Competitive Adsorption of Heavy Metals onto Natural and Activated Clay: Equilibrium, Kinetics and Modeling
The aim of this work is to present a low cost adsorbent
for removing toxic heavy metals from aqueous solutions. Therefore,
we are interested to investigate the efficiency of natural clay minerals
collected from south Tunisia and their modified form using sulfuric
acid in the removal of toxic metal ions: Zn(II) and Pb(II) from
synthetic waste water solutions. The obtained results indicate that
metal uptake is pH-dependent and maximum removal was detected to
occur at pH 6. Adsorption equilibrium is very rapid and it was
achieved after 90 min for both metal ions studied. The kinetics results
show that the pseudo-second-order model describes the adsorption
and the intraparticle diffusion models are the limiting step. The
treatment of natural clay with sulfuric acid creates more active sites
and increases the surface area, so it showed an increase of the
adsorbed quantities of lead and zinc in single and binary systems. The
competitive adsorption study showed that the uptake of lead was
inhibited in the presence of 10 mg/L of zinc. An antagonistic binary
adsorption mechanism was observed. These results revealed that clay
is an effective natural material for removing lead and zinc in single
and binary systems from aqueous solution.
[1] N. Unlu, M. Ersoz, Adsorption characteristics of heavy metal ions onto a
low cost biopolymeric sobent from aqueous solutions. J. Hazard. Mater.
B 136, 2006, pp. 272–280
[2] V.C. Srivastava, I.D. Mall, I.M. Misha, Characterisation of mesoporous
rice husk ash (RHA) and adsorption kinetics of metal ions from aqueous
solution onto RHA. J. Hazard. Mater. B 134, 2006, pp. 257–267.
[3] F. Boudrahem, F. Aissani-Benissad, A. Soualah, Adsorption of lead(II)
from aqueous solution by using leaves of date trees as an adsorbent. J.
Chem. Eng. Data 56, 2011, pp. 1804–1812.
[4] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters. A
review. J. Environ. Manage, 92, 2011, pp.407–418.
[5] Y.S. Al-Degs, M.I. El-Barghouthi, A.A. Issa, M.A. Khraisheh, G.M
.Walker, Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents:
Equilibrium and kinetic studies. Water Res. 40, 2006, pp. 2645–2658.
[6] L.Lv, M.P. Hor, F.Sa, X.S.Zhoo, Competitive adsorption of Pb2+, Cu2+
and Cd2+ ions on microporous titanosilicate ETS-10.J. Colloids. Surf. Sci
287, 2005, 178-184.
[7] A. Sdiri, T. Higashi, T. Hatta, F. Jamousssi, N. Tase, Evaluating the
adsorptive capacity of montmorillonitic and calcareous clays on the
removal of several heavy metals in aqueous systems. Chem Eng J
172(1), 2011, pp. 37–46
[8] K.G. Bhattacharyya, S.S. Gupta, Pb(II) uptake by kaolinite and
montmorillonite in aqueous medium: influence of acid activation of the
clay. Colloids Surf. A. 277, 2006, pp.191–200.
[9] I. Chaari, E. Fakhfakh, S. Chakroun, J. Bouzid, N. Boujelben, M. Feki,
F. Rocha, F. Jamoussi, Lead removal from aqueous solutions by a
Tunisian smectitic clay. J. Hazard. Mater. 156, 2008, pp. 545–551.
[10] L. Khalfa, M.L. Cervera, M. Bagane, N.S. Soaad, Modeling of
equilibrium isotherms and kinetic studies of Cr (VI) adsorption into
natural and acid-activated clays. Arab. J. Geosci. 9, 2016, 75.
[11] M. Ben M'barek Jemaï, , A. Sdiri, E. Errais, J. Duplay, I. Ben Saleh,
M.F. Zagrarni, S. Bouaziz, Characterization of the Ain Khemouda
halloysite (western Tunisia) for ceramic industry. J. Afr. Earth Sci. 111,
2015, pp.194–201.
[12] M. Eloussaief, M. Benzina, Efficiency of natural and acid-activated
clays in the removal of Pb(II) from aqueous solutions. J. Hazard. Mater.
178, 2010, pp. 753–757.
[13] A.A .Rouff, E.J. Elzinga, R.J. Reeder, The effect of aging and pH on
Pb(II) sorption processes at the calcite–water interface. Environ. Sci.
Technol. 40, 2006, pp.1792–1798.
[14] V.C. Srivastava, I.D. Mall, I.M. Misha, Removal of cadmium (II) and
zinc(II) metal ions from binary aqueous solution by rice husk ash .
Colloid. Surf. Physicochem. Eng. Aspects. 312, 2008, pp. 172–184.
[15] F. Nekouei, S. Nekouei, I. Tyagi, V.K. Gupta , Kinetic, thermodynamic
and isotherm studies for acid blue 129 removal from liquids using
copper oxide nanoparticle-modified activated carbon as a novel
adsorbent, J. Molec. Liq. 201, 2015, pp.124–133.
