Bioresource Technology 102 (2011) 52975304

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

The biosorption of heavy metals from aqueous solution by Spirogyra

and Cladophora lamentous macroalgae
Yi-Chao Lee, Shui-Ping Chang
Department of Environmental Engineering, Kun Shan University, Yung-Kang City, Tainan Hsien 71003, Taiwan, ROC

a r t i c l e

i n f o

Article history:
Received 30 July 2010
Received in revised form 23 December 2010
Accepted 27 December 2010
Available online 1 January 2011
Keywords:
Pb(II)
Cu(II)
Spirogyra spp.
Cladophora spp.
Biosorption

a b s t r a c t
The aim of this research was to develop a low cost adsorbent for wastewater treatment. The prime objective of this study was to search for suitable freshwater lamentous algae that have a high heavy metal ion
removal capability. This study evaluated the biosorption capacity from aqueous solutions of the green
algae species, Spirogyra and Cladophora, for lead (Pb(II)) and copper (Cu(II)). In comparing the analysis
of the Langmuir and Freundlich isotherm models, the adsorption of Pb(II) and Cu(II) by these two types
of biosorbents showed a better t with the Langmuir isotherm model. In the adsorption of heavy metal
ions by these two types of biosorbents, chemical and physical adsorption of particle surfaces was perhaps
more signicant than diffusion and adsorption between particles. Continuous adsorptiondesorption
experiments discovered that both types of biomass were excellent biosorbents with potential for further
development.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Industrial activity often creates wastewater containing heavy
metals that ows into natural waters. Heavy metal contamination
poses a potential health hazard to animals and humans alike
(Volesky and Holan, 1995). Conventional methods of metal
removal from wastewater are expensive and not always effective
for metals in low concentrations (Pan et al., 2009). Adsorption by
activated carbon is the most efcient classical way but the cost
of its production is prohibitive and it cannot be regenerated and
recycled (Farooq et al., 2010). Adverse effects of heavy metals on
the environment and their accretion through the food chain have
lead to research in the development of efcient, low cost techniques for wastewater treatment (Ahluwalia and Goyal, 2007;
Juwarkar et al., 2010; Pan et al., 2009; Sahan et al., 2010; Singh
et al., 2007), with methods using algae biomass receiving a great
deal of attention (Andrade et al., 2005; Bishnoi et al., 2007; Gupta
et al., 2006; Murphy et al., 2007; Mehta and Gaur, 2005; Singh et
al., 2007; Tuzen and Sari, 2010).
Algae are primary producers in ecological systems, widely distributed around the world, and closely connected with human life.
In this study, we chose Spirogyra and Cladophora spp. as biosorption materials due to their similar habitat distribution and close
taxonomic grouping. Both are benthic lamentous macroalgae
belonging to Division Chlorophyta. These species are naturally
abundant throughout the world (Simons and van Beem, 1990;
Corresponding author. Tel./fax: +886 6 2055011.
E-mail address: spchang@mail.ksu.edu.tw (S.-P. Chang).
0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.12.103

Whitton, 1970) and ease of harvesting. In recent years, many studies have applied both living and dead specimens of these two macroalgae to nutrient removal (DeBusk et al., 2004), biomonitoring
(Oertel, 1993), tannery and textile wastewater treatment (Khalaf,
2008; Mohan et al., 2002; zer et al., 2006; Onyancha et al.,
2008), and pharmaceutical ingredients (Mihranyan et al., 2004).
Obviously, these two genera of algae have high developmental
potential as biomaterials.
The aim of this research is to develop a low cost adsorbent for
wastewater treatment. The prime objective of this study is to
search for suitable freshwater lamentous algae that have high
heavy metal ion removal capability. This study evaluates the biosorption capacity of green algae, Spirogyra, and Cladophora spp.,
for Pb(II) and Cu(II) from aqueous solutions. We performed adsorption experiments using the aforementioned types of biosorption
materials on Pb(II) and Cu(II), two important hazardous heavy
metals. Through these adsorption experiments, we tested the
parameters of contact time, initial pH, and initial Pb(II) and Cu(II)
concentrations. Since more than one type of heavy metal is often
present in wastewater, such as the simultaneous presence of Pb(II)
and Cu(II) in the lead chemical fertilizer and the battery manufacturing industries. Conditions of biosorption material of different
divalent cation combinations can more accurately represent actual
environmental problems. For this reason, we explored the effects
of the simultaneous presence of Pb(II) and Cu(II) on their respective adsorption, using batch experiments to study kinetics and
adsorption equilibrium. To understand desorption efciency, we
also performed continuous adsorptiondesorption experiments
on Spirogyra and Cladophora spp. algae powder for Pb(II) and Cu(II).

