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Bioresource Technology 102 (2011) 5297–5304 Contents lists available at ScienceDirect Bioresource Technology

Contents lists available at ScienceDirect

Bioresource Technology

journal homepage: www.elsevi er.com/locate/biortech The biosorption of heavy metals from aqueous solution by

The biosorption of heavy metals from aqueous solution by Spirogyra and Cladophora filamentous macroalgae

Yi-Chao Lee, Shui-Ping Chang

Department of Environmental Engineering, Kun Shan University, Yung-Kang City, Tainan Hsien 71003, Taiwan, ROC

article info

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

abstract

The aim of this research was to develop a low cost adsorbent for wastewater treatment. The prime objec- tive of this study was to search for suitable freshwater filamentous 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 fit 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 significant than diffusion and adsorption between particles. Continuous adsorption–desorption 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 flows 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 efficient 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 efficient, low cost tech- niques 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 dis- tributed around the world, and closely connected with human life. In this study, we chose Spirogyra and Cladophora spp. as biosorp- tion materials due to their similar habitat distribution and close taxonomic grouping. Both are benthic filamentous 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 stud- ies have applied both living and dead specimens of these two mac- roalgae to nutrient removal ( DeBusk et al., 2004 ), biomonitoring ( Oertel, 1993 ), tannery and textile wastewater treatment ( Khalaf, 2008; Mohan et al., 2002; Özer 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 filamentous algae that have high heavy metal ion removal capability. This study evaluates the bio- sorption capacity of green algae, Spirogyra, and Cladophora spp., for Pb(II) and Cu(II) from aqueous solutions. We performed adsorp- tion 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 manufac- turing 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 respec- tive adsorption, using batch experiments to study kinetics and adsorption equilibrium. To understand desorption efficiency, we also performed continuous adsorption–desorption experiments on Spirogyra and Cladophora spp. algae powder for Pb(II) and Cu(II).

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Many studies have reported that Spirogyra and Cladophora spp. have a very high capacity for binding with metals due to the pres- ence 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

2.1. Preparation of the test algae and chemicals

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 filter paper to reduce water content. The biomass was then sun-dried for 4 days, followed by oven dry- ing 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 L 1 metal solutions were prepared using Pb(NO 3 ) 2 , and Cu(NO 3 ) 2 3H 2 O (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.

2.2. Optical microscopes examination and Fourier transform infrared

(FT-IR) spectroscopy analysis

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 filter. Fourier transform infrared (FT-IR) spectroscopy (Spectrum GX) was used to detect vibration fre- quency changes in dried Cladophora spp. biomass before and after Pb(II) and Cu(II) biosorption. Spectra within the range of 4000–

400

cm 1 were collected.

2.3.

Batch experiments for single-ion solution

2.3.1. Effect of pH

The experiment was conducted for biosorption at a concentra- tion of 100 mg L 1 of Cu(II) ions and 1.0 g L 1 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 L 1 and a biomass dose of 1.0 g L 1 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 L 1 were studied.

2.3.4. Effect of biosorbents dose

Different amounts of biomass doses ranging from 0.1 to

10.0 g L 1 for 50 mL of Pb(II) and Cu(II) solutions in a 250 mL Erlen- meyer flask were used, while maintaining a pH of 5.0, a tempera- ture of 25 C and concentrations of the Pb(II) and Cu(II) ions at

100 mg L 1 .

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 L 1 ) 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:

q ¼ ð C 0 C e Þ V= W

ð 1Þ

where q is the amount of Pb(II) or Cu(II) adsorbed by biomass (mgg 1 ), C 0 is the initial concentration of Pb(II) or Cu(II) ions (mg L 1 ), C e is the concentration of Pb(II) or Cu(II) at equilibrium (mg L 1 ), 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:

q e ¼ ðQ max bC e Þ =ð 1 þ bC e Þ

ð

2Þ

The logarithmic form of the equation is:

1= q e ¼ 1=Q max þ 1= C e ð bQ max Þ

ð

3Þ

where q e is the amount of metal ions sorbed (mgg 1 ) and C e is the equilibrium concentration (mg L 1 ). Q max represents maximum adsorption and b is the affinity between biosorbent and biosor- bate.The Freundlich isotherm is given as:

q e ¼ KC

1=n

e

The logarithmic form of the equation is given as:

log q e ¼ log K þ 1=n log C e

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

ð

4Þ

ð 5Þ

2.6. Successive adsorption–desorption 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 al- gae widely distributed throughout the world. We selected these two algae genera as adsorption materials and used optical micro- scopes 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 epi- phytic algae such as Chlorophyta, Cyanophyta, and Euglenophyta.

