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 for removal of different heavy metals from aqueous solutions
of copper, chromium, nickel, and lead from aqueous solutions via bio- (Dönmez et al., 1999; Gupta et al., 2001; Kaewsarn, 2002; Nuhoglu
sorption using nonliving algae species, Chara sp. and Cladophora sp. et al., 2002; Terry and Stone, 2002).
Optimum pH values for biosorption of copper (II), chromium (III), nickel Algae, bacteria, fungi, and yeasts have proven to be potential
(II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3
metal biosorbents (Ekinci Doğan et al., 2006). Chara sp. and
for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum
Cladophora sp., green filamentous macro-algae, have been widely
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 used as wastewater pollution monitors because of their ability to
for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, bind and accumulate many metals strongly. Algae grow in fresh
copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for and/or saltwater over a wide range of temperatures and pH values
copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for (Sternberg and Dorn, 2002). They are ubiquitous and native to
copper (II) and 11.76 for nickel (II)]. Significantly high correlation almost all parts of the world.
coefficients indicated for the Langmuir adsorption isotherm models can be Studies on biosorption using algae species in Turkey are not as
used to describe the equilibrium behavior of copper, chromium, nickel, and extensive as in other countries. Turkey is a developing country;
lead adsorption onto Cladophora sp. and Chara sp. Water Environ. Res., 79, thus, biosorption studies are gaining importance. In addition, the use
1000 (2007).
of algae in heavy metal removal is inexpensive when compared with
KEYWORDS: biosorption, copper, chromium, nickel, lead Chara sp., other systems, and climate and geographical conditions in Turkey
Cladophora sp. are suitable for the plant biomass. A survey of literature indicated
doi:10.2175/106143007X183961 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
Introduction nonliving Chara sp. and Cladophora sp. for copper (II), chromium
The accumulation of heavy metals in the environment has (III), nickel (II), and lead (II) from aqueous solution. Further, the
received a great deal of attention because of the threat to public use of these materials has been insufficiently addressed in the
health. Traditional technologies used for heavy metal removal literature. Results obtained in this study could be useful for
include chemical precipitation, ion exchange, reverse osmosis, and developing pilot- and full-scale studies. The biosorption capacities
solvent extraction. Although these processes tend to be efficient, are evaluated from equilibrium adsorption isotherms.
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. Materials and Methods
It has been demonstrated that biosorption is a potential alternative Preparation of the Algae for Biosorption. Fresh samples of
to the traditional treatment process of metal ions removal (Gupta Chara sp. and Cladophora sp. used in all experiments were
et al., 2001). Biosorption uses the ability of the biological materials collected from Uluabat Lake, Bursa, Turkey. Before use, all
to accumulate heavy metals from waste streams by either meta- samples of algae were washed several times with distilled water and
bolically mediated or purely physicochemical pathways of uptake kept on coarse filter paper to reduce the water content. Following
(Fourest and Roux, 1992). The biosorption process has been demon- the prewashing step, the biomass was dried at 608C for 24 hours
strated in a wide range of algae, such as Spyrogira sp., Chlorella before grinding. After this processes, algae species were grinded
sp., Scenedesmus sp., Synechocystis sp., Ulotrix sp., and Padina sp., and sieved to select particles between 0.3 and 0.7 mm for use.
For biosorption studies, 10 g/L inactivated dried algae species
Department of Environmental Engineering, Uludag University, Bursa, were suspended in distilled water and homogenized for 0.5 hours
Turkey. in a homogenizer (Yellowline, DI 25 basic, Sheffield, United
* Uludag University, Faculty of Engineering and Architecture, Department Kingdom) at 8000 r/min, then stored in a refrigerator until use.
of Environmental Engineering, Gorukle Campus, 16059, Bursa, TURKEY; Biosorption Studies. Sorption studies were conducted at
e-mail: [email protected]. room temperature (22 6 18C) in 150-mL flasks. For isotherm

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 Elmaci et al.

