Journal of Environmental Management 166 (2016) 589e595

Contents lists available at ScienceDirect

Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Research article

Removal of Cr(III) from chrome tanning wastewater by adsorption

using two natural carbonaceous materials: Eggshell and powdered
marble
Saliha Elabbas a, b, Laila Mandi a, b, Fatima Berrekhis c, Marie Noelle Pons d,
Jean Pierre Leclerc d, Naaila Ouazzani a, b, *
a
Laboratoire d'Hydrobiologie, Ecotoxicologie et Assainissement (LHEA, URAC 33), Facult
e de Sciences Semlalia, BP2390, Universit

e Cadi Ayyad, Marrakech,
Morocco
b

Centre National d'Etude et de Recherche sur l'Eau et l'Energie (CNEREE), BP511, Universit
e Cadi Ayyad, Marrakech, Morocco
c
Equipe de Physico-chimie des Mat


eriaux, Ecole Normale Sup
erieure, Universit

e Cadi Ayyad, BP2400, 40000 Marrakech, Morocco
d
Laboratoire R
eactions et G

enie des Proc

ed

es, (UMR CNRS 7274), Universit
e de Lorraine, 1 rue Grandville, 54001 Nancy cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: In the present paper, eggshell and powdered marble, two carbonaceous materials, were used to remove
Received 24 June 2015 Cr(III) ions from a real chrome tanning wastewater. The effects of initial efuent pH, adsorbent dose,
Received in revised form contact time and temperature were studied. The maximum uptake of chromium ions was obtained at pH
5 November 2015
5.0 with the dose 20 g L
1 and 12 g L
1 for eggshell and powdered marble respectively. Adsorption
Accepted 7 November 2015
Available online 18 November 2015
equilibrium was reached after 14 h contact time for eggshell and only after 30 min for powdered marble.
Under these conditions, almost 99% Cr(III) was removed from chrome tanning wastewater having an
initial concentration of chromium of 3.21 g L
1. Kinetic data were satisfactorily described by a pseudo-
Keywords:
Chromium
second order chemical sorption model. The equilibrium rate constant was notably greater for
Eggshell powdered marble than for eggshell with 1.142$10
3 (g mg
1 min
1) and 0.041$10
3 (g mg
1 min
1)
Powdered marble respectively. The adsorption isotherm were well described by a Langmuir model and showed that the
Tanning wastewater interaction of chromium with the two adsorbents surface is a localized monolayer adsorption with a
Adsorption smaller energy constant for the powdered marble than for eggshell (0.020 (L mg
1) and 0.083 (L mg
1)
Toxicity respectively). The powdered marble was able to adsorb faster a large amount of Cr (III) in comparison to
eggshell. The use of a standardized lettuce seed bioassay allowed evaluating a better effectiveness of the
Cr adsorption on the powdered marble, removing up to 40% of the treated efuent toxicity than by
eggshell 25%.
The powdered marble could be considered as an effective, low cost carbonaceous material to be used
for chromium removal from tanning wastewater.
2015 Elsevier Ltd. All rights reserved.

1. Introduction being relatively stable and largely predominant (Sumathi et al.,

The large release of heavy metals into the environment caused
by industrial wastewater discharge presents a serious danger for
aquatic ecosystems. Chromium is one of most toxic metals from the
hazardous heavy metals list. It can exist in a different oxidation
states, with the trivalent (Cr(III)) and hexavalent (Cr(VI)) states
* Corresponding author. Laboratoire d'Hydrobiologie, Ecotoxicologie et Assai-
nissement (LHEA, URAC 33), Faculte
de Sciences Semlalia, BP2390, Universite

Cadi
Ayyad, Marrakech, Morocco.
E-mail address: ouazzani@uca.ac.ma (N. Ouazzani).
2005). The differences in the oxidation state of chromium inu-
ence its toxicity and its chemical properties in water. Hence,
trivalent chromium is approximately 300 times less toxic than the
hexavalent chromium form, but it can cause more structural dis-
turbances in erythrocyte membranes (Suwalsky et al., 2008). The
major source of a chromium released into the environment are
industries of metallurgical, electroplating, battery manufacturing,
agrochemicals, basic steel, paper and pulp, petrochemicals, fertil-
izer industries and tanneries (El-Sherif et al., 2013).
Several methods are available to remove chromium species
from wastewater (Fu and Wang, 2011), such as chemical

http://dx.doi.org/10.1016/j.jenvman.2015.11.012
0301-4797/ 2015 Elsevier Ltd. All rights reserved.
590 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595

precipitation (Meunier et al., 2006), ion exchange (Sahu et al., Table 1

2009), membrane ltration (Religa et al., 2011), electro- Main characteristics of raw wastewater tested.

