneous vehicular emission model
VT-Micro is utilized to calculate CO emission factors of individual vehicles.
For environmental management of traffic and controlling vehicular emissions
through ITS applications, regression models of relationship between vehicles
CO emissions and corresponding time headway is introduced. Performance of
models has been statistically assessed. Models showed acceptable goodness of
fit with average R2 of 0.96.
P P
Vehicles Time Headway and Carbon Monoxide Emissions Relationships: Egypt

1 Introduction
The transportation sector plays a vital role in every nation’s economy. But, steady growth
in vehicular population in urban centers has put environmental stress on urban area particu-
larly by decreasing air quality through vehicular emissions. Unfortunately, Global demand of
transport is projected to increase by 45% by year 2030 (IEA, 2009). This is led by an in-
crease in road transport and consequently more vehicular emissions. Unlike emissions from
industry, vehicular emissions are produces at ground level and consequently their impacts on
the recipient population are more effective and harmful (Dubey et al., 2013).
Emission rates depend mainly on the characteristics of traffic (Pandian, S. et al., 2009).
Therefore, achieving sustainable transportation such as energy consumption and environ-
mental pollution is dominated by the ability of managing and controlling traffic characteris-
tics in the direction of decreasing emissions. Traffic characteristics affect vehicular emission
in different matters including traffic speed, acceleration and deceleration, traffic situation;
idling-stop and go-free flow.
A recent survey of transportation related-literature in Egypt indicated a clear absence of
studying the effect of the time headway (time interval between two vehicles passing a point
as measured from the front bumper to the front bumper), which is one of the important traffic
characteristics, on emission rates of vehicles. So, the objective of this paper is to investigate
the relationship between CO emission factors of vehicles in traffic and corresponding time
headway. This might be helpful for the environmental management of traffic in urban areas
specially with Intelligent Transportation Systems, ITS applications.
The paper is divided into three main sections. In the first section, time headway charac-
teristics and distribution of vehicles in traffic have been analyzed based on field measure-
ments of traffic conducted in 2 lanes per direction road network link in New Borg El-Arab
City-Egypt. In the second part, VT-Micro emission factor model have been applied to calcu-
late instantaneous CO emission factor of individual vehicles in the traffic flow using field
measurements of speed and acceleration as inputs. Analysis of outputs has been performed.
Finally, in the third section, the relationship between time headway of individual vehicles
and corresponding CO emission factor have been modeled for Passenger Cars (PCs), Heavy
Vehicles (HVs), and for all vehicle in the traffic. The three models have been statistically
assessed to evaluate models performance.

2 Field measurements
Field measurements of traffic data have be conducted on 2 asphalt concrete lanes per di-
rection with a 4m median and lane width of 3.75m per each at the first industrial zone of
New Borg El-Arab City which locates 45Km South-West of Alexandria city-Egypt. These
measurements were performed during morning peak hours 7:06AM – 9:42AM. Traffic data
was collected using Time-Mark Delta NT traffic analyzer. The collected data by the traffic
analyzer is transferred to the computer where Time-Mark’s VIAS2 application calculates
axle spacing and classify each vehicle. Data were collected for 2091 passenger cars and 669
heavy vehicles including all types of trucks besides buses.
 Ahmed Elkafoury et al.

3 Analysis of time headway data

Many traffic operations depend on the availability of large headways in the traffic flow.
Consequently, the distribution of headways has an effect on delays, which is properly ame-
nable of amount of emissions from vehicles. Therefore, studding the distribution of time
headway of the flow is very important for the management of traffic. In this section, the
paper introduces the statistical analysis of the distribution of time headway observed values
on the micro scale.
The distribution of the observations of time headway of Passenger cars (PCs) and Heavy
Vehicles (HVs) including single truck, truck and trails, and buses show that the observed
number of vehicles in the time headway interval decreases with the increase of time headway
interval values. For observed values in the study area, 1686 vehicles representing about 81%
of PCs and 523 vehicles representing about 78% of HVs have time headway less than 5 sec.
This indicates that the dominating car-following attitude of PCs and HVs drivers in the study
area is to flow with small headways. In the second rank, 309 vehicles representing about
15% of PCs and 93 vehicles representing about 14% of HVs have time headway between 5
sec and 10 sec. In the third rank, about 3% and 5% of PCs and HVs respectively have time
headway between 10 sec and 15 sec. Only 15 vehicles representing about 0.7% of PCs and
11 vehicles representing about 0.6% of HVs have time headway more than 20 sec. This
matches the headway distribution explained by Highway Capacity Manual (HCM2010)
(TRB, 2010) which indicated high frequency of time headway between 0 to 5 sec, and less
frequency of time headway more than 5 sec. Figure 1 represents the distribution of observed
number of vehicle in different headway category is shown in. Figure 2. illustrates percentage
of PCs and HVs in different headway categories.