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. concentration in the solution. Adsorption isotherm tests were run in
(1 g/L) were thoroughly mixed individually with 90 mL of metal triplicate, and average values were reported.
solutions, with varying concentrations of copper (II), chromium Batch sorption experiments were performed at various pH values
(III), nickel (II), and lead (II) solutions (20, 30, 40, 50, and 60 mg between 2.0 and 8.0. pH measurements were made using a pH meter
metal/L [AccuTrace Reference Standard (1000 mg/L [1000 ppm]) (model T10, Cyberscan, Ayer Rajah Crescent, Singapore). The pH
AccuStandard Inc., New Haven, Connecticut]) by diluting with values of solutions were monitored continuously and adjusted using
distilled water (Dönmez et al., 1999; Dönmez and Aksu, 2001; 0.1 M sulfuric acid or 0.1 M sodium hydroxide (supplied from
Terry and Stone, 2002). The suspensions were shaken on the orbital Merck, Darmstadt, Germany), if deviations were observed.
shaker (Nuve SL 350, Ankara, Turkey) at 200 r/min for 24 hours. The residual concentrations in the liquid of copper (II), chromium
Samples collected at required time intervals were centrifuged (Nuve (III), nickel (II), and lead (II) were determined using an atomic
nf 815) at 3000 r/min for 10 minutes. The supernatant was filtered absorption spectrophotometer (ATI Unicam 929 AA Spectrometer,
through 0.45-lm filter paper and analyzed for residual metal Cambridge, United Kingdom) (APHA et al., 1995).

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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 the biosorption process (Dönmez et al., 1999; Fourest et al., 1994;
acid followed by through rinsing with deionized water before use. All Gupta et al., 2001). The pH affects the solution chemistry of the
reagents used were of analytical reagent grade. Deionized water was metals, activity of the functional groups in the biomass, and
used throughout the study. All analyses were done in triplicate. competition of metallic ions (Ekinci Doğan et al., 2006; Sanchez
et al., 1999). Therefore, the effect of pH on metal adsorption of
Results and Discussion Chara sp. and Cladophora sp. was studied first. Removal
Effect of pH on Copper (II), Chromium (III), Nickel (II), and efficiencies of metal ions for each species studied are given in
Lead (II) Biosorption. Earlier studies on heavy metal biosorption Figures 1a and 1b under different pH values. As seen from the
have indicated that pH was the most important parameter affecting figure, for Cladophora sp., the adsorption of chromium (III) and

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 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