coagulation (Golder et al., 2007), inltration percolation (Tiglyene Parameter Value SD

et al., 2008) and phytoremediation (Mandi et al., 2009). Among pH (at 25  C) 3.81 0.10
these methods, biosorption merits a special attention because of its EC (mS cm
1) (at 25  C) 60.0 3.0
relative simplicity and low cost. Many studies have been carried out Cl
(g L
1) 11.6 0.5
using different natural materials for chromium removal including COD (g L
1) 3.75 0.10
SO4 2
(g L
1) 1.6 0.2
orange peel (Lugo-Lugo et al., 2012), modied potato starch (Pillai
NH4 (mg L
1) 33.2 0.4
et al., 2013), chitosan (Santana cadaval Jr et al., 2013), waste con- Total P (mg L
1) 7.0 0.2
taining chitin (Fabbricino et al., 2013) and polymeric nanobers (El- PO4 3
(mg L
1) 2.1 0.1
Sherif et al., 2013). Several other researchers have tested materials HCO3
(g CaCO3 L
1) 0.41 0.01
Cr(III) (g L
1) 3.21 0.05
composed mostly of calcite such as dolomite (Albadarin et al.,
2012), eggshell (Rajendran and Mansiya, 2011) and nano- SD Standard Deviation.
carbonate-hydroxylapatite (Tang et al., 2013). All these studies
showed very interesting removal capacities of such type of carbo-
naceous materials towards chromium: 10.01 mg g
1 at waste. The collected eggshells were just washed with distilled
C0 50 mg L
1 of Cr(VI) for dolomite, 9 mg g
1 from a solution of water to remove the adhering membranes then they were dried at
2910.1 mg L
1 of Cr(III) using eggshell and 37 mg g
1 from a so- the ambient atmosphere for several days. The dried eggshells were
lution of 75 mg L
1 of Cr(III) using nano-carbonate-hydroxylapatite. ground, sieved and stored in a desiccator for further use. The
It was reported that chromium elimination is produced mainly via powdered marble was coming from a large private marble pro-
exchange reaction with the calcium carbonate (Ghazy and Gad, cessing unit and was used in the experiment without any prior
2014). treatment.
Numerous researches have tested the eggshell as a mean of
removal of Cr(VI) (Daraei et al., 2014, 2015), Cr(III) (Chojnacka, 2.3. Adsorbent characterization
2005), Cd(II) and Cu(II) (Zheng et al., 2007), Pb(II) (Liao et al.,
2010) and reactive red dye (Elkady et al., 2011) from different The morphology of eggshell and powdered marble samples was
types of industrial wastewater but it has not been tested on chrome captured by scanning electron microscopy (Jeol 6490LV, Croissy-
tanning wastewater. Some of them have worked on synthetic so- sur-Seine, France). The chemical composition was obtained by X-
lutions with low initial concentrations of pollutants. The powdered ray uorescence (XRF) Microanalyser (Unisantis XMF-104, Ger-
marble was used mainly for removal of Zn(II) ions (Ghazy and Gad, many). The specic surface area was measured by a nitrogen
2008), Al(III) ions (Ghazy and Gad, 2014) and phosphorus (Eljamal adsorption using the BrunauereEmmetteTeller method (Micro-
et al., 2013) from synthetic solutions but never or rarely for chro- meretics/Gemini-2372). The Surface Weighted Mean has been
mium. Concerning the evaluation of the toxicity before and after carried out with a laser granulometry model Mastersizer 2000 Ver.
treatment, very few studies have been published in literature 5.60. The median pore diameter (Area) was measured by poros-
(Yatribi and Nejmeddine, 2000; Charles et al., 2011). Most of them imeter. The pHzpc (pH isoelectric point) of both samples were
have been carried out on solutions containing only one or a few determined by the procedure described by RiveraeUtrilla et al.
pollutants (Charles et al., 2011). (2001).
The present study is aimed to:
2.4. Batch adsorption tests
(i) Evaluate and compare the adsorption capacity of two low
cost carbonaceous adsorbents: eggshell and powdered Batch sorption experiments were carried out by adding a given
marble on chromium removal from highly concentrated mass of adsorbent from 0.2 to 4.5 g for eggshell and from 0.1 to 1 g
chrome tanning wastewater. The effects of adsorbent dose, for powdered marble into series of 100 mL vessels containing 50 mL
contact times, efuent pH and temperature were studied. of chrome tanning wastewater at temperature of 25  C. The desired
Batch kinetics and adsorption isotherms have been also pH of de solution was adjusted by 0.1 M HCl or 0.1 M NaOH. The
analyzed. suspensions were mixed on a shaker agitator at 250 rpm during a
(ii) Assess the toxicity of the raw and both treated efuents using given time and ltered through lter paper (2 mm). Kinetic tests
the standardized lettuce Lactuca sativa seeds bioassay. were carried out in order to determine the equilibrium time for
each adsorbate. For this purpose, 20 g and 12 g of eggshell and
powdered marble, respectively, were separately added to 50 mL of
2. Materials and methods chrome tanning wastewater. With an initial Cr(III) concentration
equal to 3.21 g L
1 at pH 3.81.
2.1. Efuent sample The Cr(III) ions uptake was determined by measuring the Cr
concentration in the solution before and after treatment, by atomic
Wastewater samples used in this work were obtained from a adsorption spectrophotometer (UNICAM iCE 3000 SERIES). The
chromium tanning tank in a small semi-traditional tannery in chromium calibration curve was prepared using standard solutions
Marrakech city, having a capacity of treatment of about 500 skin/ from Prolabo (France).
day. Generally the main inorganic contaminant of chrome tanning The quantity of chromium adsorbed at equilibrium (mg g
1) was
wastewater is chromium with a concentration range of 0.5e5 g L
1 calculated by the following expression:
(Sahu et al., 2009). Table 1 resumes the characteristics of the raw
wastewater tested. C0
Cf
qe V (1)
m
2.2. Preparation of the adsorbents
Where m is the mass of adsorbent (g), V is the volume of the so-
The eggshell used in this study was coming from local cafeterias lution (L), C0 is the initial concentration of metal (mg L
1) and Cf is
 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595
the equilibrium metal concentration (mg L
1).
For the calculation of chromium adsorption percentage R (%),
the following expression was used:
C0
Cf
R%  100
C0
All experiments were conducted in triplicate. The mean values
and standard deviation of each experiment were used to calculate
the sorption isotherm model parameters and sorption metal af-
nity. Microsoft Ofce Excel was used for data analysis.
2.5. Effect of solution temperature
The effect of temperature (25e55  C) on the adsorption of
chromium was evaluated. These curves were developed for an
initial concentration of chromium 3.21 g L
1 at a constant pH value
of 3.81, with an adsorbent concentration of 12 g L
1and 20 g L
1 for
eggshell and powdered marble respectively, for a contact time of
24 h at 250 rpm.
The thermodynamic parameters of the sorption process Gibbs
energy, DG (Kj mol
1), standard entropy change, DS (J mol
1 K
1)
and standard enthalpy change, DH (Kj mol
1) were determined
using the Van't Hoff equation:
DG
RTlnKd
 
