Algal Biosorption of Heavy Metals

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Chapter

5

Algal Biosorption of Heavy Metals M. Jerold, C. Vigneshwaran, A. Surendhar, B.G. Prakash Kumar, and Velmurugan Sivasubramanian CONTENTS 5.1 Introduction 5.2 Salient Features of Brown Algae 5.2.1 A Comparison with Other Algae 5.2.2 Brown Macroalgae 5.3 Hi-Tech Crams of Algal Biosorption 5.3.1 Mechanisms of Heavy Metal Uptake by Algae 5.3.2 Key Functional Groups in the Algal Cell Wall 5.3.3 Ion Exchange 5.3.4 Complexation 5.3.5 Alginate and Its Role in Selectivity 5.4 Biosorption by Seaweed 5.5 Conclusion References

132 135 135 136 137 137 138 138 138 139 140 140 143

Abstract Metal-bearing effluent can be removed by conventional treatment such as chemical precipitation, electrochemical cells, reverse osmosis, and ion exchange; however, each treatment method has limitations. Sorption, particularly biosorption, has become one of the alternative treatments to conventional treatments of wastewaters and industrial 131

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effluents. The treatment of industrial wastewater from aqueous solutions employing biosorption technology is an advanced and novel technology. Basically, sorption is the process of assimilation of particles from one phase to another phase. The particles move from the bulk liquid and get amalgamated in the solid surface. The particles bound to the solid surface by physical (Van der Waal’s forces) or chemical interaction (chemical bonds). Biosorption has been chosen as an alternative remedial solution because of its high metal-uptake capacity, greater surface area with reactive sorbents, and, above all, low cost. Many biomaterials available in nature have been employed as biosorbents for the desired pollutant removal. Algae are of special interest for the development of new biosorbent material due to their high sorption capacity and ready availability in practically unlimited quantity. Particularly, macroalgae are found to have greater metal uptake capacity. Seaweed (macroalgae) collected from the ocean has shown impressive biosorption of metals. Brown algae, especially, contain high amounts of alginate, which are well protected within brown algae’s cellular structures, and copious carboxylic groups capable of capturing cations present in solutions. This chapter discusses the significance of the algal resource in the removal of metals from waste streams and provides a brief overview of marine brown algae, its properties, and their potential applications for biosorption.

5.1 INTRODUCTION Today, heavy metal pollution is one of the major problems in the environment. Various industries contribute to environmental pollution by the release of various hazardous materials. Such toxic materials are released including the mining and smelting industry, battery industry, energy and fuel production, fertilizer and chemical industry and application, iron and steel industry, electroplating, electrolysis, leatherworking, photography, electric appliance manufacturing, and nuclear power plants (Wang and Chen, 2009). Particularly, in the industrialized city, the following categories are important concerns (Volesky, 2007): • Accumulated acid mine drainage (AAMD), coupled with mining source • Waste metal solution from the electroplating industry (enlarged polluting industry)

Algal Biosorption of Heavy Metals    ◾   133

• Thermal power plants (throughput of coal and other hazardous materials)

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• Nuclear power plants (usage of toxic chemicals, such as uranium and polonium) The heavy metals are grouped into three main categories: toxic metals, radionuclides, and precious metals (Wang and Chen, 2006, 2009). Mercury, chromium, lead, copper, nickel, cadmium, and cobalt are listed under the category of toxic metals. The metals such as uranium, thorium, radium, and polonium are included under radionuclides. Precious metals include platinum, palladium, gold, and silver. There are three methods for the removal of metal ion from aqueous solution: physical, chemical, and biological technologies. Conventional methods have been practiced for many years for the removal of metal ions from various aqueous solutions (such as chemical precipitation, chemical and electrocoagulation, filtration, ion exchange, electrochemical treatment, membrane technologies, adsorption on activated carbon, zeolite, and evaporation). However, its operation is restricted nowadays due to various limitations and drawbacks. The membrane technologies and activated carbon adsorption process cannot be adopted for large-scale operations because they are extremely expensive and only a low concentration of heavy metals can be treated. The various other advantages and disadvantages of the conventional metal removal technologies are summarized by Volesky (2001). In order to improve the competitiveness of industrial operation processes, it is essential to develop and implement a cost-effective process for removal/recovery of metals. The various drawbacks such as high cost, less efficiency, release of secondary pollutants, etc. have led to the evolution of novel and sophisticated separation technologies (Volesky and Naja, 2007). Biohydrometallurgy is a modern trend based on the application of microbial interaction for the extraction of metals from specific raw materials. The biotechnological approach has opened up various processes for the recovery of metals. Therefore, integration of such promising technology in the recovery of metal from primary material (such as ores and concentrates) and secondary waste materials (such as mining, metallurgical, and power plant wastes) would certainly improve the process of metal recovery. The most promising biotechnological approach covers all the cutting-edge areas of biohydrometallurgy, which include bioleaching,

