Adsorption of Nickel in Water by Brown Algae:

Laminaria japonica and Undaria pinnatifida

GONG Zheng-jun
School of Environmental Science & Engineering,
Southwest Jiaotong University,
Chengdu, China
gongzhengjun@126.com

CHEN Yu
Department of Environmental Science & Engineering
Southwest Jiaotong University
Chengdu, China
butter_cy@163.com


ZHANG Zhi-peng
School of Environmental Science & Engineering,
Southwest Jiaotong University,
Chengdu, China
zzpwss123@126.com

WANG Dong-mei
School of Environmental Science & Engineering,
Southwest Jiaotong University,
Chengdu, China
caroline040308@126.com

AbstractThis paper has researched on the adsorption of Ni in
water using Laminaria japonica and Undaria pinnatifida. The
dependence on pH and nickel concentration of the adsorption
was studied. Batch experiments results showed that the
adsorptive capacity of Laminaria japonica and Undaria
pinnatifida was 2.933mg/g and 0.985 mg/g of adsorbent. The
Langmuir model was used to describe the adsorption equilibrium
of nickel on Laminaria japonica and Undaria pinnatifida. The
Langmuir constants for adsorption of Ni on Laminaria japonica
and Undaria pinnatifida were determined.
Keywords-brown algae; adsorption; nickel
I. INTRODUCTION
Metals like Cd, Pb, Cu, and Zn are, at elevated
concentrations, detrimental to human health and ecosystem
stability, and threshold values have been set for these metals
for waste water discharged into environment and for drinking
water. In order to reduce pollution, contaminated waters need
to be cleaned. Common cleaning methods comprise chemical
precipitation, ion exchange, electrolysis, membrane filtration,
and sorption to metal oxides, clays and organic sorbents.
These methods differ with respect to cost, complexity and
efficiency [1-3].
The aqueous-phase separation of toxic heavy metal ions by
biosorption has attracted much attention in recent years.
Biosorption employs inexhaustible, inexpensive,
nonhazardous materials, and generates low volumes of
nonhazardous waste. Microorganisms [4-6], algae [7, 8], and
other types of biomass [9] have been investigated for use in
this application. An abundant source of potentially metal-
sorbing biomass is marine algae. They are widely available
and are ecologically acceptable. Moreover, marine algae can
be used as biosorbents without intricate pretreatment such as
centrifugation and immobilization.
Based on the Langmuir equation, the adsorption of Nickel
in water by Laminaria japonica and Undaria pinnatifida will bi
discussed.
II. EXPERIMENTAL
A. Reagents and metal solution
All the chemicals used, including Ni(NO
3
)
2
6H
2
O, HCl,
NaOH, etc. were of analytical-reagent grade and were used
without further purification.
All solutions were made with deionized water.
The stock solution of nickel was prepared by dissolving the
Ni(NO
3
)
2
6H
2
O (Shanghai Chemical Regent Plant, Shanghai,
PR China) in deionized water. The test solutions containing
single nickel ions were prepared by diluting 1 g/l stock metal
ion solution. The initial metal ion concentration ranged from
50 to 500 mg/l. The pH of each solution was adjusted to the
required value with HCl or NaOH before mixing the
adsorbent.
B. Preparation of adsorbent
A sun-dried sample of Laminaria japonica and Undaria
pinnatifida was obtained from market were dried at room
temperature for 3 days after collection. These algae were
further dried at 60C for 2 days and stored in a desiccator. The
resulting product was directly used as adsorbent. The dried
algae were then cut into small pieces and were powdered
using domestic mixer. In the present study the powdered
materials in the range of 100-200m particle size were then
directly used as adsorbents without any pretreatment.
C. Analysis of nickel
The concentration of initial and final nickel in the
adsorption experiments was determined by using atomic
absorption spectrophotometer (Hitachi Z-5000, Japan) at a
wavelength of 234.8 nm, slit width 1.3 nm and lamp current
9.0 mA.
The results are given as a unit of adsorbed and unadsorbed
nickel concentrations per gram of brown algae adsorbent in
solution at equilibrium and calculated by
2010 International Conference on Challenges in Environmental Science and Computer Engineering
978-0-7695-3972-0/10 $26.00 2010 IEEE
DOI 10.1109/CESCE.2010.136
241
2010 International Conference on Challenges in Environmental Science and Computer Engineering
978-0-7695-3972-0/10 $26.00 2010 IEEE
DOI 10.1109/CESCE.2010.136
240