[16] K.D. Belaid, S. Kacha, M. Kameche , Z. Derriche , Adsorption kinetics
of some textile dyes onto granular activated carbon, J. Environ. Chem.
Eng. 1, 2013, pp. 496–503.
[17] Q. Peng, M. Liu, J. Zheng, C. Zhou, Adsorption of dyes in aqueous
solutions by chitosan–halloysite nanotubes composite hydrogel beads,
Micr. and Mes. Mater. 201, 2015, pp.190–201.
[18] A. Sari, M. Tuzen, D. Citak, M. Soylak, Equilibrium, kinetic and
thermodynamic studies of adsorption of Pb(II) from aqueous solution
onto Turkish kaolinite clay. J. Hazard. Mater. 149, 2007, pp. 283–291.
[19] A. Sdiri, T. Higashi, F. Jamoussi, Adsorption of copper and zinc onto
natural clay in single and binary systems. Int. J. Environ. Sci. Technol.
11, 2014, pp.1081–1092.
[20] M. Mazzotti, Equilibrium theory based design of simulated moving bed
processes for a generalized Langmuir isotherm, J. Chromatogr. A 1126,
2006, pp.311–322.
[21] M. Raoov, S. Mohamad, M.R. Abas, Removal of 2,4-dichlorophenol
using cyclodextrin-ionic liquid polymer as a macroporous material:
Characterization, adsorption isotherm, kinetic study, thermodynamics, J.
Hazard. Mater. 263, 2013, pp. 501– 516.
[22] V.C. Srivastava, I.D. Mall, I.M. Mishra, Equilibrium modeling of single
and binary adsorption of cadmium and nickel onto bagasse fly ash,
Chem. Eng. J. 117, 2006, pp.79–91.
[23] V.C. Srivastava, I.D. Mall, I.M. Mishra, Modeling individual and
competitive adsorption of cadmium (II) and zinc (II) metal ions from
aqueous solution onto bagasse fly ash, Sep. Sci. Technol. 41, 2006, pp.
2685–2710.
[24] D. Mohan, K.P. Singh, Single and multi-component adsorption of
cadmium and zinc using activated carbon derived from bagasse- an
agricultural waste, Water Res. 36, 2002, pp. 2304–2318.
[1] N. Unlu, M. Ersoz, Adsorption characteristics of heavy metal ions onto a
low cost biopolymeric sobent from aqueous solutions. J. Hazard. Mater.
B 136, 2006, pp. 272–280
[2] V.C. Srivastava, I.D. Mall, I.M. Misha, Characterisation of mesoporous
rice husk ash (RHA) and adsorption kinetics of metal ions from aqueous
solution onto RHA. J. Hazard. Mater. B 134, 2006, pp. 257–267.
[3] F. Boudrahem, F. Aissani-Benissad, A. Soualah, Adsorption of lead(II)
from aqueous solution by using leaves of date trees as an adsorbent. J.
Chem. Eng. Data 56, 2011, pp. 1804–1812.
[4] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters. A
review. J. Environ. Manage, 92, 2011, pp.407–418.
[5] Y.S. Al-Degs, M.I. El-Barghouthi, A.A. Issa, M.A. Khraisheh, G.M
.Walker, Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents:
Equilibrium and kinetic studies. Water Res. 40, 2006, pp. 2645–2658.
[6] L.Lv, M.P. Hor, F.Sa, X.S.Zhoo, Competitive adsorption of Pb2+, Cu2+
and Cd2+ ions on microporous titanosilicate ETS-10.J. Colloids. Surf. Sci
287, 2005, 178-184.
[7] A. Sdiri, T. Higashi, T. Hatta, F. Jamousssi, N. Tase, Evaluating the
adsorptive capacity of montmorillonitic and calcareous clays on the
removal of several heavy metals in aqueous systems. Chem Eng J
172(1), 2011, pp. 37–46
[8] K.G. Bhattacharyya, S.S. Gupta, Pb(II) uptake by kaolinite and
montmorillonite in aqueous medium: influence of acid activation of the
clay. Colloids Surf. A. 277, 2006, pp.191–200.
[9] I. Chaari, E. Fakhfakh, S. Chakroun, J. Bouzid, N. Boujelben, M. Feki,
F. Rocha, F. Jamoussi, Lead removal from aqueous solutions by a
Tunisian smectitic clay. J. Hazard. Mater. 156, 2008, pp. 545–551.
[10] L. Khalfa, M.L. Cervera, M. Bagane, N.S. Soaad, Modeling of
equilibrium isotherms and kinetic studies of Cr (VI) adsorption into
natural and acid-activated clays. Arab. J. Geosci. 9, 2016, 75.
[11] M. Ben M'barek Jemaï, , A. Sdiri, E. Errais, J. Duplay, I. Ben Saleh,
M.F. Zagrarni, S. Bouaziz, Characterization of the Ain Khemouda
halloysite (western Tunisia) for ceramic industry. J. Afr. Earth Sci. 111,
2015, pp.194–201.