DH DS
lnKd

RT R Fig. 1 exhibits the SEM images of the eggshell (a) and powdered
Where Kd is the thermodynamic distribution coefcient, R is the
universal gas constant, 8.314 (J mol
1 K
1), and T is the absolute
temperature (K).
2.6. Ecotoxicity
In order to study the ecotoxicity of chrome tanning wastewater
before and after adsorption, a bioassay tests using lettuce seeds
were used. Mineral water was used for control. 3 ml of studied
samples were added to glass vessels containing adsorbent paper at
the bottom where twelve seeds were placed. Then vessels were
covered with perforated aluminum foil, stored in plastic bags and
placed in a dark drawer at room temperature. Five days later, the
number of germinated seeds was counted and the shoot and root
lengths were measured.
These assays follow the methodology proposed by Sobrero and
Ronco (2004).
Lc
Ls
RT%  100
Lc
Where LC is the seed length for the control solution and LS is the
seed length for the tested sample.
 
RTi
RTF
TRemoval %  100
RTi
Where RTi and RTf are the relative ecotoxicity of initial and nal
solution sample.
3. Results and discussion
3.1. Characteristics of eggshell and powdered marble
3.1.1. XRF analysis of eggshell and powdered marble
The XRF analysis showed high levels of Ca (96.11%, 92.1%) and
591
Mg (1.11%, 1.61%) in eggshell and powdered marble respectively,
with small amounts of several other elements. Calcium is mainly
presented in the form of calcium carbonate, which is the mean
component of the two biomaterials. The two materials have a
similar composition despite their very different origins.
(2)
3.1.2. BET surface area, granulometry and porosity analysis
The results of the BET method showed that the average specic
surface area of the eggshell and the powdered marble are
0.38 m2 g
1 and 3.32 m2 g
1 respectively. It can be concluded from
these values that the powdered marble is a materiel with 10 fold
larger surface area comparatively to eggshell. The median pore
diameter of eggshell and powdered marble is 144.5 nm and
162.2 nm respectively. This range between 0.1 mm and 2.5 mm in-
dicates that both materials are mesoporous adsorbents (Ledru,
2009) and that they seem to have larger pore diameters than
conventional adsorbents (Lorenc-Grabowska and Gryglewicz,
2007). In addition the average particle size is 158.64 mm for
eggshell and 6.61 mm for powdered marble.
3.1.3. pHPZC analysis
The pHZPC of eggshell and powdered marble are found around
10.9 and 11 respectively. The values are approximately equal and
are both superior to 7 indicating that the powdered marble and
(3) eggshell surfaces are initially positively charged under the used
experimental conditions.
3.1.4. SEM analysis
marble (b); the morphological aspects of the two biomaterials
showed the presence of particles agglomerates with irregular
shape. In addition, powdered marble particles present clearly
higher surface and certainly higher porosity than eggshell particles
in accordance with the results obtained with porosity analysis.
3.2. Effect of adsorbent dose
The effect of eggshell and powdered marble dose, ranging from
4 to 50 g L
1 and from 1 to 20 g L
1 respectively was examined for a
contact time of 24 h (Fig. 2). The chromium removal increases as the
amount of the adsorbent increases and reaches a maximum value
(ca. 100%) at 20 g L
1 and at 12 g L
1 for eggshell and powdered
marble respectively. The adsorbents dose strongly affects chro-
mium removal efciency. The results could be attributed to the
increase of the adsorbent surface areas, augmenting the number of