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bioprecipitation, bioflotation, bioflocculation, biooxidation, biosorption, bioreduction, bioaccumulation, and biosensors. These techniques are not only cost effective but also environmentally friendly. Biosorption is one such significant and widely applied biological process, whereby the sorption of metals takes place on the surface of the biomass. Microbial biomass provides a natural metal sink, by the process of biosorption where various toxic hazardous materials are adsorbed by the biomass. The biosorbents derived from microbial cells are effective for the removal of several metal ions from the solution, except the alkali metal ions such as Na+ and K+. However, this can be passively removed by living or dead organisms (Gadd, 1993). Biosorption is an entirely different form of bioaccumulation where sorption takes place on the surface of the biomass, which was pioneered by Volesky and his team in 1981 at McGill University (Montreal) (Tsezos and Volesky, 1981). Earlier, most research was carried out with live organisms (Lesmana et al., 2009). However, it was noticed that dead biomass possessed a greater metal removal capacity (Volesky, 1990), therefore, most researchers turned their attention towards biosorption (Asthana et al., 1995; Bossrez et al., 1997; Fourest and Roux, 1992; Holan et al., 1993; Niu et al., 1993; Selatnia et al., 2004; Yetis et al., 2000; Zhou, 1999). The research and development in biosorption have exploited various inactive and dead biomasses for the removal of toxic metal pollutants from wastewater. Hence, biomass derived from agro waste (Kuyucak, 1990), algal biomass, aquatic ferns, and dead microbial cells are used as biosorbents. Out of which macroalgae are reported to have an excellent biosorptive behavior (Kuyucak and Volesky, 1990) due to the presence of alginate in their cell walls. Algae in nature are broadly classified into microalgae and macroalgae, of which macroalgae is reported to have an imperative biosorption property. These macrophytes flourish largely in shallow coastal areas and are also present in the many areas of the oceanic parts of world. Generally macroalage (seaweed) are of three types based on their color: red, green, and brown, of which brown algae belonging to the class Phaeophyta is found to be an excellent biosorbent for the removal of metal ion from the aqueous solution. Various researchers have reported the inherent potential of brown algae (Hamdy, 2000; Kuyucak and Volesky, 1990; Ofer et al., 2003; Zhou et al., 1998). Thus, this chapter will describe the involvement

Algal Biosorption of Heavy Metals    ◾   135

of algae in the biosorption of heavy metals. Also, the behavior of brown algae in the sequestration of heavy metals is summarized.

5.2 SALIENT FEATURES OF BROWN ALGAE

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5.2.1 A Comparison with Other Algae Algae are an extensive and divergent group present in nature that possess chlorophyll and carry out oxygenic photosynthesis. Blue-green algae are also oxygenic phototrophs but they belong to a separate class of eubacteria (true bacteria). Basically algae are microscopic in morphological shape. Hence, they are also included under the group of microorganisms. Bold and Wynne (1985) classified algae into the following divisions: Cyanophyta, Prochlorophyta, Phaeophyta, Chlorophyta, Charophyta, Euglenophyta, Chrysophyta, Pyrrhophyta, Cryptophyta, and Rhodophyta. In our context we mainly discuss Phaeophyta (brown algae). The storage products distinguish the Phaeophyta from the other two groups Chlorophyta (green algae) and Rhodophyta (red algae). Laminaran is the main storage product in the case of Phaeophyta, whereas floridean starch is produced and stored in the Rhodophyta groups. Motility is a salient feature of the organism. Rhodophyta lacks the flagellar system; however, it is present in Chlorophyta and Phaeophyta. The cell wall chemistry plays an important role in the biosorptiom mechanism(s); however, the electrostatic attraction and complexation also contribute to the biosorption process. The other groups of algae are not suitable for the sorption, because Cryptophyta lacks cell walls (Lee, 1989) and Pyrrhophyta (dinoflagellates) can be “naked” or protected by cellulosic “thecal” plates (Bold and Wynne, 1985; Lee, 1989). Last, Chrysophyta can be either “naked” or even have an enveloped cell wall (Lee, 1989). The forms of algae commonly used in the sorption process are Phaeophyta, Rhodophyta, and Chlorophyta. These possess cellulose made of fibrillar skeleton material. However, the cellulose can be modified with xylan in Chlorophyta and Rhodophyta. Perhaps, in some cases, mannan is present in the Chlorophyta. In Phaephyta, the cell wall is embedded with alginate or alginic acid with trace amounts of sulfated glycans, whereas Rhodaphyta contains a large quantity of sulfated galactans. The extra polysaccharide accessories present in the cell wall are important factors for the sorption of metals. Hence, these classes of algae are potentially excellent for the biosorption of heavy metals.