[12] M. Eloussaief, M. Benzina, Efficiency of natural and acid-activated
clays in the removal of Pb(II) from aqueous solutions. J. Hazard. Mater.
178, 2010, pp. 753–757.
[13] A.A .Rouff, E.J. Elzinga, R.J. Reeder, The effect of aging and pH on
Pb(II) sorption processes at the calcite–water interface. Environ. Sci.
Technol. 40, 2006, pp.1792–1798.
[14] V.C. Srivastava, I.D. Mall, I.M. Misha, Removal of cadmium (II) and
zinc(II) metal ions from binary aqueous solution by rice husk ash .
Colloid. Surf. Physicochem. Eng. Aspects. 312, 2008, pp. 172–184.
[15] F. Nekouei, S. Nekouei, I. Tyagi, V.K. Gupta , Kinetic, thermodynamic
and isotherm studies for acid blue 129 removal from liquids using
copper oxide nanoparticle-modified activated carbon as a novel
adsorbent, J. Molec. Liq. 201, 2015, pp.124–133.
[16] K.D. Belaid, S. Kacha, M. Kameche , Z. Derriche , Adsorption kinetics
of some textile dyes onto granular activated carbon, J. Environ. Chem.
Eng. 1, 2013, pp. 496–503.
[17] Q. Peng, M. Liu, J. Zheng, C. Zhou, Adsorption of dyes in aqueous
solutions by chitosan–halloysite nanotubes composite hydrogel beads,
Micr. and Mes. Mater. 201, 2015, pp.190–201.
[18] A. Sari, M. Tuzen, D. Citak, M. Soylak, Equilibrium, kinetic and
thermodynamic studies of adsorption of Pb(II) from aqueous solution
onto Turkish kaolinite clay. J. Hazard. Mater. 149, 2007, pp. 283–291.
[19] A. Sdiri, T. Higashi, F. Jamoussi, Adsorption of copper and zinc onto
natural clay in single and binary systems. Int. J. Environ. Sci. Technol.
11, 2014, pp.1081–1092.
[20] M. Mazzotti, Equilibrium theory based design of simulated moving bed
processes for a generalized Langmuir isotherm, J. Chromatogr. A 1126,
2006, pp.311–322.
[21] M. Raoov, S. Mohamad, M.R. Abas, Removal of 2,4-dichlorophenol
using cyclodextrin-ionic liquid polymer as a macroporous material:
Characterization, adsorption isotherm, kinetic study, thermodynamics, J.
Hazard. Mater. 263, 2013, pp. 501– 516.
[22] V.C. Srivastava, I.D. Mall, I.M. Mishra, Equilibrium modeling of single
and binary adsorption of cadmium and nickel onto bagasse fly ash,
Chem. Eng. J. 117, 2006, pp.79–91.
[23] V.C. Srivastava, I.D. Mall, I.M. Mishra, Modeling individual and
competitive adsorption of cadmium (II) and zinc (II) metal ions from
aqueous solution onto bagasse fly ash, Sep. Sci. Technol. 41, 2006, pp.
2685–2710.
[24] D. Mohan, K.P. Singh, Single and multi-component adsorption of
cadmium and zinc using activated carbon derived from bagasse- an
agricultural waste, Water Res. 36, 2002, pp. 2304–2318.
@article{"International Journal of Earth, Energy and Environmental Sciences:73010", author = "L. Khalfa and M. Bagane and M. L. Cervera and S. Najjar", title = "Competitive Adsorption of Heavy Metals onto Natural and Activated Clay: Equilibrium, Kinetics and Modeling", abstract = "The aim of this work is to present a low cost adsorbent
for removing toxic heavy metals from aqueous solutions. Therefore,
we are interested to investigate the efficiency of natural clay minerals
collected from south Tunisia and their modified form using sulfuric
acid in the removal of toxic metal ions: Zn(II) and Pb(II) from
synthetic waste water solutions. The obtained results indicate that
metal uptake is pH-dependent and maximum removal was detected to
occur at pH 6. Adsorption equilibrium is very rapid and it was
achieved after 90 min for both metal ions studied. The kinetics results
show that the pseudo-second-order model describes the adsorption
and the intraparticle diffusion models are the limiting step. The
treatment of natural clay with sulfuric acid creates more active sites
and increases the surface area, so it showed an increase of the
adsorbed quantities of lead and zinc in single and binary systems. The
competitive adsorption study showed that the uptake of lead was
inhibited in the presence of 10 mg/L of zinc. An antagonistic binary
adsorption mechanism was observed. These results revealed that clay
is an effective natural material for removing lead and zinc in single
and binary systems from aqueous solution.", keywords = "Lead, zinc heavy metal, activated clay, kinetic study,
competitive adsorption, modeling.", volume = "10", number = "5", pages = "583-7", }
