Received: 27 December, 2009. Accepted: 4 September, 2010.
Original Research Paper
Bioremediation, Biodiversity and Bioavailability ©2011 Global Science Books
Effects of Adsorbent Activation on Bioremediation of Hg (II)
and Cd (II) Ions from Aqueous Solution using Boiler Fly Ash
Nnenna E. Okoronkwo
*
• Jude C. Igwe • Chibuike C. Aniekwu
Department of Industrial Chemistry, Faculty of Biological and Physical Sciences, Abia State University, P.M.B. 2000 Uturu, Nigeria
Corresponding author: * nnennaejijeokoronkwo@yahoo.com
ABSTRACT
Heavy metal (HM) removal from wastewater has attracted much attention in the past few decades. The search for low cost sorbents
became the focus recently as a result of the expensive nature of conventional adsorbents. The use of unactivated and nitric acid activated
boiler fly ash an agricultural by-product in the bioremediation of mercury (Hg) (II) and cadmium (Cd) (II) ions from aqueous solution was
investigated in this work. The amount adsorbed increased as the initial metal ion concentration was increased. For unactivated boiler fly
ash (BFA), the amount of Hg (II) ion adsorbed was higher than the amount of Cd (II) ion that was adsorbed. The acid-activated BFA
adsorbed more than the unactivated BFA, with the influence of activation much more on the amount of Cd (II) ion adsorbed. The sorption
process was modeled using two kinetic models: pseudo-first order and the pseudo-second order equations; and also six isotherm models
namely Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Temkin, Harkins-Jura (H-J) and Smith equations. For the kinetic models,
the pseudo second-order equation gave a better fit to the sorption process. The differences in fitness of the isotherm models to the sorption
process were not significant by two-way ANOVA. Also, analysis of the equilibrium sorption data in accordance with the six isotherm
models and applying a normalized standard deviation q revealed that the Harkins-Jura isotherm model gave a better fit to experimental
data. The apparent energy of sorption E (KJ mol
-1
) from the D-R equation gave values of 26.72, (unactivated), 223.61 (activated) for Cd
(II) ion and 50.00 (unactivated), 158.11 (activated) for Hg (II) ion, all in KJ mol
-1
. Hence, activation increased the sorption capacity of the
adsorbent and the values of apparent energy of sorption. Also, from the values of E, the sorption process could be said to follow a
chemisorption mechanism.
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Keywords: adsorption, agricultural by-products, environment, heavy metal ions, isotherms, surface chemistry
Keywords: BFA, boiler fly ash; HM, heavy metal
INTRODUCTION
The treatment of effluent water from industries and other
sources have been achieved through adsorption principles.
In recent times the use of agricultural residues or waste
materials in the removal of HM ions has revealed good pot-
ential in wastewater treatment (Brandley and Duong 1988;
Sun and Shi 1998; Igwe and Abia 2003; Okoronkwo 2008).
This recent research and development of agricultural waste
materials as adsorbents are based on a need to increase
utility and for better adaptation of renewable materials to
specific ends in order to make better use of limited resour-
ces available and to meet with consumers’ needs and wishes
compared to the use of ion exchanged resin, precipitation
and other conventional methods which are also effective
methods of removing metals from effluent water, but which
are costly (Brandley and Duong 1988; Lin and Liu 2000).
Heavy metals (HMs) are poisonous metallic elements in
the environment. The toxicity of HMs to marine life and
consequently to man has for many years been established.
Cadmium (Cd), a naturally occurring HM can be found in
food, water and cigarette smoke. It is a known human carci-
nogen. Exposure of people to Cd may not only be through
foods but also through drinking contaminated water (Sun
and Shi 1998). Mercury (Hg) is one of the most problematic
of all toxic HMs because despite its dangerous and known
roles as a neurotoxin, many people have it implanted in
their mouth, injected into their blood stream or are con-
suming it daily in fish. The removal of these HMs from
solution by unmodified and modified cellulosic materials
such as maize cob has been reported (Okeimen and Oriaki
1987; Okeimen and Okundaye 1989; Igwe and Abia 2003;
Abia et al. 2005).
Similar works have been carried out by researchers
which include the removal of lead from aqueous solution by
palm kernel fiber (Ofomaja et al. 2005), the use of polyami-
nated highly porous chitosan (Takatsuji and Yoshida 1998),
the use of chemically modified and unmodified waste (Abia
and Igwe 2005). Furthermore the role of pH, temperature
and particle size effect of some of these biosorbents has
been investigated (Ho 2003; Igwe et al. 2005). Also sorp-
tion kinetics and intraparticulate diffusivities of Cd, Pb, and
Zn ions on maize cob have been reported (Abia et al. 2005).
The modeling of some of these biosorbents with an adsorp-
tion isotherm has been shown to follow some well known
isotherms.
Boiler fly ash (BFA), which is a porous substance,
results from the burning of mainly fruit bunch and kernels
for boiler fuel. It is known that every tonne of fresh fruit
bunch (FFB) produces about 4 to 6 kg of BFA (Majid et al
1999). BFA has also been reported to be made up of phos-
phorus (0.28-1.33%), potassium (1.02-4.31%), calcium
(0.39-3.24%) and magnesium (0.29-2.60%) (Rusnani and
Ma 1999). BFA has been applied as a soil conditioner
because of these mineral contents. It has also been used as a
landfill because its generation has been enormous from the
numerous palm oil mills that exist. BFA have also been
used in various other ways such as an adsorbent for removal
of HMs from aqueous solution (Pandy et al. 1985; Mathur
and Rupainwar 1988; Weng and Huang 1994; Hashim et al.
1996) and in the reduction of BOD, TSS and colour from
palm oil mill effluent (POME) (Majid et al. 1999).
Therefore, this work aimed to investigate the effect of
concentration of these HMs on the adsorption capacity of
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