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5.2.2 Brown Macroalgae Brown algae are classified into 265 genera and more than 1500 species (Bold and Wynne, 1985). The presence of carotenoid fucoxanthin in their chloroplast yields a brown color for these classes of algae. In addition the brown color is also due to the presence of pheophycean tannins. These algal species are found mainly in the littoral zone of the marine environment. These species are scattered in the brackish environment and known to exhibit as salt fenland fauna (Lee, 1989). The brown algae class Phaeophyta is divided into 13 orders (Bold and Wynne, 1985); however, only two orders are important for biosorption, namely, Laminariales and Fucales. These two orders are richly available in the marine environment. Among these two orders, Fucales is a huge and diversified order, with a range of morphological diversity (Bold and Wynne, 1985). One of the best genus of Fucales tested for biosorption is Sargassum. Figure 5.1 shows the cell wall structure in brown algae. A semispeculative model of brown algae with regard to the structure of the cell wall has been proposed (Kloareg et al., 1986). As discussed earlier, cellulose forms the strong backbone structural network in which biopolymers such as xylofucoglucans, xylofucoglycuronans, alginates, and homofucans are linked. The alginic content of various Sargassum species is summarized in Table 5.1. The biosorption performance is also due to the presence of two common moieties: sulfate esters in the cellular polysaccharides and the presence

Outside Outer cell wall amorphous embedding matrix

Cellulose fibers

Inner cell wall fibrillar skeleton

Protein

Phospholipid

Alginate and fucoidan matrix

Inside

FIGURE 5.1 Cell wall structure in brown algae. (From Schiewer, S., Volesky, B., 2000, Biosorption by marine algae, in Remediation, edited by J.J. Valdes, 139–169, Dordrecht, Netherlands: Kluwer Academic Publishers.)

Algal Biosorption of Heavy Metals    ◾   137 TABLE 5.1

Alginic Acid Contents of Sargassum

Sargassum Species

Alginic Acid (Percent of Dry Weight)

Sargassum longifolium Sargassum wightii Sargassum tenerium Sargassum fluitans Sargassum oligocystum

17% 30% 35% 45% ≈45%

Source: Adapted from Davis, T.A. et al., Water Research 37:4311– 4330, 2003.

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TABLE 5.2

Binding Groups in Brown Algae

Binding Chemical Group

Ligand Atom

Carboxyl Thiol Sulfonate Amine Amide

Oxygen Sulfur Sulfur Nitrogen Nitrogen

Biopolymer

Alginic acid Amino acids Sulfate polysaccharides fucoidan Amino acids peptidoglycan Amino acids

Source: Adapted from Ofer, R. et al., Biotechnology and Bioengineering 87: 451–458, 2004.

of polyuronides (Holan et al., 1993). Hence, the presence of functional groups in the uronic acids and the availability of sulfated moieties serve as excellent ligands for the sorption of metal ions from aqueous solution (Crist et al., 1991). Table 5.2 lists the major binding groups present in the brown algae.

5.3 HI-TECH CRAMS OF ALGAL BIOSORPTION 5.3.1 Mechanisms of Heavy Metal Uptake by Algae Apparently, there is no complete evidence for the mechanism behind the biosorption of metal. However, it is believed that metal biosorption is due to the formation of ions on the surface of the biomass. Biosorption of metals is a two-step process. First, the metals ions bind and, second, the metal ions accumulate on the binding sites (Ahluwalia and Goyal, 2003). The metal uptake capacity of algal biomass depends on the availability of polysaccharide contents such as alginates and fucoidans on the cell surface (Herrero et al., 2006). Perhaps, marine brown alga has rich content of extracellular polysaccharide. Hence, they exhibit a prosperous metal sorption compared to other algal species (Herrero et al., 2006).

