Biosorption Characteristics of Copper (II),
Chromium (III), Nickel (II), and Lead (II) from
Aqueous Solutions by Chara sp. and
Cladophora sp.
Aysxe Elmaci*, Taner Yonar, Nihan Özengin
ABSTRACT: The aim of this research was to expose individual removals
of copper, chromium, nickel, and lead from aqueous solutions via bio-
sorption using nonliving algae species, Chara sp. and Cladophora sp.
Optimum pH values for biosorption of copper (II), chromium (III), nickel
(II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3
for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum
adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for
lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25
for lead (II)] for chromium (III) and lead (II) are similar. On the other hand,
copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for
copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for
copper (II) and 11.76 for nickel (II)]. Significantly high correlation
coefficients indicated for the Langmuir adsorption isotherm models can be
used to describe the equilibrium behavior of copper, chromium, nickel, and
lead adsorption onto Cladophora sp. and Chara sp. Water Environ. Res., 79,
1000 (2007).
KEYWORDS: biosorption, copper, chromium, nickel, lead Chara sp.,
Cladophora sp.
doi:10.2175/106143007X183961
Introduction
The accumulation of heavy metals in the environment has
received a great deal of attention because of the threat to public
health. Traditional technologies used for heavy metal removal
include chemical precipitation, ion exchange, reverse osmosis, and
solvent extraction. Although these processes tend to be efficient,
they are often ineffective or expensive (Dönmez and Aksu, 2001;
Kaewsarn, 2002; Sternberg and Dorn, 2002). The need for eco-
nomical and effective methods for metal removal resulted in the
search for alternative materials and methods.
It has been demonstrated that biosorption is a potential alternative
to the traditional treatment process of metal ions removal (Gupta
et al., 2001). Biosorption uses the ability of the biological materials
to accumulate heavy metals from waste streams by either meta-
bolically mediated or purely physicochemical pathways of uptake
(Fourest and Roux, 1992). The biosorption process has been demon-
strated in a wide range of algae, such as Spyrogira sp., Chlorella
sp., Scenedesmus sp., Synechocystis sp., Ulotrix sp., and Padina sp.,
Department of Environmental Engineering, Uludag University, Bursa,
Turkey.
* Uludag University, Faculty of Engineering and Architecture, Department
of Environmental Engineering, Gorukle Campus, 16059, Bursa, TURKEY;
e-mail: aelmaci@uludag.edu.tr.
1000
for removal of different heavy metals from aqueous solutions
(Dönmez et al., 1999; Gupta et al., 2001; Kaewsarn, 2002; Nuhoglu
et al., 2002; Terry and Stone, 2002).
Algae, bacteria, fungi, and yeasts have proven to be potential
metal biosorbents (Ekinci Doğan et al., 2006). Chara sp. and
Cladophora sp., green filamentous macro-algae, have been widely
used as wastewater pollution monitors because of their ability to
bind and accumulate many metals strongly. Algae grow in fresh
and/or saltwater over a wide range of temperatures and pH values
(Sternberg and Dorn, 2002). They are ubiquitous and native to
almost all parts of the world.
Studies on biosorption using algae species in Turkey are not as
extensive as in other countries. Turkey is a developing country;
thus, biosorption studies are gaining importance. In addition, the use
of algae in heavy metal removal is inexpensive when compared with
other systems, and climate and geographical conditions in Turkey
are suitable for the plant biomass. A survey of literature indicated
that not much work has been done so far on the nonliving biomass
of Cladophora sp. and Chara sp. for heavy metal removal. The
objective of this study is to evaluate the biosorption capacity of the
nonliving Chara sp. and Cladophora sp. for copper (II), chromium
(III), nickel (II), and lead (II) from aqueous solution. Further, the
use of these materials has been insufficiently addressed in the
literature. Results obtained in this study could be useful for
developing pilot- and full-scale studies. The biosorption capacities
are evaluated from equilibrium adsorption isotherms.
Materials and Methods
Preparation of the Algae for Biosorption. Fresh samples of
Chara sp. and Cladophora sp. used in all experiments were
collected from Uluabat Lake, Bursa, Turkey. Before use, all
samples of algae were washed several times with distilled water and
kept on coarse filter paper to reduce the water content. Following
the prewashing step, the biomass was dried at 608C for 24 hours
before grinding. After this processes, algae species were grinded
and sieved to select particles between 0.3 and 0.7 mm for use.
For biosorption studies, 10 g/L inactivated dried algae species
were suspended in distilled water and homogenized for 0.5 hours
in a homogenizer (Yellowline, DI 25 basic, Sheffield, United
Kingdom) at 8000 r/min, then stored in a refrigerator until use.
Biosorption Studies. Sorption studies were conducted at
room temperature (22 6 18C) in 150-mL flasks. For isotherm
Water Environment Research, Volume 79, Number 9

