Applied Clay Science 29 (2005) 145 – 148

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Technical Note

Adsorption of some heavy metal ions on sulfate- and

phosphate-modified kaolin
K.O. Adebowale*, I.E. Unuabonah, B.I. Olu-Owolabi
Department of Chemistry, University of Ibadan, Ibadan—Nigeria
Received 11 August 2003; received in revised form 15 April 2004; accepted 30 September 2004

Abstract

Kaolin (bright white lumps) from Ubulu-Ukwu in Delta State of Nigeria was modified with 200 Ag mL
1 of phosphate and
sulphate anions to give phosphate- and sulfate-modified adsorbents, respectively. The adsorption of four metal ions (Pb2+, Cd2+,
Zn2+, and Cu2+) was studied as a function of metal ions concentration.
The metal ions showed stronger affinity for the phosphate-modified adsorbent with Pb2+, Cu2+, Zn2+, and Cd2+ giving an
average of 93.28%, 80.94%, 68.99%, and 61.44% uptake capacity. The order of preference for the various adsorbents shown by
the metal ions was as follows:

Pb2þ NCu2þ N Zn2þ N Cd2þ

Desorption studies showed that the phosphate-modified adsobent had the highest affinity for the metal ions, followed by the
sulfate-modified clay while the unmodified clay had the least affinity.
The experimental data were fitted by both the Langmuir and Freundlich models.
D 2004 Published by Elsevier B.V.

Keywords: Kaolin; Heavy metal ions; Adsorption

1. Introduction waters, and ground water resources with heavy

metals throughout the world (Paulson, 1997). The
Extraction and processing of metal ions and heavy metals through natural weathering and trans-
wastewater effluents from chemical-based industries port processes are dispersed beyond their sources
have led to the contamination of soil, surface to surrounding soils, surface, and ground waters,
endangering the quality of water and plant used for
human consumption (Fuge et al., 1993). Some
* Corresponding author. remediation technologies have been used to restore
E-mail address: ko.adebowale@mail.ui.edu.ng contaminated sites. The technologies include exca-
(K.O. Adebowale). vation and land filling of metal-contaminated soils
0169-1317/$ - see front matter D 2004 Published by Elsevier B.V.
doi:10.1016/j.clay.2004.10.003
146 K.O. Adebowale et al. / Applied Clay Science 29 (2005) 145–148

and waste which is expensive and in situ chemical 2.4. Metal ion adsorption
immobilization involving the addition of chemicals
like phosphates (Vangronsveld and Cunningham, About 30 mL of the standardised metal ion solutions
1998). Adsorption technique is one of the most (Pb2+, Cd2+, Zn2+, and Cu2+) of concentrations 300–700 mg
efficient methods of cleaning the environment of L
1 was added to 0.5 g each of the modified and unmodified
clay. The pH of Pb2+, Cd2+, and Zn2+ solutions was adjusted
heavy metal pollutant. In this case, the adsorbent
to 7.0, while that of Cu was adjusted to 6.0. The dispersions
should possess high selectivity with respect to the were placed on a rotary shaker for 24 h. The supernatants
heavy metal ions and should be relatively cheap obtained after centrifugation were analysed by Atomic
and readily available (Dipa and Bhattachayya, Absorption Spectrophotometry (AAS 200A Buck Scientific
2002). Model). The amount adsorbed was calculated from the
Due to dearth of information on the adsorption of concentration difference.
heavy matal ions with phosphate and sulphate
modified kaolinite, this article therefore reports the 2.5. Metal ion desorption
change in the CEC, retention ability, and selectivity
for Pb, Cd, Zn, and Cu in aqueous solution. Desorption studies were carried out by shaking the
washed dispersions used for the adsorption studies with
three portions of 1 M NH4Cl (at pH 5) for 45 min. The
2. Materials and methods suspensions were centrifuged and the supernatant analysed
by Flame Atomic Absorption Spectrophotometry (FAAS).
2.1. Materials

Kaolin, in bright white lumps, was collected from Ubulu- 3. Results and discussions
Ukwu, Delta State, Nigeria. After collection, stones and
other heavy particles were removed from the sample. The 3.1. Physicochemical properties
clay was then crushed, ground, and sieved through a 230-
mesh sieve. A part of the kaolin was kept dispersed in The mineralogical composition of the kaolin
doubly deionised water in a 1-L beaker for several hours. It
showed that it consisted mainly of kaolinite (c61%).
was further purified using the method of Moore and
Reynolds (1989).
Other components are shown in the Table 1. The
surface area of the kaolin by methylene blue adsorption
2.2. Measurement of physicochemical properties was 12.8 m2 g
1.