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Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

Many studies have reported that Spirogyra and Cladophora spp.

have a very high capacity for binding with metals due to the presence of polysaccharides, proteins, or lipids on the surface of cell
walls. These contain functional groups such as aminos, hydroxyls,
carboxyls, and sulfates, which can act as binding sites for metals
(Alimohamadi et al., 2005; Deng et al., 2007; Gupta and Rastogi,
2008; Tuzen and Sari, 2010). This study also uses Fourier transform
infrared (FT-IR) spectroscopy to identify the main functional
groups involved in the interaction between algae and metals.
2. Methods

2.4. Sorption of Pb(II) and Cu(II) from binary metal solution

The sorptions of Pb(II) and Cu(II) were also determined from a
binary solution containing different concentrations (0, 100, and
200 mg L1) of both metals. Biomass concentration and other
experimental conditions were similar to those described earlier.
2.5. Analysis of experimental data
2.5.1. Analysis of Pb(II) and Cu(II)
Amounts of Pb(II) and Cu(II) adsorbed by the biomass were
calculated using the following equation:

2.1. Preparation of the test algae and chemicals

q C 0  C e V=W

Fresh algae biomass was collected upstream of the Tseng-Wen

Reservoir, Taiwan. Before use, it was washed with distilled water
to remove dirt and kept on lter paper to reduce water content.
The biomass was then sun-dried for 4 days, followed by oven drying at 70 C for 24 h, and ground in a gate stone pistol mortar. The
biomass was then sieved to select particles between 150 and 250
mesh size for use.
Stocks of 1000 mg L1 metal solutions were prepared using
Pb(NO3)2, and Cu(NO3)23H2O (analytical grade) in deionized water.
Nitrate was chosen as the counter ion because of its low tendency
to form metal complexes. The solutions were then diluted to the
desired concentrations and analyzed.

where q is the amount of Pb(II) or Cu(II) adsorbed by biomass

(mgg1), C0 is the initial concentration of Pb(II) or Cu(II) ions
(mg L1), Ce is the concentration of Pb(II) or Cu(II) at equilibrium
(mg L1), V is the volume of the metal solution (L), and W is the
mass of adsorbent (g). All experiments were conducted at room
temperature (25 C).

2.5.2. Biosorption isotherm

Adsorption data for a wide range of adsorbate concentrations
are best conveniently described by various adsorption isotherms,
such as the Langmuir and Freundlich isotherms.
The Langmuir model can be described as:

qe Q max bC e =1 bC e
2.2. Optical microscopes examination and Fourier transform infrared
(FT-IR) spectroscopy analysis

The logarithmic form of the equation is:

1=qe 1=Q max 1=C e bQ max

Researchers examined the algae with optical microscopes. Fresh
samples for optical microscopy were suspended in distilled water
on standard microscope slides with cover slips. Optical microscopy
was performed on an Olympus BX-51T transmission microscope
with a monochromatic lter. Fourier transform infrared (FT-IR)
spectroscopy (Spectrum GX) was used to detect vibration frequency changes in dried Cladophora spp. biomass before and after
Pb(II) and Cu(II) biosorption. Spectra within the range of 4000
400 cm1 were collected.
2.3. Batch experiments for single-ion solution
2.3.1. Effect of pH
The experiment was conducted for biosorption at a concentration of 100 mg L1 of Cu(II) ions and 1.0 g L1 of biosorbent dose
in a 50 mL metal solution for 60 min with varying pH from 3 to
7. Solution pH value was adjusted using 1 M HCl or 1 M NaOH.
2.3.2. Effect of contact time
The pH of the test solution was adjusted to 5 0.2, with a
constant metal concentration of 100 mg L1 and a biomass dose
of 1.0 g L1 in 50 mL of solution. Samples were taken after
5, 10, 15, 20, 30, 40, 50, and 60 min.
2.3.3. Effect of initial metal ions concentration
Effects of initial metal ion concentration on the biosorption of
Pb(II) and Cu(II) from 50 to 300 mg L1 were studied.
2.3.4. Effect of biosorbents dose
Different amounts of biomass doses ranging from 0.1 to
10.0 g L1 for 50 mL of Pb(II) and Cu(II) solutions in a 250 mL Erlenmeyer ask were used, while maintaining a pH of 5.0, a temperature of 25 C and concentrations of the Pb(II) and Cu(II) ions at
100 mg L1.

3
1

where qe is the amount of metal ions sorbed (mgg ) and Ce is the

equilibrium concentration (mg L1). Qmax represents maximum
adsorption and b is the afnity between biosorbent and biosorbate.The Freundlich isotherm is given as:

qe KC 1=n
e

The logarithmic form of the equation is given as:

log qe log K 1=n log C e

where K and 1/n are isotherm constants, respectively.

2.6. Successive adsorptiondesorption cycle studies
Pb(II) and Cu(II) ions sorbed onto Spirogyra and Cladophora spp.
biomass was separately desorbed using 10 mL of 0.5 M HCl.
Pb(II) and Cu(II) solution contents were determined by Atomic
absorption spectrometry (AAS). To use the biomass for subsequent
experiments, the biomass was sequentially washed with an excess
of 0.5 M HCl solution and distilled water.
3. Results and discussion
3.1. Comparison of biosorbents characteristics
Spirogyra and Cladophora spp. are benthic freshwater green algae widely distributed throughout the world. We selected these
two algae genera as adsorption materials and used optical microscopes to observe fresh samples, these two genera of algae could
be easily differentiated by their characteristics. The plant bodies
of Cladophora spp. showed branches. The Spirogyra spp. did not
show any branching. Spirogyra chloroplast bands a spiral belt. On
the plant bodies of Cladophora spp., we could observe a large
amount of epiphytic algae, mainly Bacillariophyta, and small epiphytic algae such as Chlorophyta, Cyanophyta, and Euglenophyta.

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Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

Conversely, on the plant bodies of Spirogyra spp., less species and

amounts of epiphytic algae were observed. Various algae having
different extracellular polymeric substances (Tien et al., 2002)
caused the differences between epiphytic algae on Cladophora
spp. and Spirogyra spp. When comparing the tested portion of
Cladophora FT-IR functional groups, we discovered that the mainly
functional groups were present in proteins and polysaccharides,
and that the wave number of the portion that experienced change
after adsorption occurred mainly in the carboxylic group. Onyancha et al. (2008) proposed the primary functional groups of
Spirogyra were hydroxyls, amines, alkyl, and carboxylic group. A
comparison of optical microscope observations and FT-IR test
results for the aforementioned types of adsorbents are shown in
Table 1. After adsorbing Pb(II) and Cu(II), the FT-IR analysis showed
that amines, carboxylic, C@O and CO could combine intensively
with metal ions.
3.2. Adsorption comparison for single heavy metal ions
3.2.1. Effects of contact time
Ideal biosorption materials are able to rapidly adsorb high concentrations of heavy metals from waste emissions and use chemical agents to desorb heavy metals from biosorption material (Singh
et al., 2007). For these reasons, the results of Spirogyra and Cladophora spp. adsorption on Pb(II) and Cu(II) used the relationship between heavy metal adsorption and contact time as a function, as
shown in Fig. 1a.
During the rst 30 min, adsorption rate of both materials was
extremely high, comprising approximately 95% of the total adsorption. Then, the rate began to drop toward a steady state, with insignicant levels of adsorption. The two adsorption materials reached
steady state for the same type of metal ion simultaneously, but
achieved steady state at different times for different metal ions.
As observed in the adsorption curve, the rapid adsorption of lead
in the rst twenty minutes, and the rapid adsorption of copper in
the rst thirty minutes, may be due to physical adsorption or ion
adsorption on the surface of the algae powder. Slower adsorption
that followed may have involved other mechanisms, such as complexation, micro-precipitation, and binding site saturation. This
study observed three phases of Spirogyra and Cladophora spp.
adsorption materials in the contact time adsorption curve: the initial phase, with rapid adsorption of heavy metal ions; the second
phase, with gradual slowing of the adsorption rate; and the