Figure 1—(a) Effect of pH on biosorption of copper (II), chromium (III), nickel (II), and lead (II) ions by (a) Chara sp. and
(b) Cladophora sp.
determination, nonliving samples of Chara sp. and Cladophora sp.
(1 g/L) were thoroughly mixed individually with 90 mL of metal
solutions, with varying concentrations of copper (II), chromium
(III), nickel (II), and lead (II) solutions (20, 30, 40, 50, and 60 mg
metal/L [AccuTrace Reference Standard (1000 mg/L [1000 ppm])
AccuStandard Inc., New Haven, Connecticut]) by diluting with
distilled water (Dönmez et al., 1999; Dönmez and Aksu, 2001;
Terry and Stone, 2002). The suspensions were shaken on the orbital
shaker (Nuve SL 350, Ankara, Turkey) at 200 r/min for 24 hours.
Samples collected at required time intervals were centrifuged (Nuve
nf 815) at 3000 r/min for 10 minutes. The supernatant was filtered
through 0.45-lm filter paper and analyzed for residual metal
September 2007
Elmaci et al.
concentration in the solution. Adsorption isotherm tests were run in
triplicate, and average values were reported.
Batch sorption experiments were performed at various pH values
between 2.0 and 8.0. pH measurements were made using a pH meter
(model T10, Cyberscan, Ayer Rajah Crescent, Singapore). The pH
values of solutions were monitored continuously and adjusted using
0.1 M sulfuric acid or 0.1 M sodium hydroxide (supplied from
Merck, Darmstadt, Germany), if deviations were observed.
The residual concentrations in the liquid of copper (II), chromium
(III), nickel (II), and lead (II) were determined using an atomic
absorption spectrophotometer (ATI Unicam 929 AA Spectrometer,
Cambridge, United Kingdom) (APHA et al., 1995).
1001
Elmaci et al.
Figure 2—Effect of initial metal concentration on copper (II), chromium (III), nickel (II), and lead (II) biosorption by (a)
Chara sp. and (b) Cladophora sp.
All glassware used for the analyses was carefully cleaned with nitric
acid followed by through rinsing with deionized water before use. All
reagents used were of analytical reagent grade. Deionized water was
used throughout the study. All analyses were done in triplicate.
Results and Discussion
Effect of pH on Copper (II), Chromium (III), Nickel (II), and
Lead (II) Biosorption. Earlier studies on heavy metal biosorption
have indicated that pH was the most important parameter affecting
1002
the biosorption process (Dönmez et al., 1999; Fourest et al., 1994;
Gupta et al., 2001). The pH affects the solution chemistry of the
metals, activity of the functional groups in the biomass, and
competition of metallic ions (Ekinci Doğan et al., 2006; Sanchez
et al., 1999). Therefore, the effect of pH on metal adsorption of
Chara sp. and Cladophora sp. was studied first. Removal
efficiencies of metal ions for each species studied are given in
Figures 1a and 1b under different pH values. As seen from the
figure, for Cladophora sp., the adsorption of chromium (III) and
Water Environment Research, Volume 79, Number 9
 Elmaci et al.

Table 1—Comparison of the Langmuir and Freundlich This situation explains the similarity and the difference between the
adsorption constants for copper (II), chromium (III), nickel heavy metal removal rates of two algae species.
(II), and lead (II) for Cladophora sp. and Chara sp. Adsorption Isotherms. The adsorption isotherm was obtained
under the best pH values for each metal, as determined above. The
Cladophora sp. Chara sp. most widely used models to describe the equilibrium behavior of
metal adsorption are the well-known Freundlich and Langmuir
Q0 b R2 Q0 b R2 sorption isotherms. These two models were used to correlate the
Langmuir model isotherm data in this study. The Langmuir equation is expressed in
Copper 14.28 0.36 0.9935 6.506 2.54 0.754
eq 1, as follows:
Chromium 6.55 4.34 0.9904 0.404 10.54 0.9118 Q0  b  Ceq
Nickel 16.75 1.98 0.9902 11.76 0.272 0.7948 qeq ¼ ð1Þ
1 þ b  Ceq
Lead 23.25 2.56 0.9778 61.72 0.819 0.9955
Cladophora sp. Chara sp. Where

