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Journal of Environmental Management 166 (2016) 589e595

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Journal of Environmental Management


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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 Reactions 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 L1 and 12 g L1 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 L1. 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$103 (g mg1 min1) and 0.041$103 (g mg1 min1)
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 mg1) and 0.083 (L mg1)
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.,


2005). The differences in the oxidation state of chromium inu-
The large release of heavy metals into the environment caused ence its toxicity and its chemical properties in water. Hence,
by industrial wastewater discharge presents a serious danger for trivalent chromium is approximately 300 times less toxic than the
aquatic ecosystems. Chromium is one of most toxic metals from the hexavalent chromium form, but it can cause more structural dis-
hazardous heavy metals list. It can exist in a different oxidation turbances in erythrocyte membranes (Suwalsky et al., 2008). The
states, with the trivalent (Cr(III)) and hexavalent (Cr(VI)) states major source of a chromium released into the environment are
industries of metallurgical, electroplating, battery manufacturing,
agrochemicals, basic steel, paper and pulp, petrochemicals, fertil-
* Corresponding author. Laboratoire d'Hydrobiologie, Ecotoxicologie et Assai-
izer industries and tanneries (El-Sherif et al., 2013).
nissement (LHEA, URAC 33), Faculte de Sciences Semlalia, BP2390, Universite
 Cadi Several methods are available to remove chromium species
Ayyad, Marrakech, Morocco. from wastewater (Fu and Wang, 2011), such as chemical
E-mail address: ouazzani@uca.ac.ma (N. Ouazzani).

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 cm1) (at 25  C) 60.0 3.0
relative simplicity and low cost. Many studies have been carried out Cl (g L1) 11.6 0.5
using different natural materials for chromium removal including COD (g L1) 3.75 0.10
SO4 2 (g L1) 1.6 0.2
orange peel (Lugo-Lugo et al., 2012), modied potato starch (Pillai
NH4 (mg L1) 33.2 0.4
et al., 2013), chitosan (Santana cadaval Jr et al., 2013), waste con- Total P (mg L1) 7.0 0.2
taining chitin (Fabbricino et al., 2013) and polymeric nanobers (El- PO4 3 (mg L1) 2.1 0.1
Sherif et al., 2013). Several other researchers have tested materials HCO3  (g CaCO3 L1) 0.41 0.01
Cr(III) (g L1) 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 g1 at waste. The collected eggshells were just washed with distilled
C0 50 mg L1 of Cr(VI) for dolomite, 9 mg g1 from a solution of water to remove the adhering membranes then they were dried at
2910.1 mg L1 of Cr(III) using eggshell and 37 mg g1 from a so- the ambient atmosphere for several days. The dried eggshells were
lution of 75 mg L1 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 L1 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 g1) was
wastewater is chromium with a concentration range of 0.5e5 g L1 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 L1) and Cf is
S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595 591

the equilibrium metal concentration (mg L1). Mg (1.11%, 1.61%) in eggshell and powdered marble respectively,
For the calculation of chromium adsorption percentage R (%), with small amounts of several other elements. Calcium is mainly
the following expression was used: presented in the form of calcium carbonate, which is the mean
component of the two biomaterials. The two materials have a
C0  Cf similar composition despite their very different origins.
R%  100 (2)
C0
3.1.2. BET surface area, granulometry and porosity analysis
All experiments were conducted in triplicate. The mean values
The results of the BET method showed that the average specic
and standard deviation of each experiment were used to calculate
surface area of the eggshell and the powdered marble are
the sorption isotherm model parameters and sorption metal af-
0.38 m2 g1 and 3.32 m2 g1 respectively. It can be concluded from
nity. Microsoft Ofce Excel was used for data analysis.
these values that the powdered marble is a materiel with 10 fold
larger surface area comparatively to eggshell. The median pore
2.5. Effect of solution temperature
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-
The effect of temperature (25e55  C) on the adsorption of
dicates that both materials are mesoporous adsorbents (Ledru,
chromium was evaluated. These curves were developed for an
2009) and that they seem to have larger pore diameters than
initial concentration of chromium 3.21 g L1 at a constant pH value
conventional adsorbents (Lorenc-Grabowska and Gryglewicz,
of 3.81, with an adsorbent concentration of 12 g L1and 20 g L1 for
2007). In addition the average particle size is 158.64 mm for
eggshell and powdered marble respectively, for a contact time of
eggshell and 6.61 mm for powdered marble.
24 h at 250 rpm.
The thermodynamic parameters of the sorption process Gibbs
3.1.3. pHPZC analysis
energy, DG (Kj mol1), standard entropy change, DS (J mol1 K1)
The pHZPC of eggshell and powdered marble are found around
and standard enthalpy change, DH (Kj mol1) were determined
10.9 and 11 respectively. The values are approximately equal and
using the Van't Hoff equation:
are both superior to 7 indicating that the powdered marble and
DG RTlnKd (3) eggshell surfaces are initially positively charged under the used
experimental conditions.
 
