3rd AMIREG International Conference (2009): Assessing the Footprint of 19

Resource Utilization and Hazardous Waste Management, Athens, Greece

Application of bentonite modified with L-Histidine for the adsorption of

toxic elements in mine wastewaters

E.N. Bakatula, H. Tutu and E.M. Cukrowksa

Environmental Analytical Chemistry, School of Chemistry, University of the Witwatersrand, South
Africa

I.M. Weiersbye
Restoration & Conservation Biology Research Group, School of Animal, Plant & Environmental
Sciences, University of the Witwatersrand, South Africa

L. Mihaly-Cozmuta and A. Mihaly-Cozmuta

Chemistry-Biology Department of North University of Baia Mare, Romania

ABSTRACT several methods have been used and proposed

world-wide for the removal of pollutants from
This study proposes the use of bentonite modi-
wastewaters leaching from such facilities. Some
fied with L-histidine for the capture of toxic
examples include: ion exchange and adsorption
elements in mine wastewater. The surface area
onto charcoal, activated carbon, zeolites, clays,
of the natural bentonite and the bentonite-
plant materials, membrane filtration. The chal-
histidine were found to be 73.8 and 61.2 m2/g,
lenge of achieving high adsorption efficiencies
respectively. The elemental analysis showed an
still remains as well as the development of
increased amount of 0.258% of carbon and
cheaper materials for adsorption. The sorption
0.066% of nitrogen for the bentonite-histidine.
of dissolved substances by a biomaterial is an
Batch kinetic and batch isotherm studies were
attractive technology that has gained importance
carried out to evaluate the effect of initial con-
due to its advantages over conventional separa-
centration, pH, contact time and temperature on
tion techniques. These advantages are the reus-
the adsorption. The bentonite-histidine showed
ability of biomaterial, low operating cost, im-
higher adsorption capacity (up to 99%) than the
proved selectivity for specific metals of interest,
natural bentonite for the metal ions studied. It
removal of heavy metal from effluent irrespec-
was found that a contact time of 30 minutes was
tive of toxicity, short operation time and no pro-
necessary for the adsorption to reach the equi-
duction of secondary compounds which might
librium. The maximum adsorption value was
be toxic (Spinti et al., 1995; Srinath et al.,
obtained at pH 5 for Ni, Zn, Co, Cu and U on
2002).
the natural bentonite. Except Ni, the metals
L-Histidine is one of the compounds released
studied presented high adsorption capacity on
by the micro-organisms and interacts with the
the functionalized bentonite at pH 2. The ex-
clay mainly through the imidazole group. Stud-
perimental biosorption equilibrium data were in
ies revealed that the adsorption capacity of ben-
good agreement with those calculated by both
tonite could be enhanced (at about ten times
Langmuir and Freundlich models.
higher) by surface modification using organo-
functional silane coupling agents (de Mello,
1. INTRODUCTION 2008; Loredo, 2007). The effects of contact
time, concentration of metal, temperature and
Wastes generated by the mining industry con- pH on the natural bentonite as well as bentonite-
tain high concentrations of metals and metal- histidine were studied.
loids which can be mobile, resulting in leaching
into groundwater and surface water. The man-
agement of such wastes poses a challenge and
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
2. MATERIALS AND METHODS
2.1 Natural bentonite
The natural bentonite used as adsorbent in the
present study, grey in colour, was supplied by
Sigma-Aldrich (Pty.) Ltd. South Africa. The ad-
sorbent was dried for 24 hours at 60o C before
the experiments.