FIG. 1 – Number of vehicles in different time headway categories

Vehicles Time Headway and Carbon Monoxide Emissions Relationships: Egypt

FIG. 2 – Distribution of observed PCs and HVs among different time headway categories

4 Incorporating VT-micro emission model

VT-Micro is an instantaneous emission model developed in Virginia Tech - The Transpor-
tation Infrastructure and Systems Engineering Program (TISE). It is a microscopic vehicle
fuel consumption and emission modeling tool that allows users to estimate vehicle instanta-
neous fuel consumption and emission levels. The VT-micro model was developed based on
chassis dynamometer data collected at the Oak Ridge National Laboratory (ORNL) from 60
light duty vehicles and trucks (Swidan H., 2011). It was developed as a regression model
from experimentation with numerous polynomial combinations of speed and acceleration
levels (Rakha, H., et al. 2003). VT-Micro relates the dependent variables (instantaneous
emission) to a set of quantitative independent variables, namely, instantaneous speed and
acceleration levels. The regression model includes a combination of linear, quadratic, and
cubic speed and acceleration terms because it provides the least number of terms with a
relatively good fit to the original data (R2 between modeled and measured values excess 0.92
) (Rakha, H., et al. 2003).
The ultimate expansion of this model is its implementation within microscopic traffic
simulation software. These models can then be utilized to evaluate the environmental im-
pacts of microscopic vehicle behaviors, such as ramp metering, traffic signal coordination,
and alternative ITS strategies (Rakha, H., et al. 2004). More detailed description of the model
is provided in the literature (Ahn et al. 2002).

4.1 Application of VT-Micro emission model for calculating instantane-

ous CO emission factors
In this part, the instantaneous vehicular emission model VT-Micro has been applied to
calculate the instantaneous CO emission rate (gm/s) of individual vehicles. This is to find the
relationship between CO emission rate (gm/s) of individual vehicle and the instantaneous
time headway of the vehicle as a step toward controlling emission from traffic through con-
trolling the time headway of vehicles.
 Ahmed Elkafoury et al.

In the case study, the application of VT-Micro emission model includes running the
MATLAP file (VTMicro.P) and preparing a CVS file includes columns of speed (km/hr) and
acceleration (km/hr/s). For studying CO emissions emission factors (gm/sec) of different
types of vehicles, 3 CVS files were prepared for All types of vehicles, HVs, PCs respective-
ly. The output files contain the instantaneous CO emission factors (gm/sec) of individual
vehicles. Figure 3. shows the interface of VT-Micro emission model.

FIG. 3. Interface of VT-Micro emission and fuel consumption model.

4.2 Analysis of instantaneous CO emission factors data

The analysis of the distribution of total observed vehicles among different CO emission
factor categories indicates that 87% of observed vehicles have low instantaneous CO emis-
sion factors (less than 0.1 gm/sec). This shows that the traffic situation makes the majority of
vehicles in the flows have combinations of acceleration and speed that lead to lower CO
emission factors. Only 12.1% of the total number of observed vehicles during measurements
has CO emission factors between 0.1 - 0.3 (gm/sec). Figure 4. Illustrates percentage share of
vehicles in different CO emission factor categories.
Analysis of resulting data indicates that for PCs, at lower time headway intervals, an in-
crease of CO emission factor occurs with the decrease of time headway. The reason is that, at
lower time headway, the traffic flows with a car following behavior with an acceleration and
deceleration attitude. This is associated with an increase of CO emission factor. Then at high
values of time headways more than 50 (sec/veh) when the speed of traffic increases, CO
emission factor of PCs decreases (Han Xue et al. 2013).
For HVs, at lower time headway intervals, average CO emission factor (gm/sec) decreases
slightly with the increase of time headway. This is because the acceleration and deceleration
rate of heavy vehicles is very slow at lower values of time headway. Then, at time headways
values more than 50 (sec/veh), CO emission factors of HVs dramatically drop. This can be
explained by that heavy vehicles in the study area are diesel powered. In which, at high
speeds, a complete combustion at higher temperatures occurs. At this condition, CO emis-
sions are very low for diesel-powered engines as CO emission produced at lower combustion
temperature (Dubey et al. 2013).
Vehicles Time Headway and Carbon Monoxide Emissions Relationships: Egypt