n KF R2 n KF R2 Q0 5 maximum amount of the metal ion per unit weight of algae

Freundlich model
Copper 4.81 32.93 0.9484 15.57 12.85 0.0945
Chromium 3.787 10.17 0.9411 1.301 87.11 0.5355
Nickel 6.93 18.93 0.9344 17.55 11.91 0.6786
Lead 4.68 41.22 0.9808 42.37 18.83 0.0483
nickel (II) were effective at pH 7, and copper (II) and lead (II) were
effective at pH 6 and 3, respectively. For Chara sp., the adsorption
of copper (II) and nickel (II) were effective at pH 5, and chromium
(III) and lead (II) were effective at pH 3 and 4, respectively.
Solution pH influences both cell surface and metal binding sites and
metal chemistry in water. These results have shown that the bio-
sorption characteristics of these algae species are strongly de-
pendent on pH for the removals of heavy metals [copper (II),
chromium (III), nickel (II), and lead (II)] from solution. Chara sp.
prefers acidic conditions, and Cladophora sp. prefers slightly acidic
conditions.
Effect of Initial Metal Concentration on Copper (II),
Chromium (III), Nickel (II), and Lead (II) Biosorption. The
initial concentration provides an important driving force to overcome
all mass transfer resistance of metal ions between the aqueous and
solid phases (Dönmez and Aksu, 2002). Initial metal concentrations
ranged between 20 and 60 mg/L. Higher metal ion uptake was
observed at lower concentrations of metal ions. Effects of initial
metal concentration on copper (II), chromium (III), nickel (II), and
lead (II) biosorption by Cladophora sp. and Chara sp. are shown in
Figures 2a and b. The results showed that copper (II) and chromium
(III) biosorption was similar for Cladophora sp. and Chara sp. at 20
mg/L. Nickel (II) biosorption of Cladophora sp. at low concen-
trations is higher than that of Chara sp. Lead (II) was adsorbed at all
concentrations for Cladophora sp. and Chara sp.; therefore, higher
removal efficiencies were observed at low concentrations.
Differences between algal species in the magnitude of change in
metal ion binding capacity may be a result of the properties of the
metal sorbates (i.e., ionic size, atomic weight, or reduction potential
of the metal) and of the algae (i.e., structure, functional groups,
surface area, genera, and species) (Dönmez et al., 1999). Cell walls
of prokaryotic and eukaryotic microalgae contain polysaccharides
as basic building blocks, which have ion exchange properties,
proteins, and lipids, and therefore offer a host of functional groups
capable of binding to heavy metals. These functional groups, such
as amino, carboxylic, suphydryl, phosphate, and thiol groups, differ
in their affinity and specificity for metal binding (Aksu et al., 1996).
to form a complete monolayer on the surface bound at
final (equilibrium) concentration of solute in the solution
(mg/g),
Ceq 5 final (equilibrium) concentration (mg/L), and
b 5 a constant related to the affinity between the biosorbent
and sorbate.
The lower the value of b, the higher the affinity of algae. The
variable Q0 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. Equation
1 may be written in a linearized form, as follows:
Ceq 1 Ceq
¼ 0 þ 0 ð2Þ
qeq Q b Q
The variables Q0 and b can be determined from the linear plot of
Ce2qe versus Ceq (Dönmez and Aksu, 2002; Dönmez et al., 1999).
The empirical Freundlich equation based on sorption on a
heterogeneous surface is as follows:
1=n
qeq ¼ Kf  Ceq ð3Þ
Where
Kf and n 5 Freundlich constants characteristic of the system, and
qe 5 concentration of adsorbant in solution (g/L).
The variables Kf and n are indicators of adsorption capacity and
adsorption intensity of the sorbent, respectively. The higher the
values of Kf and n, the higher the affinity of algae. Equation 3 can
be linearized in logarithmic form to determine the Freundlich
constants (Dönmez and Aksu, 2002; Dönmez et al., 1999).
The correlation coefficient and the constants of the Langmuir and
Freundlich model obtained for all metals and plants studied in this
work are summarized in Table 1. The regression coefficient (R2) for
each biosorbent shows the most suitable model for describing these
sorption processes. As seen from Table 1, significantly high regres-
sion correlation coefficients for the Langmuir isotherm model was
found. The Langmuir model makes several assumptions, such as
monolayer coverage and constant adsorption energy, while the
Freundlich equation deals with physicochemical adsorption on
heterogeneous surfaces. The applicability of both Langmuir and
Freundlich isotherms, as also demonstrated in other studies (Acar
and Malkoc, 2004; Arica et al., 2004; Tsai et al., 2004), implies that
both monolayer biosorption and heterogeneous surface conditions
exist under the experimental conditions used in this study. The heavy
metal biosorption capacity and isotherm constants (b, n, and KF) of