DH DS 3.1.4. SEM analysis
lnKd 
RT R Fig. 1 exhibits the SEM images of the eggshell (a) and powdered
marble (b); the morphological aspects of the two biomaterials
Where Kd is the thermodynamic distribution coefcient, R is the
showed the presence of particles agglomerates with irregular
universal gas constant, 8.314 (J mol1 K1), and T is the absolute
shape. In addition, powdered marble particles present clearly
temperature (K).
higher surface and certainly higher porosity than eggshell particles
in accordance with the results obtained with porosity analysis.
2.6. Ecotoxicity
3.2. Effect of adsorbent dose
In order to study the ecotoxicity of chrome tanning wastewater
before and after adsorption, a bioassay tests using lettuce seeds
The effect of eggshell and powdered marble dose, ranging from
were used. Mineral water was used for control. 3 ml of studied
4 to 50 g L1 and from 1 to 20 g L1 respectively was examined for a
samples were added to glass vessels containing adsorbent paper at
contact time of 24 h (Fig. 2). The chromium removal increases as the
the bottom where twelve seeds were placed. Then vessels were
amount of the adsorbent increases and reaches a maximum value
covered with perforated aluminum foil, stored in plastic bags and
(ca. 100%) at 20 g L1 and at 12 g L1 for eggshell and powdered
placed in a dark drawer at room temperature. Five days later, the
marble respectively. The adsorbents dose strongly affects chro-
number of germinated seeds was counted and the shoot and root
mium removal efciency. The results could be attributed to the
lengths were measured.
increase of the adsorbent surface areas, augmenting the number of
These assays follow the methodology proposed by Sobrero and rez Marn et al., 2009). However any
available adsorption sites (Pe
Ronco (2004).
further increase in adsorbent concentration greater than the
Lc  Ls maximum values obtained does not have signicantly improved
RT%  100 (5) the percentage of metal removal because the equilibrium between
Lc
chromium ions and the solid phase was reached. The difference
Where LC is the seed length for the control solution and LS is the between the equilibrium doses obtained for the two adsorbents can
seed length for the tested sample. be explained by the difference of their surface areas.
  Therefore, the obtained results may suggest that the number of
RTi  RTF activate sites are more concentrated onto the surface of powdered
TRemoval %  100 (6)
RTi marble than onto the surface of the eggshell, requiring larger
dosing.
Where RTi and RTf are the relative ecotoxicity of initial and nal
solution sample. 3.3. Effect of contact time

3. Results and discussion The change of chromium capacity adsorption onto eggshell and
powdered marble versus time is presented in Fig. 3. The adsorption
3.1. Characteristics of eggshell and powdered marble capacity and the time required to reach the equilibrium are in-
dicators of the absorbate transfer kinetics from the liquid phase to
3.1.1. XRF analysis of eggshell and powdered marble the adsorbent surface. The adsorption equilibrium of 99% of chro-
The XRF analysis showed high levels of Ca (96.11%, 92.1%) and 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.

calcium carbonate solubility and metal speciation in the solution


(Chojnacka, 2005). In these experiences, the initial concentration of
Cr(III) (3.21 g L1), the amount of eggshell and powdered marble
(20 g L1 and 12 g L1 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
Fig. 2. Evolution of the Cr removed by (a) eggshell and (b) powdered marble versus
adsorption. At higher pH (4 and 5), the important removal of
adsorbent dose; (C0 3.21 g L1; pH 3.81).

Fig. 3. Effect of contact time on the adsorption of Cr (III) ions by eggshell (20 g L1) and powdered marble (12 g L1) adsorbents; (C0 3.21 g L1 and pH 3.81).

840 min for eggshell. Adsorption rate of chromium on powdered chromium in the range can be attributed to: (i) the competitive
marble (262 mg g1) was found to be highly faster than that for effect (H vs. Cr3) which becomes weaker, increasing the
eggshell (159 mg g1). adsorption of Cr(III) (Chojnacka, 2005); (ii) the adsorption of hy-
During the rst stage, the adsorption rate increases more rapidly drolysis products and precipitation of the metal as colloidal insol-
in the case of powdered marble due to the availability of a higher uble hydroxides, Cr(OH)3. Similar results were also reported for
number of active sites at this adsorbent surface than for eggshell. Cu(II) adsorption onto eggshell (Rais et al., 2012) and for Al(III)
The reaction becomes lower when the remaining active sites are adsorption onto powdered marble (Ghazy and Gad, 2014).
less available and the equilibrium phase is reached (Pe rez Marn On the other hand, despite that calcite is the main principal
et al., 2009). component of both sorbents, there is a difference between their
Cr(III) sorption capacities versus pH. This may be explained by the
3.4. Effect of pH fact that eggshells are composed of layers of calcite (CaCO3), con-
taining embedded proteins that make eggshells less prone to
The pH of the solution have an important role in sorption pro- dissolution compared to calcite alone (Solomon, 1999; Ahmed et al.,
cess since it is responsible for protonation of metal binding sites, 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