FIG. 4– Percentage share of vehicles in different instantaneous CO emission factor catego-

ries
For all types of vehicles, the overall trend of the mixed traffic (PCs and HVs) shows very
slight increase of average CO emission factor (gm/sec) with the increase of time headway at
low time headway values ( less than 40 sec/veh). Then, a significant increase of average CO
emission factor (gm/sec) of about 144.5% occurs when transferring from time headway in-
terval 30-40 (sec/veh) to the time headway interval 40-50 (sec/veh). The increase of time
headway is always associated with the vehicle driver attitude to accelerate which lead to an
increase of vehicles CO emission factor. Then, CO emission factor increases at high values
of time headways as speed of traffic increases. Figure 5. shows the distribution of average
instantaneous CO emission factor for different vehicles types in different time headway cate-
gories.

FIG. 5– Average instantaneous CO emission factor in different time headway categories for
different vehicles types
 Ahmed Elkafoury et al.

5 Modeling the relationship between time headway and CO

emission factors
In this section, regression analysis using MATLAB R2013a curve fitting tool was carried
out to provide statistical models describing the relationship between time headway of vehi-
cles during traffic and instantaneous CO emission factors (gm/sec) of individual vehicles.
This aims to evolve regression models can be used with the help of real-time field measure-
ments of traffic time headways to calculate and control vehicles CO emissions. This is an
important issue in the environmental management of traffic systems specially in the applica-
tion of Intelligent Transportation Systems (ITS).
Correlation Coefficients (CC) between CO emission factors (gm/sec) and time headway
of vehicles have been investigated for PCs, HVs, and all types of vehicles. Results indicated
that, CO emission factors of PCs have CC of (0.061) with time headway. This is high CC
with comparison to that between CO emission factors of HVs and time headway, which is (-
0.0252). The overall CO emission factors of all types of vehicles have CC of (0.061) with
time headway.
Regression analysis has been performed for three data sets of the three vehicles categories
in the study area; PCs, HVs, and all types of vehicles. The best fit resulting models are
shown in Table 1. Where CO is the carbon monoxide emission factor of the vehicle in
(gm/sec), and H is the time headway of the vehicle in (sec/veh).
The analysis of the best fit models indicate that, the model of all types of vehicles indi-
cates Root Mean Square of Errors (RMSE) higher than the models of PCs and HVs. But, the
three models still represents goodness of fit as they have high values of R2 (0.9883, 0.9088,
and 0.9833 for PCs, HVs and All types of vehicles) respectively.
Also, the analysis indicates that PCs, HVs, and all types of vehicles have model factor of
(0.00305), (-0.004804), (0.001904) respectively with (log H). The model factors match the
CC of CO emission factors with time headway. On the other hand, model factor of PCs mod-
el is higher that of HVs model. This advocates what has been mention above that HVs pro-
duces less CO emissions than PCs. Consequently, less dependence of CO emission factors of
HVs on time headway.
Type of vehicle Time headway regression model R2 RMSE

PCs CO = 0.00305logH + 0.02304 0.9883 0.0015

HVs CO = -0.004804logH + 0.1137 0.9088 0.0151

All types of vehicles CO = 0.001904logH + 0.03634 0.9833 0.038

TAB. 1 – Regression models of the relationship between time headway and CO emission
factors for different vehicles categories.
To assess the performance of models, different statistical indicators shown in Table 2 have
been calculated and investigated. The tree models show relatively small biases from moni-
tored vales. This can be shown from the small values of average of errors. These values are (-
Vehicles Time Headway and Carbon Monoxide Emissions Relationships: Egypt