equilibrium phase, with no signicant increase in the removal rate.

Mohan et al. (2002) described similar results. It observed that two
biomaterials performed for various durations in different phases,
due to different adsorbed heavy metals. For the adsorption of Pb(II)
and Cu(II) single heavy metals, we discovered that the adsorption
capacity of Spirogyra algae was signicantly higher than that of
Cladophora algae. In comparing the characteristics of biomass,
FT-IR testing showed that functional groups were similar. However, plant bodies of Cladophora spp. often have large amounts of
epiphytic algae, thus causing differences in adsorption volume.
Furthermore, differences in adsorption volume may be due to differences in proteins, lipids, or the composition of other carbohydrates affecting the number of adsorption sites. The differences
may be due to the epiphytic algae on Cladophora spp., which affects
the quality of algae powder production.
3.2.2. Effects of pH on metal ion adsorption
Numerous studies show that pH is an important factor affecting
adsorption of heavy metals by biosorbents (Fourest and Roux,
1992; Lia et al., 2006). Thus, higher pH value may affect the number of negatively charged sites, which is highly dependent on the
dissociation of functional groups. In addition, H+ competes with
Pb(II) and Cu(II) for the same adsorption position (Gupta and
Rastogi, 2008; Gupta et al., 2006).
The results of the pH value effects of Cladophora and Spirogyra
algae powder on heavy metal adsorption are shown in Fig. 1b.
When pH value was below 5, the amount of heavy metal ions
that Spirogyra and Cladophora algae powder were able to absorb increased with increases in the pH value. In optimal pH and FT-IR
testing for metal ion adsorption, these two types of algae powder
included carboxylic groups capable of playing a predominant role
in the adsorption of Pb(II) and Cu(II) (Singh et al., 2007). When
pH was 5, the two types of algae powder reached their maximum
adsorption volume. The capacity of Spirogyra to adsorb Pb(II) and
Cu(II) was 87.2 mgg1 and 38.2 mgg1, respectively. The capacity
of Cladophora to adsorb Pb(II) and Cu(II) was 45.4 mgg1and
13.7 mgg1, respectively. However, when pH exceeded 5, the
capacity to absorb Pb(II) and Cu(II) decreased for both biosorbents.
This may have been due to the precipitation of copper hydroxides
and lead hydroxides (Gupta et al., 2006).
The formation of the precipitation of copper hydroxides and
lead hydroxides was related to Ksp, and the optimal pH value
was inuenced by the concentration of Cu2+ and Pb2+; therefore,

Table 1
Comparison of characteristics between Spirogyra spp. and Cladophora spp.
Characteristics

Cladophora spp.

Spirogyra spp.

