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Procedia Engineering 83 (2014) 386 393

SYMPHOS 2013, 2nd International Symposium on Innovation and Technology in the

Phosphate Industry

Removal of Cadmium from water using Natural phosphate as

Adsorbent
H. Yaacoubia,b, O. Zidania,b, M. Moufliha, M.Gouraib, S. Sebtib*
a

Laboratory of Georesources Sedimentlogy and Environment, , University of Hassan II Mohammedia-Casablanca, Faculty of Sciences Ben
M'Sik,Casablanca (Morocco).
b
Laboratory of Organic Chemistry Catalysis and Environment, University of Hassan II Mohammedia-Casablanca, Faculty of Sciences Ben
M'Sik,Casablanca (Morocco)

Abstract
Adsorption process is being widely used by various researchers as an effective process of advanced waste water treatment of
industrial effluent containing metals. The present work involves an investigation of the use of natural phosphate (NP), which being
locally abundant and cheap material in Morocco, as adsorbent for removal of cadmium from aqueous solutions. .The kinetic of
Cadmium on natural phosphate adsorption efficiency and adsorption process were evaluated and analyzed using Langmuir and
Freundlich model of adsorption equilibrium. The effects of various experimental parameters, such as initial cadmium concentration,
contact time were investigated. The natural phosphate had the monolayer adsorption capacity to 26mg/g at pH of 5.0. Adsorption
measurements show that the process is very fast and physical in nature. The extent of the cadmium removal increase with decrease
in the initial concentration. These results show that natural phosphate is a good adsorbent for cadmium from aqueous solutions and
could be used as a purifier for water and wastewater.
2014
2014 The
The Authors.
Authors. Published

Published by
by Elsevier
Elsevier Ltd.
Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Scientific Committee of SYMPHOS 2013.
Peer-review under responsibility of the Scientific Committee of SYMPHOS 2013
Keywords: Naturel phosphate ; Adsorption; Heavy metals; Cadmium ; Environment.

* Corresponding author. Tel.: +212 661 46 48 19; fax: +212 522 70 46 75.
E-mail address: said.sebti@univh2m.ac.ma

1877-7058 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license

(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Scientific Committee of SYMPHOS 2013
doi:10.1016/j.proeng.2014.09.039

H. Yaacoubi et al. / Procedia Engineering 83 (2014) 386 393

1.

387

Introduction

In recent year, water pollution due to human activity becomes a crucial problem and represents one of the major
environmental concerns throughout the world as more as contaminants enter the marine environment every year.
The removal of those toxic heavy metals has become project of many studies in the surface and groundwater to
protect the natural environment and improve the quality of water.
There are many processes and Common techniques including precipitation, ion exchange, distillation, oxidation,
reduction, filtration, electrochemical treatment, evaporationetc to remove metals from wastewater. However, these
processes are expensive this why its interesting to develop more effective and cheap treatment.
Among these pollutants, cadmium is a heavy metal that is found in aquatic environments under different physical
forms (dissolved, colloidal, and particulate) and in different chemical forms (organic and inorganic).
Cadmium is one of the most toxic metals affecting man, its excretion from the body is very low and it has
synergistic toxicity with other metals. Thus the removal of cadmium from polluted water is of great importance. Only
very few studies have been done on the level of cadmium in the environment. Several sorbents have been suggested
in the literature for the removal of toxic metals (including cadmium) from water. These include activated carbon,
naturel zeolite, clays and biomassetc [1-2].
Natural phosphate included more than two hundred mineralogical species. But the most widely prevalent belong
to the family of apatite is Fluorapatite (Ca10 (PO4)6F2), which crystallized in the hexagonal system.
Apatite has been used as adsorbent to remove metals from wastewater and aqueous solutions [3-4-5-6-7-8-9-1011-12-13-14-15-16-17-18-19]. The mechanism of metal removal depends to the adsorbate, adsorbent and initial
conditions of solution.
Natural phosphates are an important natural resource in Morocco which needs to be valorised. They can be used
not only as fertilisers but also they have been successfully utilized as catalysts (either alone or conveniently-modified)
in a wide range of organic reactions [20-21-22-23-24] and as adsorbent to remove metals from waste water [17-1819].
In this work, we have assessed the retention of cadmium by natural phosphate. This study was based on the
influence of concentration, adsorbent mass and modeling of interaction metal phosphate adsorption isotherms.
2.