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5.3.2 Key Functional Groups in the Algal Cell Wall A typical brown algal biomass consists of abundant carboxylic groups that are principally acidic functional groups. Esterification of carboxylic sites occurs during the reduction of cadmium and lead by Sargassum biomass (Fourest and Volesky, 1996). Fourier transform infrared (FTIR) analysis reveals that formation of complex with the carboxylate groups of alginate moieties (Fourest and Volesky, 1996) as explained by Rees and coworkers (Rees et al., 1982; Thom et al., 1982) in the “egg-box” model. Sulfonic acid is the second most abundant functional group present in brown algae. However, it plays only a secondary role in the biosorption process and shows its action only at the acidic pH level. Likewise, hydroxyl groups are present in all polysaccharides, which are less abundant in brown algae and comes into existence only at pH >10. 5.3.3 Ion Exchange Ion exchange is the principal mechanism for algal biosorption (Herrero et al., 2006; Kaewsarn, 2002; Ofer et al., 2004). It is known that alginate plays an important role in algal biosorption, therefore, it is appropriate that ion exchange takes place between the binding of metals and alginate moiety (Myklestad, 1968). In the biosorption of cobalt by Ascophyllum nodosum, there was an enhanced release of ions, including Ca2+, K+, Mg2+, and Na+, from the algae in the cobalt-bearing solution compared to the cobalt-free solution (Kuyucak and Volesky, 1989a,b,c). Hence, it is proved and concluded that ion exchange was the prevailing mechanism behind the biosorption. Treated biomass has been shown to have high sorption. The treatment can be made by any one of the chemical modifications. First, the protonation of biomass with strong acid will displace the light metals occupying the binding sites such as carboxylic, sulfonic, and others. Second, treating the biomass at high concentration of the given metal solution possibly most of the sites are occupied with potassium or calcium. Raw Sargassum, when allowed contact with heavy metal ion solution, releases light metal ions from the biomass because, generally, the raw biomass contains light metal ions such as K+, Na+, Ca2+, and Mg2+, which bind to the acid functional group of alga. 5.3.4 Complexation Complex formation is also a kind of mechanism for metal biosorption. The metal complexation in brown algae is well addressed by the binding

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of metal ions with alginate. Haug (1961) reported that during the binding of metal-ion to the alginic acid extracted from Laminaria digitata protons are released into the solution, which get diminished in the order Pb2+ > Cu2+ > Cd2+ > Ba2+ > Sr2+ > Ca2+ > Co2+ > Ni2+ > Mn2+ > Mg2+. Therefore, the metal sequestration is a complexation or coordination process of centralized heavy metals to the alginate, a multidendate ligand. Further, the egg-box model explains the steric interaction of ligand and metal ion supported by x-ray diffraction (Mackie et al., 1983) and nuclear magnetic resonance spectroscopic analyses (Steginsky et al., 1992). 5.3.5 Alginate and Its Role in Selectivity A description of ion exchange and its involvement in the biosorption process was given in the preceding section. Thus, we will briefly cover the importance of the macromolecular structure alginate in the metal selectivity process of biosorption. Alginate is the common term applied to a polysaccharide family containing acid residues 1,4-linked α-D-mannuronic (M) and R-L-guluronic (G) in blockwise fashion, as shown in Figure 5.2. The affinity of alginate toward the divalent metal ion is determined by the availability of M and G residues in the alginate macromolecular structures (Haug, 1967). COO–

COO– O O

HO

HO

O

O O

HO

HO

HO

HO

HO

O

O

O

HO

COO–

COO–

(a)

COO– O

COO–

HO O OH

OH O

O

HO

O OH

OH O

O

O

O (b)

HO

COO– HO

COO–

Main sections of alginic acid: (a) poly(D-mannuronosyl) segment and (b) poly(L-gluronosyl) segment.