2.2 Bentonite-histidine
For the synthesis of the bentonite-histidine ad-
sorbent, 10 g of natural bentonite interacted at
60oC for 48 h at pH 8 with 100 ml of solution
containing L-Histidine hydrochloride which was
the same amount as the CEC value of the ben-
tonite. Then, the synthesized sorbent was
washed several times with de-ionized water to
remove the possible unreacted L- Histidine. The
sorbent was resuspended in de-ionized water,
stirred for about 1 hr at room temperature and
separated by filtration. The suspension was
dried in the oven for 24 hrs at 60oC.
2.3 Reagents and standards
All chemicals used were analytical reagent
grade. Standards used for quantification were
high purity having trace metals below the detec-
tion limits. A concentration of 1000 mg L-1 was
prepared for each trace metal (Cu, Zn, Ni, U,
Co, Hg and Fe). Appropriate aliquots were
taken from these standards for subsequent dilu-
tion to the desired concentration level.
Adsorption of metals (Cu, Zn, Ni, U, Co, Hg
and Fe) was studied on natural bentonite as well
as on bentonite-histidine. An amount of the sor-
bent was placed into 250 ml bottles and 100 ml
of metal solution of known concentration were
added. The contents were shaken for a given pe-
riod of time and temperature at 170 rpm. The
solutions were then filtered using Whatman fil-
ter paper 0.45 µm; the concentration of metals
was measured by ICP-OES. The pH of the solu-
tion was adjusted by addition of dilute HNO3 or
NaOH solution. The percentage adsorption
(Milonjic et al., 1992) and the distribution coef-
Table 1: Properties of bentonite and bentonite-histidine.
Surface Area Average Pore volume
Sample
m2/g cm2/g
Bentonite 73.8 0.103
Bentonite-
61.2 0.0087
Histidime
20
ficient (Komatsu et al., 1990) were calculated.
3. RESULTS AND DISCUSSION
The mineralogical composition of the natural
bentonite determined by XRF (in percent) was:
SiO2 52.26, Al2O3 17.25, Fe2O3 0.53, FeO 4.25,
MnO 0.07, MgO 3.67, CaO 2.05, K2O 1.38,
Na2O 0.35, TiO2 0.4, P2O5 0.09 and loss on ig-
nition (LOI) 17.72%. BET, CEC and CHNS re-
sults are given in Table1.
Elemental analysis of bentonite-histidine
showed an increased amount of carbon
(0.258%) nitrogen (0.066%).
3.1 Effect of contact time
The time-dependant behaviour of metals adsorp-
tion on natural bentonite as well as on ben-
tonite-histidine is shown in Figure 1. It was ob-
served that the rapid adsorption process oc-
curred within 30 minutes and then followed by a
slow adsorption process continued for 12 hours.
The adsorption capacity of U and Hg increased
drastically in the modified bentonite. The sorp-
tion of metals ion on natural bentonite was pro-
duced following the sequence: Fe2+ > Cu2+ >
Zn2+, Ni2+ > Co2+ > U2+ > Hg2+ whilst in ben-
tonite-histidine, the sequence was: Fe2+ > Hg2+>
Cu2+ > U2+ > Co2+, Zn2+ > Ni2+.
3.2 Effect of temperature
The adsorption isotherms of Cu, Zn Ni, Co, Fe,
U and Hg sorption on the natural and the modi-
fied bentonite were obtained at four different
temperatures while keeping all other parame-
ters, i.e. metal concentration, shaking time and
pH, constants. The results are given in Table 2.
In general, the adsorption capacity on bentonite-
histidine was high (> 99%) compared to that on
natural bentonite at 18, 22, 26 and 30 oC.
Thermodynamic parameters, i.e. free energy
∆Ho, entropy change ∆Go, activation energy Ea,
adsorption capacity Ac and reaction rate for the
sorption of Cu, Zn Ni, Co, Fe, U, Hg on ben-
tonite as well as bentonite-histidine were calcu-
CEC C H N
meq/100g % % %
64.42 0.555 1.748 0.678
42.54 0.813 1.490 0.744
3rd AMIREG International Conference (2009): Assessing the Footprint of 21
Resource Utilization and Hazardous Waste Management, Athens, Greece