September 2007 1003

Elmaci et al.

Table 2—Experimental data of the Ce2qe plots.

Cladophora sp. Chara sp.

20 30 40 50 60 20 30 40 50 60

Copper concentration (mg/L)

Ce 0.14 0.375 1.456 5.635 8.808 5.92 14.328 28.25 36.6 38.12
qe 20 31.25 39.35 44.72 51.209 14.41 15.676 10.276 13.33 21.8
Chromium concentration (mg/L)
Ce 4.8 10.944 17.924 24.47 35.562 6.36 16.476 25.776 43.55 55.392
qe 15.23 19.066 22.128 25.54 24.441 13.648 13.527 14.225 6.45 4.608
Nickel concentration (mg/L)
Ce 0.856 7.074 12.528 20.41 28.128 5.212 13.896 30.208 42.88 56.916
qe 19.45 22.96 27.47 29.622 31.88 14.8 16.12 9.795 7.12 3.084
Lead concentration (mg/L)
Ce 0.028 0.267 1.092 1.7 3.552 3.572 8.501 22.896 33.3 42.9
qe 28 33.375 39 48.571 57.29 16.46 21.521 17.11 16.7 17.105

algae are given in Table 1 for both algae species. Table 2 shows the
experimental data of the Ce2qe plots. The results have shown that
heavy metal adsorption isotherms are fit to the Langmuir model.
Maximum adsorption capacities of Chara sp. and Cladophora sp.
for chromium (III) and lead (II) are similar. On the other hand, the
copper (II) and nickel (II) biosorption capacity of Cladophora sp. is
greater than that of Chara sp. When compared with literature studies
in which algae was used (Chang et al., 1997; Dönmez et al., 1999;
Gupta et al., 2001; Jalali et al., 2002; Terry and Stone, 2002; Wong
et al., 2000), Chara sp. and Cladophora sp. are also good
biosorbents for removing heavy metals.
Conclusions
The aim of this research was to expose individual removals of
copper, chromium, nickel, and lead from aqueous solutions via
biosorption using nonliving algae species, Chara sp. and
Cladophora sp. The results obtained showed that both species of
algae are good absorbing media for the purpose of removing heavy
metals studied from aqueous solution under dilute metal conditions.
In this study, biosorption studies tend to be dependent on pH for
both species of algae. Acidic conditions are more preferable for
Chara sp. and slightly acidic conditions preferable for Cladophora
sp. In this study, for Cladophora sp., the adsorption of chromium
(III) and nickel (II) was effective at pH 7 and adsorption of copper
(II) and lead (II) was effective at pH 6 and 3, respectively. For
Chara sp., the adsorption of copper (II) and nickel (II) was
effective at pH 5 and adsorption of chromium (III) and lead (II)
was effective at pH 3 and 4, respectively. The Freundlich and
Langmuir adsorption models were used for the mathematical
description of the biosorption of copper (II), chromium (III), nickel
(II), and lead (II) ions to nonliving Cladophora sp. and Chara sp.,
and the isotherm constants were evaluated to compare the
biosorptive capacity of the dried algae for the metal ions. It was
seen that the adsorption equilibrium data fitted very well to the
Langmuir model.
Consequently, the results of this study have also supported the
fact that algal removal of chromium (III), nickel (II), copper (II),
and lead (II) seems to be possible for the development of
biosorption units for water and wastewater treatment facilities.
Algal biosorption technologies are still being developed, and much
more work is required. The results obtained in this study could be
useful for developing pilot- and full-scale studies.
Credits
Submitted for publication May 25, 2006; revised manuscript
submitted September 5, 2006; accepted for publication January 16,
2007.
The deadline to submit Discussions of this paper is December 15,
2007.
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