Branches
Length of cell
Width of cell
Length of plant
Nucleate
Cell wall
Chloroplast
Epiphytic algae
FT-IR analysis for functional
groups

Yes
20100 lm
1540 lm
10200 cm
Multinucleate
Low pectate contain
Not belt distribution
Abundance
Wave number
Band assignment
(cm1)
3351
OH hydrogen bonded alcohol

No
20200 lm
2035 lm
530 cm
Mononucleate
High pectate contain
Belt distribution
Few
Band assignment
Wave number
(cm1)*
3622
OH monomeric alcohols, phenols, NH
amine stretches
3341
OH hydrogen bonded alcohol

2896
1658
1429
1336
1163 and 1059

Alkyl chains (CH3 and CH2 sym. and asym.

stretch)
C@O aldehydes, ketones, carboxylic acid
CO bend from carboxylate ions
Amide II (CN), COO groups of the fatty
acids
CO stretches. Alcohols, ethers, carboxylic
acid, esters

FT-IR analysis of Spirogyra spp. from Onyancha et al. (2008).

2925
2360
1656

CH alkane stretches
CC triple bond (alkynes)
C@O aldehydes, ketones, carboxylic acid

1038

CO stretches. Alcohols, ethers, carboxylic

acid, esters

Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

Adsorption(mg/g dry weight)

5300

100
80

Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)

60
40
20

(a)

0
0

10

20

30

40

50

60

70

Adsorption(mg/g dry weight)

Time(min)
100
Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)

80
60
40
20

(b)
0
2

Adsorption(mg/g dry weight)

pH
100
80
Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)

60
40
20

(c)

0
0

50

100

150

200

250

300

350

Adsorption(mg/g dry weight)

C0(mg/L)
100
Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)

80
60
40
20

(d)

0
0

10

12

M(g/L)
Fig. 1. (a) Changes in the Spirogyra and Cladophora spp. algae powder removal solution Pb(II) or Cu(II) reaction time. The pH value of the solution was set as 5.0. (b) With
different pH values, Spirogyra and Cladophora spp. powder removes Pb(II) or Cu(II) heavy metal solutions from water. The dosage of algae powder was 1.0 g L1. (c) Results of
Spirogyra and Cladophora spp. adsorption under various concentrations of heavy metal solution, with a pH value of 5.0. (d) Effects of various algae dosages on adsorption of
heavy metal solutions, with heavy metal concentrations of 100 mg L1 and pH value of 5.0.

the pH value of optimal adsorption of biomass could be a variable,

with the decrease of concentration of Cu2+ and Pb2+. The pH value
of optimal operation was between the pH value of the isoelectric
point and the pH value of forming hydrate sediments. Fig. 2 shows
the result of Zeta potential of adsorption of Cladophora spp. powder
in solutions without heavy metal ions, 100 mg L1 Cu2+, and
100 mg L1 Pb2+ at different pH values. The isoelectric point in
solutions without heavy metal ions was at a pH value of 4.6. The
isoelectric points after adsorbing 100 mg L1 Cu2+ and 100 mg L1
Pb2+ were respectively at pH values of 4.9, and 5.1. We could infer
that the optimal pH value of adsorption of heavy metals by bioma-

terials with adsorption capability might uctuate at a pH value

within a small range. Lower isoelectric point, the available sites
on surface of the biomass are protonated, hence sorption of cations
is more difcult (Naja et al., 2005). Therefore, determining the pH
value of the optimal operating condition through estimating
isoelectric point is a favorable method.
3.2.3. Effect of initial concentration of metal ions
The effects of Spirogyra and Cladophora algae on initial concentrations of Pb(II) and Cu(II) are shown in Fig. 1c. In this experiment,
we compared the adsorption capacity of Spirogyra and Cladophora

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Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

10

Zeta Potential [mV]

pH
0

-5

-10
algae powder
algae powder+Cu(II)
algae powder+Pb(II)
-15
Fig. 2. Zeta Potential of Cladophora spp. algae powder at different pH.