rez Marn et al., 2009). However any
available adsorption sites (Pe
further increase in adsorbent concentration greater than the
maximum values obtained does not have signicantly improved
(5) the percentage of metal removal because the equilibrium between
chromium ions and the solid phase was reached. The difference
between the equilibrium doses obtained for the two adsorbents can
be explained by the difference of their surface areas.
Therefore, the obtained results may suggest that the number of
activate sites are more concentrated onto the surface of powdered
(6)
marble than onto the surface of the eggshell, requiring larger
dosing.
3.3. Effect of contact time
The change of chromium capacity adsorption onto eggshell and
powdered marble versus time is presented in Fig. 3. The adsorption
capacity and the time required to reach the equilibrium are in-
dicators of the absorbate transfer kinetics from the liquid phase to
the adsorbent surface. The adsorption equilibrium of 99% of chro-
mium was obtained within 30 min for powdered marble and
592 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595
Fig. 1. SEM images of eggshell (a) and powdered marble (b) at 100 mm.
Fig. 2. Evolution of the Cr removed by (a) eggshell and (b) powdered marble versus
adsorbent dose; (C0 3.21 g L
1; pH 3.81).
Fig. 3. Effect of contact time on the adsorption of Cr (III) ions by eggshell (20 g L
1) and powdered marble (12 g L
1) adsorbents; (C0 3.21 g L
1 and pH 3.81).
840 min for eggshell. Adsorption rate of chromium on powdered
marble (262 mg g
1) was found to be highly faster than that for
eggshell (159 mg g
1).
During the rst stage, the adsorption rate increases more rapidly
in the case of powdered marble due to the availability of a higher
number of active sites at this adsorbent surface than for eggshell.
The reaction becomes lower when the remaining active sites are
less available and the equilibrium phase is reached (Pe
rez Marn
et al., 2009).
3.4. Effect of pH
The pH of the solution have an important role in sorption pro-
cess since it is responsible for protonation of metal binding sites,
calcium carbonate solubility and metal speciation in the solution
(Chojnacka, 2005). In these experiences, the initial concentration of
Cr(III) (3.21 g L
1), the amount of eggshell and powdered marble
(20 g L
1 and 12 g L
1 respectively) and contact time (24 h) were
kept constant. Fig. 4 represents the sorption capacity of Cr(III) on
eggshell and powdered marble versus pH. The removal efciency of
chromium ions increased when the pH was increased but, the
eggshell sorbent present a relatively slight sorption increase which
is probably indicative of their poor pore rate and accessibility in
comparison to powdered marble absorbent.
At lower pH (2 and 3), the low chromium removal may be
attributed to: (i) the elevated concentration of protons that will
compete with chromium cations on the surface sorbent active sites
and hence reduce their adsorption; (ii) the dissolution of CaCO3, the
principal constituent of the two adsorbents which lowers the
adsorption. At higher pH (4 and 5), the important removal of
chromium in the range can be attributed to: (i) the competitive
effect (H vs. Cr3) which becomes weaker, increasing the
adsorption of Cr(III) (Chojnacka, 2005); (ii) the adsorption of hy-
drolysis products and precipitation of the metal as colloidal insol-
uble hydroxides, Cr(OH)3. Similar results were also reported for
Cu(II) adsorption onto eggshell (Rais et al., 2012) and for Al(III)
adsorption onto powdered marble (Ghazy and Gad, 2014).
On the other hand, despite that calcite is the main principal
component of both sorbents, there is a difference between their
Cr(III) sorption capacities versus pH. This may be explained by the
fact that eggshells are composed of layers of calcite (CaCO3), con-
taining embedded proteins that make eggshells less prone to
dissolution compared to calcite alone (Solomon, 1999; Ahmed et al.,
2005).
 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595 593

pseudo-rst-order model. The pseudo-second-order rate is given

by equation (8) as follow (Ho and McKay, 1999):