Materials and methods

2.1. Natural phosphate caracterisation

Morocco possesses 75 percent of the world's phosphate reserves. It is the world's first exporter (28% of the global
market) and third producer (20% of global production) from four poles: OuledAbdoun, Ganntour, Maskala and
Boucraa.
Phosphate rock used here comes from an extracted ore Ouled Abdoun (Khouribga) deposit (Morocco), it was
washed with water and only fraction between 100 and 400 Pm, which contains phosphate phases, was retained. It was
then dried in over night at 105 C and crushed to obtain the homogeneous phosphatic support having size below 125
m.
The mineralogy of natural phosphate is carbonate fluoroapatite as shown by the X-ray diffraction pattern. This
study is completed by IR analysis that we provide information on nature of the functional groups and molecular bonds
of the sample. See Figure 1.

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C: Carbonate fluorapatite

C
C
*

C
C

C
10

20

30

40

50

60

70

2 Theta

Fig.1. XRD patterns of natural phosphate.

The IR specters of NP were obtained by Fourier transform spectrometer Nicolet 205. The pellet is obtained by
crushing 0,01g of sample with 0.09g of KBr. Before using, the pellet was dried at 105C for 2h. The natural
phosphate used in this study is represented in the Figure 2 that shows the characteristic of fluorapatite bonds.

100

Transmitance %

80

OH
CO3

60

40

CO3
PO4

20

0
4000

PO4
3500

3000

2500

2000

1500

1000

500

Wave numbers

Fig. 2. FTIR spectra of natural phosphate

2.2. Adsorption studies

Aqueous solutions containing cadmium ions at various concentration were prepared from CdCl2 2,5 H2O. The
solution pH was adjusted to 5 with HCl 1N. The pH was measured with an electrode ORION, coupled with pH meter
model Bench-Top and the reaction time was conducted for 2h.
The kinetic sorption study of Cd2+ ions was used to determine the contact time required to reach equilibrium. The
solution was kept during the contact time under constant stirring at room temperature, 0.05g of NP is dispersed in
50ml of solution at concentration 100mg/l.
The concentration effect of Cd2+ ions was performed by suspended 0.05g of NP in 50ml of cadmium solution
containing 100 and 50mg/L.
The mass effect of NP on removal of cadmium was studied for mass range 0,1 4 g/L at pH 5 in 50ml of cadmium
solution containing 50mg/l .

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For the determination of adsorption capacity of Cd2+ ions in the NP, the initial concentrations of the metal ions
were varied between 10 and 300mg L1 while the dry phosphate weight of the adsorbent was kept constant at 0.05 at
pH 5.
The metal concentrations were determined by GBC 908PBMT atomic absorption spectrophotometers
3.

Results and discussion

3.1. Effect of contact time and adsorption kinetic

The results for the adsorption of Cd2+ onto natural phosphate as a function of time are shown in Figure 3. The
adsorption of Cd2+ appears to be a two-step process. In the first 20 min, the adsorption capacity increased. After this
initial fast adsorption period, the uptake of Cd2+ by NP reaches the adsorption equilibrium in about 20min.

Cadmium removal (%)

30

Cd2+

25

20

15

10

0
0

20

40

60

80

100

120

Time (min)

Fig.3. Kinetic study of adsorption of Cadmium onto NP

3.2. Effect of initial concentration

To evaluate the sorption characteristics of NP for cadmium ions, the change of sorption capacity with time for
different initial solution concentrations has been investigated. The solution concentration of cadmium was varied from
50mg/l to 100mg/l, the NP concentration is 1g/L and the solution pH was adjusted to 5 as previous studies suggested
[25]. The sorption capacity of cadmium increases with the increase of contact time Figure 4. For the both initial
concentrations, the sorption capacity increases rapidly at an initial stage of sorption and no appreciable increase were
observed beyond this time. When the initial concentration increases, the sorption capacity increases and reaches the
adsorption equilibrium in about 20min.
100mg/L
50mg/L

Cadmium Removal (%)

40
35
30
25
20
15
10
5
0
0

20

40

60

80

Time (min)
Fig.4. Effect of cadmium concentration.