algae powders. The results indicated that the Spirogyra algae power
adsorption of Pb(II) and Cu(II) was greater than that of the Cladophora algae power. When Pb(II) and Cu(II) concentrations were
100 mg L1, both adsorption materials reached their highest degree of adsorption capacity for metal ions, thereby providing maximum removal rates for the two types of heavy metals present in
the solution. Since subsequent increases in adsorption capacity
were extremely low, the removal rate for metal ions signicantly
decreased. This may be due to the saturation of available sites on
algal cell surfaces preventing further adsorption of metal ions
(Volesky, 2003). Based on the results of this experiment, we used
metal ion concentrations of 100 mg L1, in subsequent experiments on adsorption.
3.2.4. Effect of algal dosage
The results of this experiment on adsorption for these two biosorbents under different dosages on Pb(II) and Cu(II) are as shown
in Fig. 1d. For these tests, we used metal ion concentrations of
100 mg L1.
As seen in Fig. 1d, metal adsorption volume was inversely proportional to the algae dosages, while the removal rate was proportional to the algae dosages. When the biosorbent was increased,
absorption of metal ions also increased. Low dosages of biosorbent
with high concentrations of heavy metals resulted in the highest
adsorption capacity.

0.12

(a)

3.3. Comparison of adsorption isotherms

Fig. 3 shows the adsorption results of Spirogyra and Cladophora
algae powder at 25 C for Pb(II) and Cu(II), respectively, as well as
the plots of 1/qe and 1/Ce, based on the Langmuir model (Eq. (2))
described previously and the Freundlich isotherms (Eq. (4)). The
plots of log qe versus log Ce, are shown in Fig. 3. The constants obtained from Langmuir and Freundlich isotherms had very high correlation coefcients (R2) (Table 2). Comparisons between
correlation coefcients, with the adsorption correlation values for
Spirogyra and Cladophora, t the Langmuir model better than the
Freundlich model. These values indicated a strong positive
correlation.
For the tting results of Langmuir isotherms (see Table 2), the
maximum Qmax and minimum b value of the Langmuir constants
were 90.91and 0.024, respectively, for Spirogyra Pb(II) adsorption.
In comparing the b value of the two biosorbents, each demonstrated differing adsorption results for different metal ions. Qmax
represents the maximum biosorption capacity of the biosorbent,
while the b value indicates the afnity of a biosorbent towards
an adsorbate.
For the tting results of the Freundlich model (see Table 2),
higher K values, and n values are 9.22 mgg1 and 2.44, respectively,
in the adsorption results for Spirogyra algae to Pb(II). A high K value
indicated a high adsorption volume. A high 1/n value (n > 1)

2.0

Spirogyra spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Cu(II)
Cladophora spp.-Pb(II)
Regression line

0.10

1.8
1.6

log qe

1/qe

0.08
0.06

1.4

0.04

1.2

0.02

1.0

0.00
0.00

(b)

0.8
0.01

0.02

0.03

1/Ce

0.04

0.05

0.06

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

log Ce

Fig. 3. Langmuir (a) and Freundlich (b) adsorption isotherms for Pb(II) and Cu(II) using Spirogyra and Cladophora spp. algae powder.

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Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

Table 2
Langmuir and Freundlich constants for Pb(II) and Cu(II) with Spirogyra and Cladophora biomass.
Algae

Spirogyra spp.
Cladophora spp.

Heavy metal ions

Langmuir constants

Cu(II)
Pb(II)
Cu(II)
Pb(II)

Freundlich constants

Qmax

R2

KF

R2

0.040
0.024
0.061
0.025

38.61
90.91
14.71
46.51

0.995
0.991
0.993
0.996

4.15
2.44
6.91
3.03

9.67
9.22
6.29
6.63

0.958
0.981
0.937
0.980

indicated high adsorption strength. Table 2 shows a comparison of

correlation coefcients for various biosorbents in the adsorption of
Pb(II) and Cu(II) (6.299.67). The results indicated that Spirogyra is
a better biosorbent material than Cladophora.
In comparing the adsorption test results of Pb(II) and Cu(II) for
both types of adsorption materials, the adsorption of Pb(II) had a
lower b value, indicating that both types of biosorbents had a higher afnity for Pb(II).

type of multi-metal ion solution showed similar characteristics of

inhibition in related studies (Singh et al., 2007; Yan et al., 2010).
These two types of adsorbents displayed stronger adsorption
inhibition towards binary metal system Pb(II) compared to Cu(II).
This indicated a higher afnity of these adsorbents towards Pb(II).
The afnity of metal ions for the binding sites seem to be related to
electronegativity, ionic radii, state of the surface and steric conguration, etc.