t 1 t
(8)
qt K2 q2e qe

Where K2 is the rate constant of the pseudo-second-order equation

Fig. 4. Evolution of the adsorption capacity of Cr (III) on eggshell (20 g L
1) and
powdered marble (12 g L
1) versus pH; (C0 3.21 g L
1).
3.5. Thermodynamics
The values obtained for thermodynamic parameters are shown
in Table 2. The negative value of DG indicates that the adsorption
of Cr(III) on the eggshell and powdered marble is feasible and
spontaneous. In addition, the absolute DG values increased with
increasing temperature, from 298 to 328 K. Similar results were
also reported for the adsorption of Cr (III) by natural diatomite
(Gur et al., 2008). The positive value of DH shows that the nature
of adsorption is endothermic. According to Sepehr et al. (2014), the
values of enthalpy changes (102e121 Kj mol
1) suggested that the
adsorption of Cr(III) onto powdered marble and eggshell may be
dominated by chemical adsorption. The positive value of DS re-
veals the increased randomness at the solidesolution interface
during the xation of the Cr(III) ion on the active sites of the studied
adsorbents. Similar results were also observed by Torab-Mostaedi
et al. (2013), studying the adsorption of cadmium and nickel on
grapefruit peel.
3.6. Adsorption kinetics models
In order to investigate the kinetics models of Cr(III) ions
adsorption onto eggshell and powdered marble, the linear pseudo-
rst order and pseudo-second order kinetics models were tested to
t the experimental data.
The pseudo rst-order model can be expressed as equation (7):
(g mg
1 min
1).
Figs. S1 and S2 (in supplementary materials) represent the
comparison between experimental data and calculated one with
the pseudo rst order model and the second order model for
eggshell and powdered marble respectively. The corresponding
parameters are summarized in Table 3.
For eggshell, the Fig. S1 (a) and (b) represents the kinetics of
Cr(III) ion adsorption with a linear relation between log(qeeqt)
versus time and t/qt versus time respectively. The trend obtained
with the pseudo rst-order model is strongly different from the
experimental curve (Fig. S1 in supplementary materials). Moreover,
a large difference of equilibrium adsorption capacity (qe) between
the experimental and calculation was observed, indicating a poor
pseudo-rst-order t to the experimental data. Fig. S1b shows a
better correlation between experimental and simulated data and
suggest that the pseudo-second order model describe accurately Cr
(III) adsorption on eggshell.
As shown in Fig. S2 (a) and (b), the behavior of the pseudo-
second-order adsorption model on powdered marble seems
similar to the experimental data comparatively to that of the
pseudo rst (Fig. S2 as supplementary materials). Also in this case
the value of coefcient of determination R2 is relatively high
(>0.958), and the adsorption capacities calculated by the model are
close to those determined by experiments. Moreover, the values of
R2 for the pseudo-rst-order are not satisfactory (>0.784). There-
fore, it has been concluded that the pseudo-second-order adsorp-
tion model is more suitable to describe the adsorption kinetics of
chromium onto powdered marble.
It seems that the pseudo-second-order model describes better
adsorption kinetic for the two adsorbents. This suggests that the
sorption of Cr(III) onto eggshell and powdered marble most likely
to be controlled by chemisorption process (Elkady et al., 2011).
The comparison of rate constant K2 of the powdered marble and
eggshell is presented in Table 4. The difference between them may
probably be explained by more available surfaces in the powdered
marble than in eggshell leading to a faster Cr(III) rate adsorption.
3.7. Adsorption isotherms

k1 t
logqe
qt logqe
(7) The Langmuir isotherm model assumes a monolayer adsorption
2:303 with uniform distribution of adsorption heat and afnities over the
Where qe (mg g
1) is the amount of chromium adsorbed per homogeneous surfaces, i.e. The surface consists of identical sites,
unit mass of the adsorbent at equilibrium, qt (mg g
1) is the amount equally available for adsorption and with equal energies of
of a chromium absorbed per unit mass of the adsorbent at current adsorption. The linearized Langmuir equation is given by equation
time t (min), and k1 (min
1) is the equilibrium rate constant of (9):

Table 2
Thermodynamic parameters for Cr(III) adsorption using eggshell and powdered marble (C0 3.21 g L
1 and pH 3.81).

Adsorbent T (K) DG (Kj mol
1) SD DH (Kj mol
1) SD DS (j mol
1 K
1) SD

Eggshell 298
5.66 0.44 121.35 2.90 423.1 3.23

308
7.34 0.18
318
12.66 0.57
328
18.28 0.55
Powdered marble 298
6.99 0.27 102.83 3.11 368.23 4.21
308
10.25 0.59
318
14.99 0.94
328
17.66 1.17
594 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595

Table 3
Kinetic parameters for adsorption of Cr (III) ions on eggshell and powdered marble waste (C0 3.21 g L
1; pH 3.81).

Adsorbent Pseudo rst order Pseudo second order

qexp (mg g
1) SD qe (mg g
1) SD K1 (min
1) R21 qe (mg g
1) SD K2 (g mg
1 min
1) R22

3
3
Eggshell 159.31 2.87 81.47 1.17 2.3$10 0.935 200.12 1.63 0.041$10 0.998
Powdered marble 262.17 1.75 1695.5 2.93 235.3$10
3 0.784 50.24 2.47 1.142$10
3 0.958

Table 4
Isotherm parameters for adsorption of Cr (III) ions onto eggshell and powdered marble (C0 3.21 g L
1 and pH 3.81).