to form a complete monolayer on the surface bound at
Freundlich model final (equilibrium) concentration of solute in the solution
Copper 4.81 32.93 0.9484 15.57 12.85 0.0945 (mg/g),
Chromium 3.787 10.17 0.9411 1.301 87.11 0.5355 Ceq 5 final (equilibrium) concentration (mg/L), and
Nickel 6.93 18.93 0.9344 17.55 11.91 0.6786 b 5 a constant related to the affinity between the biosorbent
Lead 4.68 41.22 0.9808 42.37 18.83 0.0483 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
nickel (II) were effective at pH 7, and copper (II) and lead (II) were comparison of adsorption performance, particularly in cases where
effective at pH 6 and 3, respectively. For Chara sp., the adsorption the sorbent did not reach its full saturation in experiments. Equation
of copper (II) and nickel (II) were effective at pH 5, and chromium 1 may be written in a linearized form, as follows:
(III) and lead (II) were effective at pH 3 and 4, respectively.
Solution pH influences both cell surface and metal binding sites and Ceq 1 Ceq
¼ 0 þ 0 ð2Þ
metal chemistry in water. These results have shown that the bio- qeq Q b Q
sorption characteristics of these algae species are strongly de-
The variables Q0 and b can be determined from the linear plot of
pendent on pH for the removals of heavy metals [copper (II),
Ce2qe versus Ceq (Dönmez and Aksu, 2002; Dönmez et al., 1999).
chromium (III), nickel (II), and lead (II)] from solution. Chara sp.
The empirical Freundlich equation based on sorption on a
prefers acidic conditions, and Cladophora sp. prefers slightly acidic
heterogeneous surface is as follows:
conditions.
Effect of Initial Metal Concentration on Copper (II), 1=n
qeq ¼ Kf  Ceq ð3Þ
Chromium (III), Nickel (II), and Lead (II) Biosorption. The
initial concentration provides an important driving force to overcome Where
all mass transfer resistance of metal ions between the aqueous and
Kf and n 5 Freundlich constants characteristic of the system, and
solid phases (Dönmez and Aksu, 2002). Initial metal concentrations
qe 5 concentration of adsorbant in solution (g/L).
ranged between 20 and 60 mg/L. Higher metal ion uptake was
observed at lower concentrations of metal ions. Effects of initial The variables Kf and n are indicators of adsorption capacity and
metal concentration on copper (II), chromium (III), nickel (II), and adsorption intensity of the sorbent, respectively. The higher the
lead (II) biosorption by Cladophora sp. and Chara sp. are shown in values of Kf and n, the higher the affinity of algae. Equation 3 can
Figures 2a and b. The results showed that copper (II) and chromium be linearized in logarithmic form to determine the Freundlich
(III) biosorption was similar for Cladophora sp. and Chara sp. at 20 constants (Dönmez and Aksu, 2002; Dönmez et al., 1999).
mg/L. Nickel (II) biosorption of Cladophora sp. at low concen- The correlation coefficient and the constants of the Langmuir and
trations is higher than that of Chara sp. Lead (II) was adsorbed at all Freundlich model obtained for all metals and plants studied in this
concentrations for Cladophora sp. and Chara sp.; therefore, higher work are summarized in Table 1. The regression coefficient (R2) for
removal efficiencies were observed at low concentrations. each biosorbent shows the most suitable model for describing these
Differences between algal species in the magnitude of change in sorption processes. As seen from Table 1, significantly high regres-
metal ion binding capacity may be a result of the properties of the sion correlation coefficients for the Langmuir isotherm model was
metal sorbates (i.e., ionic size, atomic weight, or reduction potential found. The Langmuir model makes several assumptions, such as
of the metal) and of the algae (i.e., structure, functional groups, monolayer coverage and constant adsorption energy, while the
surface area, genera, and species) (Dönmez et al., 1999). Cell walls Freundlich equation deals with physicochemical adsorption on
of prokaryotic and eukaryotic microalgae contain polysaccharides heterogeneous surfaces. The applicability of both Langmuir and
as basic building blocks, which have ion exchange properties, Freundlich isotherms, as also demonstrated in other studies (Acar
proteins, and lipids, and therefore offer a host of functional groups and Malkoc, 2004; Arica et al., 2004; Tsai et al., 2004), implies that
capable of binding to heavy metals. These functional groups, such both monolayer biosorption and heterogeneous surface conditions
as amino, carboxylic, suphydryl, phosphate, and thiol groups, differ exist under the experimental conditions used in this study. The heavy
in their affinity and specificity for metal binding (Aksu et al., 1996). metal biosorption capacity and isotherm constants (b, n, and KF) of

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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 more work is required. The results obtained in this study could be
experimental data of the Ce2qe plots. The results have shown that useful for developing pilot- and full-scale studies.
heavy metal adsorption isotherms are fit to the Langmuir model.
Maximum adsorption capacities of Chara sp. and Cladophora sp. Credits
for chromium (III) and lead (II) are similar. On the other hand, the Submitted for publication May 25, 2006; revised manuscript
copper (II) and nickel (II) biosorption capacity of Cladophora sp. is submitted September 5, 2006; accepted for publication January 16,
greater than that of Chara sp. When compared with literature studies 2007.
in which algae was used (Chang et al., 1997; Dönmez et al., 1999; The deadline to submit Discussions of this paper is December 15,
Gupta et al., 2001; Jalali et al., 2002; Terry and Stone, 2002; Wong 2007.
et al., 2000), Chara sp. and Cladophora sp. are also good
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