0.00334) (gm/sec), (0.004693) (gm/sec), and (-0.00974) (gm/sec) for the CO emission factor
models of PCs, HVs, and all types of vehicles respectively. Moreover, the small values of
average of errors indicate that the errors are equally distributed between positive and nega-
tive errors (around zero error). The percentage errors of the average value of CO emission
factor are relatively acceptable; -12.1%, 4.3%, and 11.1% for the 3 models of PCs, HVs, and
all types of vehicles respectively. Values of the standard deviation of errors have small val-
ues; 0.028(gm/sec), 0.075(gm/sec), 0.056 (gm/sec) for the model PCs, HVs, and all types of
vehicles respectively. This indicates that the model correctly describes the relationship be-
tween CO emission factor and vehicles time headway. It also indicates that the model pro-
duces comparable data to measured data.
The models have Frictional Biases (FB) values of 0.13 (gm/sec), -0.02 (gm/sec), and 0.19
(gm/sec) for the CO emission factor models of PCs, HVs, and all types of vehicles respec-
tively. The value of FB indicates a small overall overestimation for PCs and all types of
vehicles CO emission factor models and small overall underestimation of HVs CO emission
factor model. These values of FB are considered acceptable as it ranges between -0.7 and 0.7
(Misra et al. 2013). On the other hand, the Normalized Mean Square of Errors NMSE for the
investigated models equals 0.000763, 0.119408, and 0.073229 for CO emission factor mod-
els of PCs, HVs, and all types of vehicles respectively. So, the performance of the model is
considered acceptable and correctly describes the processes since NMSE is less than 0.5 (N.
Sharma, 2004) and (Misra et al. 2013).
All types of
Statistical Indicator PCs model HVs model vehicles
model
Average of all errors (gm/sec) -0.00334 0.004693 -0.00974

% Error in the average -12.1 4.3 -11.1

SD (gm/sec) 0.028 0.075 0.056

FB 0.13 -0.02 0.19
NMSE 0.000763 0.119408 0.073229

TAB. 2- Model performance statistical indicators of CO emission models of different vehicles

categories in the study area

6 Conclusions
This paper has focused on modeling of the relationship between CO emission factors of
vehicles in traffic on urban areas roads and one of the important traffic flow characteristics;
time headway. CO emission factors were considered due to the great harm of CO emissions
on both environment and human health. Field measurements of traffic characteristics have
been conducted in a road network link in an urbanized area of New Borg El-Arab City at the
North-East of Egypt. The analysis process of time headway data considers Passenger Cars
(PCs), Heavy Vehicles (HVs), and All types of vehicles in the traffic flow. The distribution
 Ahmed Elkafoury et al.

of time headway indicated that major portion of vehicles (about 80% of HVs and 78% of
PCs) tend to flow with time hedway less than 5 (sec/veh).
To investigate the instantaneous emission behavior of vehicles, the emission factor model
VT-Micro has been applied for the study area to calculate the instantaneous CO emission
factor of individual vehicles using combination of vehicle speed and acceleration as inputs.
The analysis of outbuts indicates that 87% of observed vehicles have low instantaneous CO
emission factors (less than 0.1 gm/sec). Considering time headway effect, the analysis shows
that for PCs, at lower time headway intervals, an increase of CO emission factor occurs with
the decrease of time headway. The reason is that, at lower time headway, the traffic flows
with a car following behavior with an acceleration and deceleration attitude. For HVs, at
lower time headway intervals, average CO emission factor (gm/sec) decreases slightly with
the increase of time headway. Then, at time headways values more than 50 (sec/veh), CO
emission factors of HVs dramatically drop.
For environmental management of traffic systems specially for ITS applications in urban
ares, the relationship between CO emission factor of indevidual vehicle and corresponding
time headway have been modeled. Statistical regression models for PCs, HVs, and all types
of vehicles have been considered. The three models have been statistically assessed using
different statistical indicators including R2, SD, FB, and NMSE. The developed models
showed good performance and the representativeness of modeled data indicated good fitness
with high R2 of 0.9883, 0.9088, and 0.9833 for PCs, HVs and All types of vehicles respec-
tively and low RMSE of 0.0015, 0.0151, and 0.038 for PCs, HVs and All types of vehicles
respectively.