Adsorbent Langmuir Freundlich

1
1
qm (mg g ) SD b (L mg ) R21 Kf (mg g
1) n R22

Eggshell 200.25 3.63 0.083 0.995 3.45 2.57 0.722

Powdered marble 434.82 2.51 0.020 0.999 5.86 2.99 0.945

3.8. Ecotoxicity test

Ce 1 Ce
(9)
qe bqm qm In order to study the toxicity of chrome tanning wastewater

1 before and after each treatment, bioassay tests using lettuce seeds
Where qe (mg g ) is the amount of chromium adsorbed at were investigated.
equilibrium; Ce (g L
1) is equilibrium concentration of chromium in The results of percent removal toxicity of lettuce (based on the
solution; b is the Langmuir constant related to the energy of shoot growth) versus the efuent concentration are displayed in
adsorption (L g
1); qm (mg g
1) is the maximum chromium Fig. 5. According to these results, the adsorption of chromium after
adsorption capacity. treatment using eggshell and powdered marble has reduced the
Data were also analyzed with the Freundlich isotherm, which ecotoxicity observed for raw tanning efuent by about 25 and 40%
can be given in its logarithmic form as following: respectively. The low reduction of the toxicity even after high
chromium elimination (at 99%) suggests that the toxicity of the
1 tanning wastewater is due not only to chromium. Bohorquez-
lnqe lnkf lnCe (10)
n Echeverry and Campos-Pinilla (2007) reported that high concen-
trations of organic matter in an efuent could also explain its
Where kf is a Freundlich constant that shows adsorption capacity of
toxicity, as well as other concentrated components such as salts
adsorbent, n is a constant which shows greatness of relationship
(Yatribi and Nejmeddine, 2000; Komilis and Tziouvaras, 2009).
between adsorbate and adsorbent.
Consequently the efciency of the treatment must integrate the
In Freundlich adsorption isotherms, the model assumes a het-
elimination of all these components and not only the chromium
erogeneous surface with a no uniform distribution of heat of
adsorption.
adsorption over the surface (Foo and Hameed, 2010). The slope
ranges between 0 and 1 is a measure of adsorption intensity or
surface heterogeneity, becoming more heterogeneous as its value 4. Conclusion
gets closer to zero.
In this work, equilibrium data was applied onto Langmuir and The present study shows that the two carbonaceous materials
Freundlich isotherm models and the corresponding parameters are tested (eggshell and powdered marble) are very efcient adsorbent
collected in Table 4 as calculated from Figs. S3 and S4 (in supple- for chromium removal from tanning efuent. Maximum chromium
mentary materials). In the case of eggshell, these values clearly removal were found to be at pH 5 and adsorbent dose 12 g L
1 of
suggest that Langmuir isotherm shows a good correlation with the powdered marble and 20 g L
1 of eggshell, for initial concentration
experimental results. It is assumed that once the chromium ion of chromium up to 3.21 g L
1. The maximum sorption capacities
occupies a site, no further sorption can take place at that site.
Moreover, the value of constant b for the eggshell also shows great
afnity of the binding sites and chemical interaction between the
adsorbent and adsorbate. For powdered marble, after the applica-
tion of the Langmuir model to the adsorption results, the values of
the coefcients of determination strongly support that the chro-
mium adsorption data closely follow the Langmuir model. It was
found that the plots exhibit deviation from linearity, and the cor-
relation coefcients indicate that the data are not well correlated to
Freundlich isotherm compared to Langmuir one.
Comparing maximum sorption capacity of powdered marble
with that obtained for eggshell, it can be concluded that powdered
marble has high adsorption capacity and can be considered as a
promising material for use as adsorbent of chromium from the
chrome tanning wastewater. The higher Cr adsorption capacity of
powdered marble may be attributed to the higher surface area
(3.3 m2 g
1) for powdered marble compared to that of the eggshell Fig. 5. Evolution of removal toxicity of the tanning wastewater before and after
(0.38 m2 g
1). treatment versus percent concentration of the used efuent.
 S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595
and the adsorption kinetic rate noticed for powdered marble are
higher than those of eggshell. The equilibrium adsorption of
chromium by the two studied adsorbents was best represented by
the Langmuir isotherm and the pseudo-second-order kinetic model
indicating the dynamical behavior of the adsorption of chromium
onto the two adsorbents studied. The powdered marble was a more
effective adsorbent compared to eggshell due to its better specic
area and porosity. In addition the use of the seed toxicity test
conrmed the best effectiveness of the powdered marble, for
reducing a part of high tanning efuent toxicity.
Acknowledgments
The authors would like to thank Kevin Mozet Technician in the
University of Lorraine, for the physical characteristic measure-
ments. This work has been done in the frame of the project of the
Pole of Competence on Water and Environment supported by
French-Morocco cooperation (Project MESRSFC/SCAC (Recherche)
2012) (2012-2014).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2015.11.012.
References
Ahmed, M.H., Rodriguez-Navarro, A.B., Vidal, M.L., Gautron, J., Garca-Ruiz, J.M.,
Nys, Y., 2005. Changes in eggshell mechanical properties, crystallographic
texture and in matrix proteins induced by moult in hens. Br. Poult. Sci. 46,
268e279.
Albadarin, A.B., Mangwandi, C., Al-Muhtaseb, A.H., Walker, G.M., Allen, S.J.,
Ahmad, M.N.M., 2012. Kinetic and thermodynamics of chromium ions
adsorption onto low-cost dolomite adsorbent. Chem. Eng. J. 179, 193e202.
Bohorquez-Echeverry, P., Campos-Pinilla, C., 2007. Assessmentof Lactuca sativa and
Selenastrum capricornutum like indicators of water toxicity. Univ. Sci. 12,
83e98.
Charles, J., Sancey, B., Morin-Crini, N., Badot, P.M., Degiorgi, F., Truno, G., Crini, G.,
2011. Evaluation of the phytotoxicity of polycontaminated industrial efuents
using the lettuce plant (Lactuca sativa) as a bioindicator. Ecotoxicol. Environ. Saf.
74, 2057e2064.
Chojnacka, K., 2005. Biosorption of Cr(III) ions by eggshells. J. Hazard. Mater B121,
167e173.
Daraei, H., Mittal, A., Mittal, J., Kamali, H., 2014. Optimization of Cr(VI) removal on
biosorbent eggshell membrane: experimental and theoretical approaches.
Desalin. Water Treat. 52, 1307e1315.
Daraei, H., Mittal, A., Nooriseprhr, M., Mittal, J., 2015. Separation of chromium from
water samples using eggshell powder as low- cost sorbent: kinetic and ther-
modynamic studies. Desalin. Water Treat. 53, 214e220.
Eljamal, O., Okawauhi, J., Hiramasu, K., Harada, M., 2013. Phosphorus sorption from
aqueous solution using naural materials. Environ. Earth Sci. 68, 859e863.
Elkady, M.F., Ibrahim, A.M., Abd El-Latif, M.M., 2011. Assessment of the adsorption
kinetics, equilibrium and thermodynamic for the potential removal of reactive
red dye using eggshell biocomposite beads. Desalination 278, 412e423.
El-Sherif, I.Y., Tolani, S., Ofosu, K., Mohamed, O.A., Wanekaya, A.K., 2013. Polymeric
nanobers for the removal of Cr(III) from tannery waste water. J. Environ.
Manag. 129, 410e413.
Fabbricino, M., Naviglio, B., Tortora, G., d'Antonio, L., 2013. An environmental
friendly cycle for Cr(III) removal and recovery from tannery wastewater. J.En-
viron. Manag. 117, 1e6.
Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm
systems: a reiew. Chem. Eng. J. 156, 2e10.
Fu, F., Wang, Q., 2011. Removal of heavy metal ions from wastewaters: a review.
J. Environ. Manag. 92, 407e418.
Ghazy, S.E., Gad, A.H.M., 2008. Separation of Zn(II) by sorption powdered marble
wastes. Indian J. Chem. Technol. 15, 433e442.
Ghazy, S.E., Gad, A.H.M., 2014. Lead separation by sorption onto powdered marble
waste. Arab. J. Chem. 7, 277e286.
Golder, A.K., Samanta, A.N., Ray, S., 2007. Removal of trivalent chromium by elec-
trocoagulation. Sep. Purif. Technol. 53, 33e41.
595
Gr, M., Venedik, D., Murathan, A., 2008. Removal of trivalent chromium from
water using low-cost natural diatomite.J. Hazard. Mater 160, 318e323.
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption processes. Pro-
cess Biochem. 34, 451e465.
Komilis, D.P., Tziouvaras, I.S., 2009. A statistical analysis to assess the maturity and
stability of six composts. Waste Manag. 29, 1504e1513.
Ledru, Y., 2009. Voids in Aeronautical Composite Laminates. Ph.D. thesis. Universite