FIGURE 5.2

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5.4 BIOSORPTION BY SEAWEED The large surface area of seaweeds is an advantage for the biosorption process. They contain the polyfunctional groups on the metal-binding site for both cationic and anionic complexes, as shown in Figure 5.3. In the cell wall of algal biomass, a good number of cationic binding sites are present, which include carboxyl, amine, imidazole, phosphate, sulfate, sulfhydryl, and hydroxyl. In addition, some functional groups are identified in the cell proteins and sugar molecules. The ligands of seaweeds form an ionic interaction with metal ions in the solutions, which is the virtual mechanism behind the binding (Yun et al., 2001). All seaweeds collected from the oceanic regions are shown to have an impressive metal sorption property (Kuyucak and Volesky, 1990). Table 5.3 shows the application of various macroalgae in the biosorption of metals, and Table 5.4 gives a gist of various operating parameters for a higher sorption. Brown seaweeds are highly suited for the binding of metal ions because of their rich content of polysaccharides in the cell wall (Percival and McDowell, 1967). Figure 5.4 shows the surface morphological changes during Cr (VI) biosorption.

5.5 CONCLUSION The chapter has summarized the admirable achievements of algal biosorption that have been gathered over the past two decades, especially the significance of marine brown algal biosorption. It is significant to realize that

H

H –O3SO

H

CH3

OH

O H

O H

H

–O3SO

O

H H

O

CH3

H

OH H –O3SO

H H

CH3

OH

H

H O H

O H

H

O O HO

CH H 3 OH H

H

H O

CH H 3

–O3SO –O3SO

H

O H

H

O

Structure of fucoidan. (From Davis, T.A. et al., Water Research 37: 4311–4330, 2003.)

FIGURE 5.3

Algal Biosorption of Heavy Metals    ◾   141 TABLE 5.3

Macroalgae Used for the Biosorption of Metals

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Macro Algae

Ascophyllum sp. Cladophora crispata Cladophora fascicularis Fucus ceranoides Fucus serratus Fucus spiralis Gracilaria fischeri Gracilaria sp. Jania rubrens Laminaria digitata Laurencia obtusa Palmaria palmata Petalonia fascia Porphyra columbina Sargassum asperifolium Sargassum hemiphyllum Sargassum hystrix Sargassum natans Sargassum vulgaris Sargassum kjellmanianum Turbinaria conoides Ulva fascia Ulva lactuca

Sorbate Used

Reference

Pb, Cd Cd, Pb, Cu, Ag Pb Cd Cd Cu Cd, Cu Pb, Cu, Cd, Zn, Ni Pb Cd, Zn, Pb, Cu Cr, Co, Ni, Cu, Cd Cu Cu, Ni Cd Pb Cu, Ni Pb Pb Cd, Ni Cd, Cu Pb Cu, Ni Pb

Volesky and Holan, 1995 Gin et al., 2002 Deng et al., 2007 Herrero et al., 2006 Herrero et al., 2006 Murphy et al., 2007 Chaisuksant, 2003 Sheng et al., 2004 Hamdy, 2000 Sandau et al., 1996 Hamdy, 2000 Murphy et al., 2007 Schiewer and Wong, 2000 Basso et al., 2002 Hamdy, 2000 Schiewer and Wong, 2000 Jalali et al., 2002 Jalali et al., 2002 Ofer et al., 2003 Zhou et al., 1998 Senthilkumar et al., 2007 Schiewer and Wong, 2000 Hamdy, 2000

20 years prior, knowledge on the mechanism of biosorption was vague. Today, scientists and engineers have identified the various technological phenomena behind the process of biosorption. And another development is the exploitation of various bioresources for the remediation of heavy metals. Brown algae have contributed to solving the problems that have arisen due to heavy metal pollution. The various traits of brown algae and their influence over of heavy metal sequestration have been explained. Thus, it is important to recognize the key aspects of algae in metal sorption. Finally, it should be noted that algae are not only applied for biosorption of heavy metals but also for the treatment of various rare earth metals. Hence, macroalgae are considered giant biosorbents for the removal of metals.

Sargassum sp. Ulva reticulate Fucus vesiculosus Sargassum myriocystum Pithophora varia

Green

Brown Green Olivebrown Brown

Chromium (III)

60.6

179.5

135.5

69.4

Lead

Total chromium Zinc (II)

Brown

115.00

0.90 mmol/g 74.63 1.85 mmol/g

Copper (II)

Brown

147.06

439.40

Adsorption Capacity (mg/g)

Cadmium Copper (II) Copper (II)

Copper

Brown

Green

Lead

Adsorbate

Brown

Color

5.0

5.0

4.5 5.5 –

5.5

2.0

4.5

6.0

4.5

pH

20°C

25°C

– – –

30°C







30°C

Temperature

Comparison of Metal Uptake Capacity of Different Marine Algae

Turbinaria conoides Turbinaria ornata Sargassum wightii Sargassum polcysstum Ulva reticulate