The surface area was measured by methylene blue 3.2. Adsorption studies
adsorption (Barton, 1987). The silica and alumina content
of the samples were determined by Atomic absorption The metal ions showed a higher affinity for the
spectroscopy while Fe2+ and Fe3+ were determined as modified kaolin and H2PO4
modified clay displayed
described by Vogel (1996). The effective cation exchange a higher adsorption capacity than sulfate-modified
capacity was obtained by the method of Juo et al. (1976). clay at all the concentrations of the metal ion
It involves the summation of the exchangeable acidity and
concentrations (Table 2). The adsorption of the metal
the cation exchange capacity of the adsorbent. The
mineralogical composition of the clay sample was
ions by the modified and original kaolin followed the
determined with a DIANO 2100*E X-ray diffractometer order:
(CuK a radiation).
Pb2þ NCu2þ NZn2þ NCd2þ
2.3. Modification of the kaolinite
This order follows the ease of hydrolysis of the
Kaolin (0.5 g) was shaken with 30 mL of 200 Ag/mL of cations (Forbes et al. 1976; Brummer, 1986). Alkalinity
KH2PO4 /Na2SO4 in a rotary shaker for 24 h. The samples measure of pHc6 or 7 at which the adsorption was
were washed thrice with 30 mL potion of doubly deionised carried out enhanced the sorption of the monovalent
water to remove excess SO42
and H2PO4
ions. (Test for cations (such as ZnOH+), which also increases the
phosphate and sulphate was negative). adsorption (Ma and Uren, 1998).
 K.O. Adebowale et al. / Applied Clay Science 29 (2005) 145–148 147

Table 1
Physicochemical parameters of modified and unmodified kaolinite
(%) composition of the substrate
Substrates ECEC SiO2 Al2O3 MgO CaO Na2O K2O Fe2O3 FeO LOI SSA
(meq/100 g) (m2 g
1)
Kaolinite 7.81 65.14 25.62 0.40 0.30 1.38 1.21 0.74 0.41 4.79 12.80
P-modified 13.45 – – – – – – – – – –
S-modified 9.32 – – – – – – – – – –
LOI=loss on ignition, SSA=specific surface area, ECEC=effective cation exchange capacity.

The adsorption of cations on kaolin phosphate- (1981), this indicates that more Pb2+ ions have been
modified and sulfate-modified kaolin fitted the Lang- adsorbed on specific sites than the nonspecific sites,
muir and Freundlich models. When the experimental whereas a higher proportion of Cd2+ ions have been
values for he cations were fitted to both the Langmuir adsorbed on nonspecific sites. The desorption iso-
and Freundlich models, the following observations therms of Cu2+ ions could be replaced by NH4+ ions on
were obtained: the modified clay.
The desorption of Zn2+ ions showed that it
(1) The cations were adsorbed on sites whose followed a similar trend as Cu2+ and Pb2+ ions except
binding energies are uniform and therefore that the degree of desorption was higher. A similar
formed a layer on the surface of the adsorbents. trend was observed by Singh et al. (2001) on the
(2) There is no interaction between the adsorbed adsorption and desorption of Pb2+, Cd2+ and Zn2+ on
molecules. phosphatic clay.

3.3. Desorption studies

4. Conclusions
From the desorption studies, Pb2+ ions exhibited
very strong affinity for the phosphate-modified clay, The metal ions showed greater affinity for the
followed by Cu2+ and Zn2+ ions while Cd2+ ions modified kaolin compared with the unmodified
showed the least affinity. The increase in the effective sample. The phosphate-modified kaolin however
cation exchange capacity from 7.8 meq/100 g for the showed a higher adsorption capacity than the sul-
unmodified clay to 13.5 meq/100 g for the phosphate- phate-modified sample.
modified clay supported this fact. The order of
desorption was:
Acknowledgements
Unmodified N sulfate
modified Nphosphate

modified clay We acknowledge with thanks the support of the
Abdus Salam International Centre for Theoretical
The desorption isotherm of Cd2+ revealed that the Physics, ICTP and the Swedish International Devel-
kaolin exchanges Cd2+ ions more easily by NH4+ than opment Agency SIDA.
Pb2+ ions. According to Ahy-Abd-Elfattah and Wada

Table 2 References
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