de Toulouse, France. http://oatao.univ-toulouse.fr/7214/1/Ledru.pdf (accessed
10.01.15.).
Liao, D., Zheng, W., Li, X., Yang, Q., Yue, X., Guo, L., Zeng, G., 2010. Removal of lead(II)
from aqueous solutions using carbonate hydroxyapatite extracted from eggshell
waste. J. Hazard. Mater 177, 126e130.
Lorenc-Grabowska, E., Gryglewicz, G., 2007. Adsorption characteristics of Congo Red
on coal-based mesoporous activated carbon. Dyes Pigments 74, 34e40.
Lugo-Lugo, V., Barrera-Daz, C., Uren ~ a-Nn ~ ez, F., Bilyeu, B., Linares-Hern
andez, I.,
2012. Biosorption of Cr(III) and Fe(III) in single and binary systems onto pre-
treated orange peel. J. Environ. Manag. 112, 120e127.
Mandi, L., Tiglyene, S., Jaouad, A., 2009. Depuration of tannery efuent by phytor-
emediation and inltration percolation under arid climate. In: El Moujabber, M.,
Mandi, L., Trisorio-Liuzzi, G., Martn, I., Rabi, A., Rodrguez, R. (Eds.), Techno-
logical Perspectives for Rational Use of Water Resources in the Mediterranean
Region. Publisher: Bari: CIHEAM, pp. 199e205.
Meunier, N., Drogui, P., Montane
, C., Hausler, R., Mercier, G., Blais, J.F., 2006. Com-
parison between electrocoagulation and chemical precipitation for metals
removal from acidic soil leachate. J. Hazard. Mater 137, 581e590.