Adsorbent (Seaweed)

TABLE 5.4





Pseudo second order Pseudo second order – – –







Kinetic Model

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Langmuir



– Freundlich Langmuir

Langmuir



Langmuir

Langmuir

Langmuir

Isotherm

Michalak et al., 2007

Davis and Volesky, 2000 Vijayaraghavan et al., 2004 Ahmady-Asbchin and Mohammadi, 2011 Jeba et al., 2014

Senthilkumar et al., 2006

Vijayaraghavan and Prabu, 2006 Senthilkumar et al., 2010

Vijayaraghavan et al., 2004

Senthilkumar et al., 2007

Reference

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Algal Biosorption of Heavy Metals    ◾   143

5.0 kV 32.0 mm × 3.00 k SE

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(a)

10.0 µm

5.0 kV 26.8 mm × 3.00 k SE

10.0 µm

(b)

FIGURE 5.4 SEM image of Sargassum: (a) before Cr (VI) sorption, (b) after Cr

(VI) sorption.

REFERENCES Ahluwalia, S.S., Goyal, D. 2003. Removal of lead from aqueous solution by different fungi. Indian Journal of Microbiology 43, no. 4:237–241. Ahmady-Asbchin, S., Mohammadi, M. 2011. Biosorption of copper ions by marine brown alga Fucus vesiculosus. Journal of Biological and Environmental Sciences 5, no. 15:121–127. Asthana, R.K., Chatterjee, S., Singh, S.P. 1995. Investigations on nickel biosorption and its remobilization. Process Biochemistry 30:729–734. Basso, M.C., Cerrella, E.G., Cukierman, A.L. 2002. Empleo de algas marinas para la biosorcion de metales pesados de aguas contaminadas asides. Avances en Energías Renovables y Medio Ambiente 6:69–74. Bold, H.C., Wynne, M.J. 1985. Introduction to the Algae. Englewood Cliffs, NJ: Prentice-Hall. Bossrez, S., Remacle, J., Coyette, J. 1997. Adsorption of nickel on Enterococcus hirae cell walls. Journal of Chemical Technology and Biotechnology 70:45–50. Chaisuksant, Y. 2003. Biosorption of cadmium (II) and copper (II) by pretreated biomass of marine alga Gracilaria fisheri. Environmental Technology 24:1501–1508. Crist, R.H., Martin, J.R., Crist, D.R. 1991. Interaction of metals and protons with algae. Equilibrium constants and ionic mechanisms for heavy metal removal as sulfides and hydroxides. In Mineral Bioprocessing, edited by R.W. Smith and M. Misra, 275–287. Washington, DC: Minerals, Metals and Materials Society. Davis, T.A., Volesky, B., Mucci, A. 2003. A review of the biochemistry of heavy metal biosorption by brown algae. Water Research 37:4311–4330. Davis, T.A., Volesky, B., Vieira, R.H.S.F. 2000. Sargassum seaweed as biosorbent for heavy metals. Water Research 34, no. 17:4270–4278.