Acknowledgement
The first author would like to thank Egyptian Ministry of Higher Education (MoHE) for
providing him the financial support (PhD scholarship) for this research as well as the Egypt
Japan University of Science and Technology (E-JUST) for offering the facility and tools
needed to conduct this work.

References
Ahn, K., Rakha, H., Trani, A., and Van Aerde, M. (2002). Estimating Vehicle Fuel Con-
sumption and Emissions Based on Instantaneous Speed and Acceleration Levels. Journal
of Transportation Engineering, 128(2), 182-190.
Dubey, Bhawna, Asim Kumar Pal, and Gurdeep Singh (2013). Assessment of Vehicular
Pollution In Dhanbad City Using Caline 4 Model.International Journal of Geology, Earth
and Environmental Sciences. Vol. 3 (1) January-April pp.156-164.
Han Xue, Shan Jiang, Bin Liang. (2013). A Study on the Model of Traffic Flow and Vehicle
Exhaust Emission. Mathematical Problems in Engineering Volume 2013. Article ID
736285, 6 pages. DOI:10.1155/2013/736285.
IEA. World energy outlook (2008). Paris: International Energy Agency; 2009.
Vehicles Time Headway and Carbon Monoxide Emissions Relationships: Egypt

Misra, Aarshabh, Matthew J. Roorda, and Heather L. MacLean (2013). An integrated model-
ling approach to estimate urban traffic emissions. Atmospheric Environment 73; 81-91.
Pandian, S., S. Gokhale, & A.K. Ghoshal, (2009). Evaluating effects of traffic and vehicle
characteristics on vehicular emissions near traffic intersections. Transportation Research
Part D: Transport and Environment, 14(3), 180-196.
Rakha, H., K. Ahn, I. El-Shawarby, & S. Jang, (2004). Emission model development using
in-vehicle on-road emission measurements. In Annual Meeting of the Transportation Re-
search Board, Washington, DC (Vol. 2).
Rakha, H., K. Ahn, & A. Trani, (2004). Development of VT-Micro model for estimating hot
stabilized light duty vehicle and truck emissions. Transportation Research Part D:
Transport and Environment, 9(1), 49-74.
Rakha, H., K. Ahn, & A. Trani (2003). Comparison of MOBILE5a, MOBILE6, VT-MICRO,
and CMEM models for estimating hot-stabilized light-duty gasoline vehicle emis-
sions. Canadian Journal of Civil Engineering, 30(6), 1010-1021.
Sharma, N., K. K. Chaudhry, C. V. Chalapati Rao (2004). Vehicular pollution prediction
modelling: a review of highway dispersion models. Transport Reviews: A Transnational
Tran disciplinary Journal 2004; 24:4, 409-435.
Swidan, H. (2011), Integrating AIMSUN Micro Simulation Model with Portable Emissions
Measurement System (PEMS): Calibration and Validation Case Study. MS.c thesis.
Transportation Research Board (TRB), Highway Capacity Manual fourth edition (2010).
National Research Council, Washington, DC.

Summary
Contrôle des caractéristiques de trafic est essentielle pour la gestion du trafic axée sur
l'environnement. Parmi ces caractéristiques, Des progrès de temps des véhicules est au point.
Ce document révèle la relation entre progrès de temps et véhicule monoxyde de carbone
émission. Dans ce reserch, la mesure de caractéristiques de trafic ont été menées sur deux
voies par direction lien du réseau routier à l'entrée de New Borg El-Arab City-Egypte. La
distribution des fréquences de passage de temps pour les véhicules a été étudiée montrant
que près de 80% et 78% de véhicules lourds et de voitures particulières circulent respective-
ment progressé de temps inférieur à 5 (sec / véh). Le modèle d'émission des véhicules in-
stantanée VT-Micro est utilisé pour calculer les facteurs d'émission de CO des véhicules
individuels. Le modèle d'émission des véhicules instantanée VT-Micro est utilisé pour cal-
culer les facteurs d'émission de CO des véhicules individuels. Pour la gestion de l'envi-
ronnement de la circulation et de contrôle des émissions des véhicules par le biais de ses
applications, des modèles de régression de la relation entre les véhicules sur les émissions de
CO et de progrès de temps correspondant est introduit. Performance des modèles a été statis-
tiquement évaluées. Modèles ont montré bonté acceptable de forme avec R2 moyenne de
P P

0,96.