3.4. Comparison of Pb(II) and Cu(II) binary metal solution adsorption

3.5. Comparison of desorption efciency

Studying adsorption balance relationships in a systemized manner is extremely important in multi-metal systems. Adsorption is
affected by operational conditions, such as biomass surface characteristics and pH, as well as competition among various cations for
active biosorbent sites, and/or the cation screening effect, which
may interfere with biosorption capacity of the metals of interest
(Luna et al., 2010; Vilar et al., 2008).
The biosorption results of Pb(II) or Cu(II) by Spirogyra and Cladophora spp. from binary metal solutions containing various concentrations of Pb(II) and Cu(II) are shown in Fig. 4. Results clearly show
that the adsorption of the two algae tested mutually inhibit one
another. Compared with single metal ion solution adsorption, this

Numerous studies reported that HCl is very effective for desorbing heavy metals from biosorbents (Singh et al., 2007; Tuzen and
Sari, 2010). We used 0.5 M HCl on Pb(II) and Cu(II) for Spirogyra
and Cladophora algae powders to test the adsorptiondesorption
efciency. We discovered that 0.5 M HCl was highly effective, with
up to an 85% recovery rate for both Spirogyra and Cladophora algae
powders. Furthermore, these two types of biomass continued to
maintain high stability even after ve continuous adsorption
desorption processes. The results are shown in Fig. 5.
In every cycle, Cladophora Pb(II) and Cu(II) recovery rates were
more than 88.0% and 82.6%, respectively, while those for Spirogyra
Pb(II) and Cu(II) were more than 92.5% and 85.1%, respectively. As

Adsorption (mg/g)

100

(a)

80
Cu(II)-0
Cu(II)-100
Cu(II)-200
Pb(II)-0
Pb(II)-100
Pb(II)-200

60

40

20

50

100

150

200

250

300

350

C0 (mg/L)

Adsorption (mg/g)

50

(b)

40

Cu(II)-0
Cu(II)-100
Cu(II)-200
Pb(II)-0
Pb(II)-100
Pb(II)-200

30
20
10
0

50

100

150

200

250

300

350

C0(mg/L)
Fig. 4. (a) Spirogyra spp. and (b) Cladophora spp. from binary metal solutions containing various concentrations of Pb(II) and Cu(II).

Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 52975304

100

5303

Spirogyra spp.-adsorption
Spirogyra spp.-desorption
Cladophora spp.-adsorption
Cladophora spp.-desorption

(a)

Amount (%)

80

60

40

20

0
1

Cycle number

100

Spirogyra spp.-adsorption
Spirogyra spp.-desorption
Cladophora spp.-adsorption
Cladophora spp.-desorption

(b)

Amount (%)

80

60

40

20

0
1

Cycle number
Fig. 5. Adsorptiondesorption efciency for Pb(II) (a) and Cu(II) (b).

discovered in studies of this type of adsorptiondesorption cycle,

both Cladophora and Spirogyra were good biosorbents.

4. Conclusions
This study discovered that the adsorption effects of Spirogyra
spp. for Pb(II) and Cu(II) are superior to those of Cladophora spp.
FT-IR analysis indicated that the functional groups of these two
genera of algae are similar, but varied in their adsorption efciency. This may be due to the differences in protein, lipid, or other
carbohydrate content of the two genera of algae. Furthermore,
whether large amounts of epiphytic algae on Cladophora plant
bodies affect subsequent algae powder manufacturing and adsorption results warrants further study. Continuing adsorptiondesorption experiments have discovered that both types of biomass are
excellent biosorbents with potential for further development.
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