Downloaded by [JEROLD M] at 04:28 14 December 2016

144 ◾ Environmental Sustainability Using Green Technologies Deng, L., Su, Y., Su, H., Wang, X., Zhu, X. 2007. Sorption and desorption of lead (II) from wastewater by green algae Cladophora fascicularis. Journal of Hazardous Materials 143:220–225. Fourest, E., Roux, J.C. 1992. Heavy-metal biosorption by fungal mycelial byproducts—Mechanisms and influence of pH. Applied Microbiology and Biotechnology 37:399–403. Fourest, E., Volesky, B. 1996. Contribution of sulfonate groups and alginate to heavy metal biosorption by the dry biomass of Sargassum fluitans. Environmental Science and Technology 30, no. 1:277–282. Gadd, G.M. 1993. Interactions of fungi with toxic metals. New Phytologist 124:25–60. Gin, K.Y., Tang, Y.Z., Aziz, M.A. 2002. Derivation and application of a new model for heavy metal biosorption by algae. Water Research 36:1313–1323. Hamdy, A.A. 2000. Removal of Pb2+ by biomass of marine algae. Current Microbiology 41:239–245. Haug, A. 1961. The affinity of some divalent metals to different types of alginates. Acta Chemica Scandinavica 15:1794–1799. Herrero, R., Cordero, B., Lodeiro, P., Rey-Castro, C., Vicente, M.E.S.D. 2006. Interactions of cadmium (II) and protons with dead biomass of marine algae Fucus sp. Marine Chemistry 99:106–116. Holan, Z.R., Volesky, B., Prasetyo, I. 1993. Biosorption of cadmium by biomass of marine algae. Biotechnology and Bioengineering 41:819–825. Jalali, R., Ghafourian, H., Asef, Y., Davarpanah, S.J., Sepehr, S. 2002. Removal and recovery of lead using nonliving biomass of marine algae. Journal of Hazardous Materials 92:253–262. Jeba Sweetly, D., Sangeetha, K., Suganthi, B. 2014. Biosorption of heavy metal lead from aqueous solution by non-living biomass of Sargassum myriocystum. International Journal of Application or Innovation in Engineering & Management 3, no. 4:39–40. Kaewsarn, P. 2002. Biosorption of copper(II) from aqueous solutions by pretreated biomass of marine algae Padina sp. Chemosphere 4:1081–1085. Kloareg, B., Demarty, M., Mabeau, S. 1986. Polyanionic characteristics of purified sulfated homofucans from brown algae. International Journal of Biological Macromolecules 8:380–386. Kuyucak, N. 1990. Feasibility of biosorbents application. In Biosorption of Heavy Metals, edited by B. Volesky, 371–378. Boca Raton: CRC Press. Kuyucak, N., Volesky, B. 1989a. Accumulation of cobalt by marine alga. Biotechnology and Bioengineering 33, no. 7:809–814. Kuyucak, N., Volesky, B. 1989b. Desorption of cobalt-laden algal biosorbent. Biotechnology and Bioengineering 33, no. 7:815–822. Kuyucak, N., Volesky, B. 1989c. The mechanism of gold biosorption. Biorecovery 1:219–235. Kuyucak, N., Volesky, B. 1990. Biosorption by algal biomass. In Biosorption of Heavy Metals, edited by B. Volesky, 173–198. Boca Raton: CRC Press. Lee, R.E. 1989. Phycology. Cambridge, UK: Cambridge University Press.

Downloaded by [JEROLD M] at 04:28 14 December 2016

Algal Biosorption of Heavy Metals    ◾   145 Lesmana, S.O., Febriana, N., Soetaredjo, V., Sunarso, J., Ismadji, S. 2009. Studies on potential applications of biomass for the separation of heavy metals from water and wastewater. Biochemical Engineering Journal 44:19–41. Mackie, W., Perez, S., Rizzo, R., Taravel, F., Vignon, M. 1983. Aspects of the conformation of polyguluronate in the solid state and in solution. International Journal of Biological Macromolecules 5:329–341. Michalak, I., Zielinska, A., Chojnacka, K., Matula, J. 2007. Biosorption of Cr (III) by microalgae and macroalgae: Equilibrium of the process. American Journal of Agricultural and Biological Sciences 2, no. 4:284–290. Murphy, V., Hughes, H., McLoughlin, P. 2007. Cu (II) binding by dried biomass of red, green and brown macroalgae. Water Research 41:731–740. Myklestad, S. 1968. Ion-exchange properties of brown algae. Determination of rate mechanism for calcium–hydrogen ion exchange for particles from Laminaria hyperborea and Laminaria digitata. Journal of Applied Chemistry 18:30–36. Niu, H., Xu, X.S., Wang, J.H., Volesky, B. 1993. Removal of lead from aqueous-solutions by Penicillium biomass. Biotechnology and Bioengineering 42:785–787. Ofer, R., Yerachmiel, A., Yannai, S. 2003. Marine macroalgae as biosorbents for cadmium and nickel in water. Water Environmental Research 75:246–253. Ofer, R., Yerachmiel, A., Yannai, S. 2004. Mechanism of biosorption of different heavy metals by brown marine macroalgae. Biotechnology and Bioengineering 87:451–458. Percival, E.G.V., McDowell, R.H. 1967. Chemistry and Enzymology of Marine Algal Polysaccharides. London: Academic Press. Rees, D.A., Morris, E.R., Thom, D., Madden, J.K. 1982. Shapes and interactions of carbohydrate chains. In The Polysaccharides, vol. 1 (Molecular Biology: An International Series of Monographs and Textbooks), edited by G.O. Aspinall, 195–290. New York: Academic Press. Sandau, E., Sandau, P., Pulz, O., Zimmermann, M. 1996. Heavy metal sorption by marine algae and algal by-products. Acta Biotechnologica 16:103–119. Schiewer, S., Volesky, B. 2000. Biosorption by marine algae. In Remediation, edited by J.J. Valdes, 139–169. Dordrecht, Netherlands: Kluwer Academic Publishers. Schiewer, S., Wong, M.H. 2000. Ionic strength effects in biosorption of metals by marine algae. Chemosphere 41:271–282. Selatnia, A., Boukazoula, A., Kechid, N., Bakhti, M.Z., Chergui, A., Kerchich, Y. 2004. Biosorption of lead (II) from aqueous solution by a bacterial dead Streptomyces rimosus biomass. Biochemical Engineering Journal 19:127–135. Senthilkumar, R., Vijayaraghavan, K., Jegan, J., Velan, M. 2010. Batch and column removal of total chromium from aqueous solution using Sargassum polycystum. Environmental Progress and Sustainable Energy 29, no. 3:334–341. Senthilkumar, R., Vijayaraghavan, K., Thilakavathi, M., Iyer, P.V.R., Velan, M. 2007. Application of sea weeds for the removal of lead from aqueous solution. Biochemical Engineering Journal 33:211–216.