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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. Onyan- cha 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 C–O 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 con- centrations of heavy metals from waste emissions and use chemi- cal agents to desorb heavy metals from biosorption material ( Singh et al . , 2007 ). For these reasons, the results of Spirogyra and Clado- phora spp. adsorption on Pb(II) and Cu(II) used the relationship be- tween heavy metal adsorption and contact time as a function, as shown in Fig. 1 a. During the first 30 min, adsorption rate of both materials was extremely high, comprising approximately 95% of the total adsorp- tion. Then, the rate began to drop toward a steady state, with insig- nificant 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 first twenty minutes, and the rapid adsorption of copper in the first 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 com- plexation, 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 ini- tial phase, with rapid adsorption of heavy metal ions; the second phase, with gradual slowing of the adsorption rate; and the

equilibrium phase, with no significant 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 significantly higher than that of Cladophora algae. In comparing the characteristics of biomass, FT-IR testing showed that functional groups were similar. How- ever, 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 dif- ferences in proteins, lipids, or the composition of other carbohy- drates 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 num- ber 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. 1 b. When pH value was below 5, the amount of heavy metal ions that Spirogyra and Cladophora algae powder were able to absorb in- creased 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 mgg 1 and 38.2 mgg 1 , respectively. The capacity of Cladophora to adsorb Pb(II) and Cu(II) was 45.4 mgg 1 and 13.7 mgg 1 , 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 influenced by the concentration of Cu 2+ and Pb 2+ ; 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 20–100 l m 15–40 l m 10–200 cm Multinucleate Low pectate contain Not belt distribution Abundance Wave number

Band assignment

No 20–200 l m 20–35 l m 5–30 cm Mononucleate High pectate contain Belt distribution Few Wave number

Band assignment

(cm 1 )

(cm 1 ) *

3351

–OH hydrogen bonded alcohol

3622

–OH monomeric alcohols, phenols, N–H amine stretches

2896

Alkyl chains (CH 3 and CH 2 sym. and asym.

3341

–OH hydrogen bonded alcohol

1658

stretch) –C @ O aldehydes, ketones, carboxylic acid

2925

–C–H alkane stretches

1429

–CO bend from carboxylate ions

2360

–CC– triple bond (alkynes)

1336

Amide II (C–N), COO– groups of the fatty acids

1656

–C @ O aldehydes, ketones, carboxylic acid

1163 and 1059

–C–O stretches. Alcohols, ethers, carboxylic acid, esters

1038

–C–O stretches. Alcohols, ethers, carboxylic acid, esters

5300

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100 80 Spirogyra spp.-Cu(II) Cladophora spp.-Cu(II) 60 Spirogyra spp.-Pb(II) Cladophora spp.-Pb(II) 40 20 (a) 0
100
80
Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
60
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)
40
20
(a)
0
0
10
20
30
40
50
60
70
Adsorption(mg/g dry weight)

Time(min)

100 Spirogyra spp.-Cu(II) 80 Cladophora spp.-Cu(II) Spirogyra spp.-Pb(II) 60 Cladophora spp.-Pb(II) 40 20 (b) 0
100
Spirogyra spp.-Cu(II)
80
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
60
Cladophora spp.-Pb(II)
40
20
(b)
0
dry weight)Adsorption(mg/g

2345678

pH

100 80 Spirogyra spp.-Cu(II) Cladophora spp.-Cu(II) 60 Spirogyra spp.-Pb(II) Cladophora spp.-Pb(II) 40 20 (c) 0
100
80
Spirogyra spp.-Cu(II)
Cladophora spp.-Cu(II)
60
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)
40
20
(c)
0
0 50
100
150
200
250
300
350
Adsorption(mg/g dry weight)

C 0 (mg/L)

100 Spirogyra spp.-Cu(II) 80 Cladophora spp.-Cu(II) Spirogyra spp.-Pb(II) Cladophora spp.-Pb(II) 60 40 20 (d) 0
100
Spirogyra spp.-Cu(II)
80
Cladophora spp.-Cu(II)
Spirogyra spp.-Pb(II)
Cladophora spp.-Pb(II)
60
40
20
(d)
0
0
2
4
6
8
10
12
Adsorption(mg/g dry weight)

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 L 1 . (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 L 1 and pH value of 5.0.

the pH value of optimal adsorption of biomass could be a variable, with the decrease of concentration of Cu 2+ and Pb 2+ . 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 L 1 Cu 2+ , and 100 mg L 1 Pb 2+ 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 L 1 Cu 2+ and 100 mg L 1 Pb 2+ 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 fluctuate 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 difficult ( 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 concen- trations of Pb(II) and Cu(II) are shown in Fig. 1 c. In this experiment, we compared the adsorption capacity of Spirogyra and Cladophora

Y.-C. Lee, S.-P. Chang / Bioresource Technology 102 (2011) 5297–5304

5301

10 5 pH 0 2345678 -5 -10 algae powder algae powder+Cu(II) algae powder+Pb(II) -15 Zeta
10
5
pH
0
2345678
-5
-10
algae powder
algae powder+Cu(II)
algae powder+Pb(II)
-15
Zeta Potential [mV]

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 Clado- phora algae power. When Pb(II) and Cu(II) concentrations were 100 mg L 1 , both adsorption materials reached their highest de- gree of adsorption capacity for metal ions, thereby providing max- imum 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 significantly 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 L 1 , in subsequent experi- ments on adsorption.