rez Marn, A.B., Aguilar, M.I., Meseguer, V.F., Ortun
Pe ~ o, J.F., Sa

ez, J., Llore

ns, M., 2009.
Biosorption of chromium (III) by orange (Citrus cinensis) waste: Batch and
continuous studies. Chem. Eng. J. 155, 199e206.
Pillai, S.S., Mullassery, M.D., Fernandez, N.B., Girija, N., Geetha, P., Koshy, M., 2013.
Biosorption of Cr(VI) from aqueous solution by chemically modied potato
starch: equilibrium and kinetic studies. Ecotoxicol. Environ. Saf. 92, 199e205.
Rais, A., Rajeev, K., Shaziya, H., 2012. Adsorption of Cu2 from aqueous solution onto
iron Oxide coated eggshell powder: evaluation of equilibrium, isotherms, ki-
netics and regeneration capacity. Arabian J. Chem. 5, 353e359.
Rajendran, A., Mansiya, C., 2011. Extraction of chromium from tannery efuents
using waste egg shell material as an adsorbent. Br. J. Environ. Clim. Chang. 1,
44e52.
Religa, P., Kowalik, A., Gierycz, P., 2011. A new approach to chromium concentration
from salt mixture solution using nanoltration. Sep. Purif. Technol 82, 114e120.
Rivera-Utrilla, J., Bautista-Toledo, I., Ferro-Garca, M.A., Moreno-Castilla, C., 2001.
Activated carbon surface modications by adsorption of bacteria and their ef-
fect on aqueous lead adsorption. J. Chem. Technol. Biot 76, 1209e1215.
Sahu, S.K., Meshram, P., Pandey, B.D., Kumara, V., Mankhand, T.R., 2009. Removal of
chromium(III) by cation exchange resin, Indion 790 for tannery waste treat-
ment. Hydrometallurgy 99, 170e174.
Santana cadaval Jr., T.R., Camara, A.S., Dotto, G.L., Pinto, L.A.A., 2013. Adsorption of Cr
(VI) by chitosan with different deacetylation degrees ind water treatment.
Desalin. Water Treat. 51, 7690e7699.
Sepehr, M.N., Amrane, A., Karimaian, K.A., Zarrabi, M., Ghaffari, H.R., 2014. Potential
of waste pumice and surface modied pumice for hexavalent chromium
removal: characterization, equilibrium, thermodynamic and kinetic study.
J. Taiwan Inst. Chem. E 45, 635e647.
Sobrero, M.C., Ronco, A., 2004. Ensayo de toxicidad aguda con semillas de lechuga
Lactuca sativa L. In: Castillo, G. (Ed.), Ensayos toxicolo
gicos y me
todos de
evaluacio
n de calidad de aguas. IDRC/IMTA. Canad
a, Captulo, vol. 4, pp. 71e79.
Solomon, S.E., 1999. An Egg Ist Ein Ei, Es Un Huevo, Est Un Oeuf. Br. Poult. Sci. 40,
5e11.
Sumathi, K.M.S., Mahimairaja, S., Naidu, R., 2005. Use of low-cost biological wastes
and vermiculite for removal of chromium from tannery efuent. Biores Technol.
96, 309e316.
Suwalsky, M., Castro, R., Villena, F., Sotomayor, C.P., 2008. Cr(III) exerts stronger
structural effects than Cr(VI) on the human erythrocyte membrane and mo-
lecular models. Inorg. Chem. 102, 842e849.
Tang, W.Q., Zeng, R.Y., Feng, Y.L., Li, X.M., Zhen, W., 2013. Removal of Cr(VI) from
aqueous solution by nano-carbonate hydroxylapatite of different Ca/P molar
ratios. Chem. Eng. J. 223, 340e346.
Torab-Mostaedi, M., Asadollahzadeh, M., Hemmati, A., Khosravi, A., 2013. Equilib-
rium, kinetic, and thermodynamic studies for biosorption of cadmiumand
nickel on grapefruit peel. J. Taiwan Inst. Chem. E 44, 295e302.
Tiglyene, S., Jaouad, A., Mandi, L., 2008. Treatment of tannery wastewater by inl-
tration percolation: chromium removal and speciation in soil. Environ. Technol.
29, 613e624.
Yatribi, A., Nejmeddine, A., 2000. Impact e
cotoxicologique du traitement chimique
des eaux use
es de tanneries: analyse technico-e
conomique. J. Water Sci. 13,
107e118.
Zheng, W., Li, X.M., Yang, Q., Zeng, G.M., Shen, X.X., Zhang, Y., Liu, J.J., 2007.
Adsorption of Cd(II) and Cu(II) from aqueous solution by carbonate hydroxyl-
apatite derived from eggshell waste. J. Hazard. Mater 147, 534e539.