Downloaded by [JEROLD M] at 04:28 14 December 2016

146 ◾ Environmental Sustainability Using Green Technologies Senthilkumar, R., Vijayaraghavan, K., Thilakavathi, M., Iyer, P.V.R., Velan, M. 2006. Seaweeds for the remediation of wastewaters contaminated with zinc (II) ions. Journal of Hazardous Materials 136, no. 3:791–799. Sheng, P.X., Tan, L.H., Chen, J.P., Ting, Y.P. 2004. Biosorption performance of two brown marine algae for removal of chromium and cadmium. Journal of Dispersion Science and Technology 25:681–688. Steginsky, C.A., Beale, J.M., Floss, H.G., Mayar, R.M. 1992. Structural determination of alginic acid and the effects of calcium binding as determined by highfield NMR. Carbohydrate Research 225, no. 1:11–26. Thom, D., Grant, G.T., Morris, E.R., Rees, D.A. 1982. Characterisation of cation binding and gelation of polyuronates by circular dichroism. Carbohydrate Research 100:29–42. Tsezos, M., Volesky, B. 1981. Biosorption of uranium and thorium. Biotechnology and Bioengineering 23:583–604. Vijayaraghavan, K., Jegan, J., Palanivelu, K., Velan, M. 2004. Copper removal from aqueous solution by marine green alga Ulva reticulata. Electronic Journal of Biotechnology 7, no. 1:20–30. Vijayaraghavan, K., Prabu, D. 2006. Potential of Sargassum wightii biomass from copper (II) removal from aqueous solutions: Application of different mathematical models to batch and continuous biosorption data. Journal of Hazardous Materials 137, no. 1:558–564. Volesky, B. 1990. Biosorption of heavy metals. Boca Raton: CRC Press. Volesky, B. 2001. Detoxification of metal-bearing effluents: Biosorption for the next century. Hydrometallurgy 59:203–216. Volesky, B. 2007. Biosorption and me. Water Research 41:4017–4029. Volesky, B., Holan, Z.R. 1995. Biosorption of heavy metals. Biotechnology Progress 11:235–250. Volesky, B., Naja, G. 2007. Biosorption technology: Starting up an enterprise. International Journal of Technology Transfer and Commercialisation 6:196–211. Wang, J.L., Chen, C. 2006. Biosorption of heavy metals by Saccharomyces cerevisiae: A review. Biotechnology Advances 24:427–451. Wang, J.L., Chen, C. 2009. Biosorbents for heavy metals removal and their future a review. Biotechnology Advances 27:195–226. Yetis, U., Dolek, A., Dilek, F.B., Ozcengiz, G. 2000. The removal of Pb (II) by Phanerochaete chrysosporium. Water Research 34:4090–4100. Yun, Y.S., Parck, D., Park, J.M., Volesky, B. 2001. Biosorption of trivalent chromium on the brown seaweed biomass. Environmental Sciences and Technology 35:4353–4358. Zhou, J.L. 1999. Zn biosorption by Rhizopus arrhizus and other fungi. Applied Microbiology and Biotechnology 51:686–693. Zhou, J.L., Huang, P.L., Lin, R.G. 1998. Sorption and desorption of Cu and Cd by macroalgae and microalgae. Environmental Pollution 10:67–75.