m
V C C
Me
eq
) (
0

=
where Me is the adsorbed metal ion quantity per gram of
adsorbent at equilibrium (mg/g), C
0
the initial metal
concentration (mg/l), C
eq
the metal concentration concentration
at equilibrium (mg/l) and V is the working solution volume
(ml), m the brown algae adsorbent concentration (g/l).
D. Metal adsorption experiments
Adsorption experiments were conducted at 20 in batch
with 0.1 g of the Laminaria japonica (L. J.) and Undaria
pinnatifida (U. P.) in a 30ml of working solution volume.
Experiments for determining the kinetics of the process were
performed at 50-400 mg/l initial metal concentrations for
nickel. Samples were taken at desired intervals and the
adsorbent was removed by filtration using Whatman filter
paper. The heavy metal concentration in the resulting
supernatant was determined. The impact of the solution pH on
the metal biosorption was investigated in the same way except
that the initial pH of the solutions was adjusted from 3.0 to 8.0
with the addition of either 0.1M NaOH or 0.1M HCl.
E. Adsorption equilibrium
Equilibrium studies were carried out by agitating 30 ml of
nickel solutions of initial concentrations varying from 50 to
400 mg/l with 0.2 g of algae at room temperature for 24 h at a
constant stirring speed at a pH of 5.
During the adsorption, a rapid equilibrium is established
between adsorbed metal ions on the adsorbent (Me) and
unadsorbed metal ions in solution (Ceq). This equilibrium can
be represented by the Langmuir [10], which is widely used to
analyse data for water and wastewater treatment applications.
The Langmuir equation which is valid for monolayer
adsorption on to a surface a finite number of identical sites and
is given by
eq
eq
bC
bC Q
Me
+
=
1
max


where Q
max
is the maximum amount of the metal ion per unit
weight of algae to form a complete monolayer on the surface
bound at high C
eq
(mg/g), and b is a constant related to the
affinity of the binding sites (l/mg) Q
max
represents a practical
limiting adsorption capacity when the surface is fully covered
with metal ions and assists in the comparison of adsorption
performance, particularly in cases where the sorbent did not
reach its full saturation in experiments. Q
max
and b can be
determined from the linear plot of C
eq
/Me versus C
eq
[12]

III. RESULTS AND DISCUSSION
A. Acidic Sites on Brown Algae
Earlier studies on heavy metal adsorption have shown that
pH was the single most important parameter affecting the
adsorption process [11]. In all cases, metal adsorption by the
L. J. and U.P. increases with increasing pH reaching to a
maximum and then showed a rapid decline in adsorption. The
equilibrium metal uptake of the L. J. and U.P. from 50 to 400
mg/l nickel solution at various pH values is shown in Fig. 1.
The pH dependence of metal uptake could be related to the
functional groups of the biomass and also to solution
chemistry. As Fig. 1 shown, absorption of Ni is most at pH
5.0. So pH 5.0 was chosen for the further work.
0
10
20
30
3 4 5 6 7 8
pH
N
i

m
g
/
L

LJ
UP

Fig 1 Effect of pH on the adsorption of Ni on LJ and UP
B. Biosorption of Bivalent Metal Ions to Brown Algae
The adsorption equilibrium defines the distribution of a
solute phase between the liquid phases and solid phases after
the adsorption reaction reached equilibrium condition. In the
present study, equilibrium studies were carried out at room
temperature 20 . The equilibrium data were analysed using
one of the most commonly used isotherm equations, Langmuir
isotherm models.
The equilibrium data were very well represented by the
Langmuir equilibrium model (Fig. 2). The calculated isotherm
constants at room temperature 20 were given in Table 1.
The best-fit equilibrium model was determined based on the
linear regression correlation coefficient R
2
. From the table it
was observed that the adsorption data were very well
represented by Langmuir isotherm with an average higher
correlation coefficient of 0.992 (L. J.) and 0.986(U. P.). From
Table 1, for L. J., the Langmuir adsorption capacity Q
max

(mg/g) is 2.933 and the equilibrium constant b (l/mg) is
0.00327 and for U. P., the Langmuir adsorption capacity Q
max

(mg/g) is 0.985 and the equilibrium constant b (l/mg) is
0.0203.












Fig 2 Isothermal adsorption curves of Ni on L. J. and U. P.

IV. CONCLUSION
The biomass of the marine algae L. J. and U. P.
demonstrated a good capacity of nickel biosorption,
highlighting its potential for effluent treatment processes. The
adsorption process is a function of the pH and metal ion
concentration. The adsorption capacity of L. J. and U. P. was
2.933mg/g and 0.985 mg/g, confirming that those algae under
1
2
1-LJ
2-UP
0
0.5
1
1.5
2
0 100 200 300 400 500
Ceq (mg/l)
M
e
(
m
g
/
g
)
242 241

these conditions can be effectively used as adsorbent. The
experimental data gave good fit with Langmuir isotherm and
the adsorption coefficients agreed well with the conditions of
favorable adsorption.

Table 1 Equilibrium constants for Ni onto L. J. and U. P.
Langmuir
isotherm
Laminaria
japonica
Undaria
pinnatifida
b (l/mg)
0.00327 0.0203
Q
max
(mg/g)
2.933 0.985
R
2
0.992 0.986
ACKNOWLEDGEMENT
The support of this work by the Development of Science
and Technology Research Fund of Southwest Jiaotong
University (2009) and the Experiment Teaching and
Technology Project of Southwest Jiaotong University (2009)
is gratefully acknowledged.
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