100

120

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H. Yaacoubi et al. / Procedia Engineering 83 (2014) 386 393

3.3. Effect of adsorbent mass

The experimental results of sorption of cadmium on natural phosphate at various concentrations of NP are shown
in Figure 5.
Cd2+

Cadmium removal (%)

80
70
60
50
40
30
20
10
0
0

Adsorbent dose (g)

Fig.5. Influence of adsorbent dose on the adsorption of Cadmium onto NP

Increase of NP concentration increase of percentage adsorption. As NP concentration increases from 0.1 to 4 g/l,
percentage removal was increased from 4 % to 78 % at 2.5 g/l.
Its suggested that general mechanism for the ability of apatite to take up cadmium cation, the first is concerned
with the adsorption of ions on the solid surface followed by their diffusion into apatite and the second is the dissolution
of apatite in the aqueous solution containing cadmium followed by the precipitation or coprecipitation (dissolution
precipitation mechanism) [26].
3.4. Adsorption isotherm
The amount of adsorption per unit mass of NP was evaluated by using the following expression:

(1)

Here, q (mg/g) is the amount of adsorption per unit mass of NP, C0 and C are the concentrations (mg/l) of the metal
ions in the initial solution and in the aqueous phase after treatment for certain period time, respectively; V (l) is the
volume of the aqueous phase and m (g) is the amount of NP used.

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The Figure 6 shows the relationship between the different quantities of metal ions adsorbed per unit mass of NP
and the equilibrium concentration of the metal ion at room temperature for the residence time of 2 h.

Amount adsorbed(mg/g)

30

Cd2+

25

20

15

10

0
0

50

100

150

200

250

300

350

Equilibrium concentration (mg/l)

Fig.6. Plot of the amount of Cadmium adsorbed versus concentration

We note that the amount adsorbed increase and tends to the constant value 26mg/g which is the adsorption capacity
at saturation.
3.5. Langmuir isotherm
The experimental data have been generally fit by the Langmuir model: an equilibrium model able to identify
chemical mechanism involved. The Langmuir equilibrium equation is shown in equation (2), figure 7:

(2)



Where Ce (mg/l) is the equilibrium concentration, q (mg/g) is the amount of adsorption per unit mass of NP at
equilibrium, qmax is the amount of adsorbate adsorbed per unit mass of NP corresponding to complete monolayer
coverage and b is the Langmuir constant, which can be considered as a measure of adsorption energy. A linear plot of
(Ce/q) against Ce was employed to give the values of qmax and b from the slope and intercept of the plot.
Cd2+

14

y = 0,037x + 0,224
R = 0,999

12

Ce/q (g/L)

10

0
0

50

100

150

200

250

300

Ce (mg/L)
Fig.7. Plot of Langmuir equation for cadmium adsorption onto NP

350

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H. Yaacoubi et al. / Procedia Engineering 83 (2014) 386 393

Table 1: Langmuir Parameters of cadmium adsorption onto NP.
Metal Ion

b (L/mg)

qmax (mg/g)

r2

Cd2+

0.042

29.41

0.999

The Langmuir model assumes that adsorption is monolayer and is dependent on the assumption that the adsorbent
surface consists of active sites having a uniform energy and therefore, the adsorption energy is constant [27].
3.6. Freundlich isotherm
In contrast to Langmuir, the Freundlich model assumes that the adsorbent surface energy is heterogeneous. It is
assumed that the stronger binding sites are occupied first and that the binding strength decreases with the increasing
degree of site occupation. The Freundlich adsorption isotherm expression is shown in Equation (3) [28]:

 

(3)
(4)

From the Equation (4), we can determine the constants of Freundlich isotherm for the removal of Cd2+ on NP, The
values obtained for the Freundlich parameters are lower than those obtained by the Langmuir model which explains
the diffusion of ions inside the pores.
Cd2+
y = 0,429x + 1,561
R = 0,970

ln(qe)

0
0

ln(Ce)

Fig.8. Plot of Freundlich equation for cadmium adsorption onto NP

Table 2: Freundlich Parameters of cadmium adsorption onto NP.
Metal Ion

KF

1/n

r2

0.427

0.970

(mg/g)(dm3/mg)1/n
Cd2+

4.76

The effectiveness of an adsorbent is much higher than the coefficient 1 / n is small and constant KF is greater [29].

H. Yaacoubi et al. / Procedia Engineering 83 (2014) 386 393

4.

Conclusion

This study shows that:

Natural phosphate could be used as an adsorbent capable to remove cadmium from aqueous solution.
- The adsorption equilibrium obtained is 20min.
- The adsorption of metals ions depends on the concentration of the metal solutions.
- The adsorption experimental results of this metal are in a good correspondence with the Langmuir and
Freundlich isotherms.
- The adsorption is a principal mechanism of metal removal by NP at pH 5.
The abundance of natural phosphate, its low price, its non-aggressive nature towards the environment and the results
obtained in this study, classifies the natural phosphate as a new competitor of the some well-known adsorbents for
wastewater cleanup.
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