3.2.4. Effect of algal dosage The results of this experiment on adsorption for these two bio- sorbents under different dosages on Pb(II) and Cu(II) are as shown in Fig. 1 d. For these tests, we used metal ion concentrations of 100 mg L 1 . As seen in Fig. 1 d, metal adsorption volume was inversely pro- portional to the algae dosages, while the removal rate was propor- tional 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.

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/ q e and 1/ C e , based on the Langmuir model (Eq. (2)) described previously and the Freundlich isotherms (Eq. (4) ). The plots of log q e versus log C e , are shown in Fig. 3 . The constants ob- tained from Langmuir and Freundlich isotherms had very high cor- relation coefficients ( R 2 ) ( Table 2 ). Comparisons between correlation coefficients, with the adsorption correlation values for Spirogyra and Cladophora , fit the Langmuir model better than the Freundlich model. These values indicated a strong positive correlation. For the fitting results of Langmuir isotherms (see Table 2 ), the maximum Q max 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 demon- strated differing adsorption results for different metal ions. Q max represents the maximum biosorption capacity of the biosorbent, while the b value indicates the affinity of a biosorbent towards an adsorbate. For the fitting results of the Freundlich model (see Table 2 ), higher K values, and n values are 9.22 mgg 1 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)

0.12 (a) 2.0 Spirogyra spp.-Cu(II) (b) Spirogyra spp.-Pb(II) Cladophora spp.-Cu(II) 0.10 1.8 Cladophora
0.12
(a)
2.0
Spirogyra spp.-Cu(II)
(b)
Spirogyra spp.-Pb(II)
Cladophora spp.-Cu(II)
0.10
1.8
Cladophora spp.-Pb(II)
Regression line
0.08
1.6
0.06
1.4
0.04
1.2
0.02
1.0
0.00
0.8
0.00
0.01
0.02
0.03
0.04
0.05
0.06
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
1/C e
log C e
1/q e
log q e

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

Algae

Heavy metal ions

Langmuir constants

Freundlich constants

 

b

Q max

R 2

n

K F

R 2

Spirogyra spp.

Cu(II)

0.040

38.61

0.995

4.15

9.67

0.958

Pb(II)

0.024

90.91

0.991

2.44

9.22

0.981

Cladophora spp.

Cu(II)

0.061

14.71

0.993

6.91

6.29

0.937

Pb(II)

0.025

46.51

0.996

3.03

6.63

0.980

indicated high adsorption strength. Table 2 shows a comparison of correlation coefficients for various biosorbents in the adsorption of Pb(II) and Cu(II) (6.29–9.67). 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 high- er affinity for Pb(II).

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

Studying adsorption balance relationships in a systemized man- ner is extremely important in multi-metal systems. Adsorption is affected by operational conditions, such as biomass surface charac- teristics 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 Clado- phora spp. from binary metal solutions containing various concen- trations 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

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 affinity of these adsorbents towards Pb(II). The affinity of metal ions for the binding sites seem to be related to electronegativity, ionic radii, state of the surface and steric config- uration, etc.

3.5. Comparison of desorption efficiency

Numerous studies reported that HCl is very effective for desorb- ing 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 adsorption–desorption efficiency. 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 five 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

100 (a) 80 60 40 20 0 Adsorption (mg/g)
100
(a)
80
60
40
20
0
Adsorption (mg/g)

Cu(II)-0

Cu(II)-100

Cu(II)-200

Pb(II)-0

Pb(II)-100

Pb(II)-200

0 50 100 150 200 250 300 350 C 0 (mg/L) 50 (b) 40 Cu(II)-0
0
50
100
150
200
250
300
350
C 0 (mg/L)
50
(b)
40
Cu(II)-0
Cu(II)-100
Cu(II)-200
30
Pb(II)-0
Pb(II)-100
Pb(II)-200
20
10
0
0
50
100
150
200
250
300
350
Adsorption (mg/g)

C 0 (mg/L)

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

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Spirogyra spp.-adsorption Spirogyra spp.-desorption 100 (a) Cladophora spp.-adsorption Cladophora spp.-desorption 80
Spirogyra spp.-adsorption
Spirogyra spp.-desorption
100
(a)
Cladophora spp.-adsorption
Cladophora spp.-desorption
80
60
40
20
0
12345
Cycle number
100
(b)
Spirogyra spp.-adsorption
Spirogyra spp.-desorption
Cladophora spp.-adsorption
Cladophora spp.-desorption
80
60
40
20
0
12345
Cycle number
Amount (%)
Amount (%)

Fig. 5. Adsorption–desorption efficiency for Pb(II) (a) and Cu(II) (b).

discovered in studies of this type of adsorption–desorption 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 effi- ciency. 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 adsorp- tion results warrants further study. Continuing adsorption–desorp- tion experiments have discovered that both types of biomass are excellent biosorbents with potential for further development.

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