(g mg1 min1).
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
Fig. 4. Evolution of the adsorption capacity of Cr (III) on eggshell (20 g L1) and with the pseudo rst-order model is strongly different from the
powdered marble (12 g L1) versus pH; (C0 3.21 g L1). 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
3.5. Thermodynamics
pseudo-rst-order t to the experimental data. Fig. S1b shows a
better correlation between experimental and simulated data and
The values obtained for thermodynamic parameters are shown
suggest that the pseudo-second order model describe accurately Cr
in Table 2. The negative value of DG indicates that the adsorption
(III) adsorption on eggshell.
of Cr(III) on the eggshell and powdered marble is feasible and
As shown in Fig. S2 (a) and (b), the behavior of the pseudo-
spontaneous. In addition, the absolute DG values increased with
second-order adsorption model on powdered marble seems
increasing temperature, from 298 to 328 K. Similar results were
similar to the experimental data comparatively to that of the
also reported for the adsorption of Cr (III) by natural diatomite
pseudo rst (Fig. S2 as supplementary materials). Also in this case
(Gur et al., 2008). The positive value of DH shows that the nature
the value of coefcient of determination R2 is relatively high
of adsorption is endothermic. According to Sepehr et al. (2014), the
(>0.958), and the adsorption capacities calculated by the model are
values of enthalpy changes (102e121 Kj mol1) suggested that the
close to those determined by experiments. Moreover, the values of
adsorption of Cr(III) onto powdered marble and eggshell may be
R2 for the pseudo-rst-order are not satisfactory (>0.784). There-
dominated by chemical adsorption. The positive value of DS re-
fore, it has been concluded that the pseudo-second-order adsorp-
veals the increased randomness at the solidesolution interface
tion model is more suitable to describe the adsorption kinetics of
during the xation of the Cr(III) ion on the active sites of the studied
chromium onto powdered marble.
adsorbents. Similar results were also observed by Torab-Mostaedi
It seems that the pseudo-second-order model describes better
et al. (2013), studying the adsorption of cadmium and nickel on
adsorption kinetic for the two adsorbents. This suggests that the
grapefruit peel.
sorption of Cr(III) onto eggshell and powdered marble most likely
to be controlled by chemisorption process (Elkady et al., 2011).
3.6. Adsorption kinetics models The comparison of rate constant K2 of the powdered marble and
eggshell is presented in Table 4. The difference between them may
In order to investigate the kinetics models of Cr(III) ions probably be explained by more available surfaces in the powdered
adsorption onto eggshell and powdered marble, the linear pseudo- marble than in eggshell leading to a faster Cr(III) rate adsorption.
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): 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 g1) 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 g1) 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 (min1) is the equilibrium rate constant of (9):

Table 2
Thermodynamic parameters for Cr(III) adsorption using eggshell and powdered marble (C0 3.21 g L1 and pH 3.81).

Adsorbent T (K) DG (Kj mol1) SD DH (Kj mol1) SD DS (j mol1 K1) 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 L1; pH 3.81).

Adsorbent Pseudo rst order Pseudo second order

qexp (mg g1) SD qe (mg g1) SD K1 (min1) R21 qe (mg g1) SD K2 (g mg1 min1) 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$103 0.784 50.24 2.47 1.142$103 0.958

Table 4
Isotherm parameters for adsorption of Cr (III) ions onto eggshell and powdered marble (C0 3.21 g L1 and pH 3.81).

Adsorbent Langmuir Freundlich


1
1
qm (mg g ) SD b (L mg ) R21 Kf (mg g1) 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 L1) 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 g1); qm (mg g1) 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 L1 of
suggest that Langmuir isotherm shows a good correlation with the powdered marble and 20 g L1 of eggshell, for initial concentration
experimental results. It is assumed that once the chromium ion of chromium up to 3.21 g L1. 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 g1) 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 g1). treatment versus percent concentration of the used efuent.
S. Elabbas et al. / Journal of Environmental Management 166 (2016) 589e595 595

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Supplementary data related to this article can be found at http:// Biosorption of Cr(VI) from aqueous solution by chemically modied potato
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Rais, A., Rajeev, K., Shaziya, H., 2012. Adsorption of Cu2 from aqueous solution onto
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