tion is favored at higher temperature. It was ob-

served that the rate of adsorption for the metal
ions increases with the increasing of the tem-
perature with Fe metal ion being the least af-
fected while mercury was the most affected. The
values of activation energy, enthalpy change for
the reaction and free energy for the adsorption
of heavy metals on bentonite - histidine at each
temperature was greater than those obtained at
the same temperature for the natural bentonite.
This could be due to the complex formation be-
tween the metal ions and the amine groups at-
tached on the bentonite structure. The adsorp-
tion data for 18, 22, 26 and 30o C were found to
be in accordance with the Freundlich and the
Langmuir models.
3.3 Effect of pH
The effect of pH on adsorption of heavy metals
on the bentonite and the modified bentonite was
studied in the pH range 2 to 12. The results are
shown in Figure 2.
The results showed a constant adsorption rate
of Fe on natural bentonite for the all range of
pH. The adsorption rate of U, Ni, Zn, Co and Cu
on natural bentonite was found low at low pH
and the rate increased with the pH. A maximum
adsorption was reached at pH 5 for U, Ni and
Cu and at pH 7 for Zn and Co. The adsorption
Figure 1: Plots of adsorption % versus contact time for
single component system at pH 3.00 for the natural ben- rate of Hg decreased with the pH till pH 5 then
tonite and the bentonite-Histidine. before increasing.
The low adsorption rate observed at low pH
lated. The positive values of ∆Ho showed that in natural bentonite can be attributed to the fact
the sorption of metals on bentonite is an endo- that low pH implies high H+ concentration,
thermic process. Then the enthalpy increases which turns to competes with the metal ions for
with the temperature. The values of ∆Go were the adsorption sites.
negative for the metals except for Hg. These in- Also, hydrolysis of the aluminum oxide sites
dicate the spontaneity of the adsorption process. at very low pH on the natural bentonite results
∆Go becomes more negative with increasing in the loose of the crystallographic structure of
temperature which further shows that the sorp- natural bentonite and consequently its adsorbent
Table 2: Adsorption capacity (mg/g) of metals (single component system) for the natural bentonite and the bentonite-
histidine at different temperatures.
Adsorption capacity (mg/g)
Natural bentonite Bentonite-histidime
Metal 18oC 22oC 26oC 30oC Metal 18oC 22oC 26oC 30oC
Cu 4.717 4.791 4.821 4.887 Cu 4.988 4.989 4.991 4.995
Ni 4.028 4.039 4.155 4.18 Ni 4.986 4.985 4.968 4.964
Zn 4.037 4.377 4.417 4.464 Zn 4.998 4.997 4.994 4.994
Co 3.675 3.842 3.926 3.979 Co 4.997 4.998 4.992 4.992
Fe 4.997 4.985 4.98 4.978 Fe 4.998 4.998 4.998 4.998
Hg 1.623 1.462 1.205 2.018 Hg 4.982 4.993 4.99 4.99
U 3.108 2.616 3.66 3.302 U 4.991 4.992 4.994 4.951
3rd AMIREG International Conference (2009): Assessing the Footprint of 22
Resource Utilization and Hazardous Waste Management, Athens, Greece

competition for the active site of the bentonite-

histidine, and also, there is destruction of the
bentonite-histidine structure hence resulting to
low porosity and low adsorption rate. At very
high pH values, the precipitation of the metal
hydroxide out ways the adsorption of the metals
on the bentonite - histidine and hence the de-
struction of the bentonite-histidine structure
turns to decrease the rate of adsorption on the
bentonite - histidine.

4. CONCLUSION
The study showed that the adsorption capacity
of bentonite can be enhanced by modification of
the surface using a microbial component as his-
tidine. This hybrid organic-inorganic material
can be an alternative low cost material in the

Figure 2: Plots of the adsorption % versus pH on natural

bentonite of heavy metals in single component solutions.

capacity. The maximum adsorption capacity ob-

tained at the pH range 5 to 7 for all the metals
studied is due to the contribution of adsorption
as well as precipitation process since most of
the metals hydrolyze at this pH range so they
will precipitate in their hydroxide form, as metal
hydroxide. It was observed a maximum and
constant adsorption rate at the pH 7.
The results of adsorption of metals on modi-
fied bentonite (Fig. 3) showed high adsorption
rate at low pH for Co, Zn, Fe, Hg, U. An in-
crease with pH was observed for Ni whilst the
adsorption rate was constant at the all range of
pH for Cu. The formation of complex between
the metal ion and the bentonite-histidine de-
pends on the amine groups present on the ad-
sorbant. The rate of adsorption increases with
the increase of the amine group on the structure.
A decrease of adsorption rate was observed at
very low pH due to the protonation of the amine Figure 3: Plots of the adsorption % versus pH on ben-
group to form ammonium ion. tonite-histidine of heavy metals in single component solu-
At very low pH, there is H+ and metal ions tions.
3rd AMIREG International Conference (2009): Assessing the Footprint of 23
Resource Utilization and Hazardous Waste Management, Athens, Greece

treatment of mine wastewater and possibly for

the recovery of precious metals for such efflu-
ent. The adsorption rate of bentonite-histidine is
greater than that of natural bentonite at high
concentration of metals due to the structure of
bentonite-histidine.
Chemical modification by amine coupling
agents may be a useful tool for the preparation
of new adsorbents with high adsorption capaci-
ties and selectivity towards metal ions retention
for waste waters from acid mine drainage sys-
tems. Bentonite can also be used as support me-
dia for the culture of other fungi and microalgae
with higher metal-binding capacities.

ACKNOWLEDGEMENTS
The authors would like to thank the National
Research Foundation and the Carnegie Founda-
tion for the financial support.

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