Microbial and plant derived biomass for removal of heavy metals from wastewater

Bioresource Technology 98 (2007) 2243–2257

Review

Microbial and plant derived biomass for removal of heavy metals from wastewater Sarabjeet Singh Ahluwalia, Dinesh Goyal

*

Department of Biotechnology & Environmental Sciences, Thapar Institute of Engineering & Technology, Patiala 147 004, Punjab, India Received 12 July 2005; received in revised form 29 November 2005; accepted 2 December 2005 Available online 19 January 2006

Abstract Discharge of heavy metals from metal processing industries is known to have adverse effects on the environment. Conventional treatment technologies for removal of heavy metals from aqueous solution are not economical and generate huge quantity of toxic chemical sludge. Biosorption of heavy metals by metabolically inactive non-living biomass of microbial or plant origin is an innovative and alternative technology for removal of these pollutants from aqueous solution. Due to unique chemical composition biomass sequesters metal ions by forming metal complexes from solution and obviates the necessity to maintain special growth-supporting conditions. Biomass of Aspergillus niger, Penicillium chrysogenum, Rhizopus nigricans, Ascophyllum nodosum, Sargassum natans, Chlorella fusca, Oscillatoria anguistissima, Bacillus firmus and Streptomyces sp. have highest metal adsorption capacities ranging from 5 to 641 mg g 1 mainly for Pb, Zn, Cd, Cr, Cu and Ni. Biomass generated as a by-product of fermentative processes offers great potential for adopting an economical metal-recovery system. The purpose of this paper is to review the available information on various attributes of utilization of microbial and plant derived biomass and explores the possibility of exploiting them for heavy metal remediation.  2005 Elsevier Ltd. All rights reserved. Keywords: Biosorption; Non-living microbial biomass; Wastewater; Heavy metals

1. Introduction Increased use of metals and chemicals in process industries has resulted in generation of large quantities of effluent that contain high level of toxic heavy metals and their presence poses environmental–disposal problems due to their non-degradable and persistence nature. In addition mining, mineral processing and extractive-metallurgical operations also generate toxic liquid wastes. Environmental engineers and scientists are faced with the challenging task to develop appropriate low cost technologies for effluent treatment. Conventional methods for removing metals from aqueous solutions include chemical precipitation, chemical oxidation or reduction, ion exchange, filtration, electrochemical treatment, reverse osmosis, membrane technologies and evaporation recov*

Corresponding author. E-mail address: [email protected] (D. Goyal).

0960-8524/$ - see front matter  2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2005.12.006

ery. These processes may be ineffective or extremely expensive especially when the metals in solution are in the range of 1–100 mg l 1 (Nourbakhsh et al., 1994). Another major disadvantage with conventional treatment technologies is the production of toxic chemical sludge and its disposal/ treatment becomes a costly affair and is not eco-friendly. Therefore, removal of toxic heavy metals to an environmentally safe level in a cost effective and environment friendly manner assumes great importance. In light of the above, biological materials have emerged as an economic and eco-friendly option. Biomaterials of microbial and plant origin interact effectively with heavy metals. Metabolically inactive dead biomass due to their unique chemical composition sequesters metal ions and metal complexes from solution, which obviates the necessity to maintain special growth-supporting conditions. Metal-sorption by various types of biomaterials can find enormous applications for removing metals from solution and their recovery.

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Rather than searching thousands of microbial species for particular metal sequestering features, it is beneficial to look for biomasses that are readily available in large quantities to support potential demand. While choosing biomaterial for metal sorption, its origin is a major factor to be taken into account, which can come from (a) microorganisms as a by-product of fermentation industry, (b) organisms naturally available in large quantities in nature and (c) organisms cultivated or propagated for biosorption purposes using inexpensive media. Different non-living biomass types have been used to adsorb heavy metal ions from the environment (de Rome and Gadd, 1991; Tiemann et al., 1999). Seaweed, mold, bacteria, crab shells and yeast are among the different kinds of biomass, which have been tested for metal biosorption or removal (Volesky and Holan, 1995).

wastewater. Current research activity in this field is focused on evaluating, whether biosorption may eventually provide such an effective and economic alternative treatment process, while biological treatment is reasonably effective in removing organic pollutants, heavy metals however tend to accumulate in biological sludge, which is unfit as fertilizers and require incineration for its disposal (Tien and Huang, 1991).

2. Metals in wastewater and their toxicity

1. Precipitation is the most common method for removing toxic heavy metals up to parts per million (ppm) levels from water. Since some metal salts are insoluble in water and which get precipitated when correct anion is added. Although the process is cost effective its efficiency is affected by low pH and the presence of other salts (ions). The process requires addition of other chemicals, which finally leads to the generation of a high water content sludge, the disposal of which is cost intensive (Gray, 1999). Precipitation with lime, bisulphide or ion exchange lacks the specificity and is ineffective in removal of the metal ions at low concentration. 2. Ion exchange is another method used successfully in the industry for the removal of heavy metals from effluents. Though it is relatively expensive as compared to the other methods, it has the ability to achieve ppb levels of clean up while handling a relatively large volume. An ion exchanger is a solid capable of exchanging either cations or anions from the surrounding materials. Commonly used matrices for ion exchange are synthetic organic ion exchange resins. The disadvantage of this method is that it cannot handle concentrated metal solution as the matrix gets easily fouled by organics and other solids in the wastewater. Moreover ion exchange is nonselective and is highly sensitive to pH of the solution. 3. Electro-winning is widely used in the mining and metallurgical industrial operations for heap leaching and acid mine drainage. It is also used in the metal transformation and electronics and electrical industries for removal and recovery of metals. Metals like Ag, Au, Cd, Co, Cr, Ni, Pb, Sn and Zn present in the effluents can be recovered by electro-deposition using insoluble anodes (Gray, 1999). 4. Electro-coagulation is an electrochemical approach, which uses an electrical current to remove metals from solution. Electro-coagulation system is also effective in removing suspended solids, dissolved metals, tannins and dyes. The contaminants presents in wastewater are maintained in solution by electrical charges. When these ions and other charged particles are neutralized with

Effluents from textile, leather, tannery, electroplating, galvanizing, pigment and dyes, metallurgical and paint industries and other metal processing and refining operations at small and large-scale sector contains considerable amounts of toxic metal ions. These toxic metals ions are not only potential human health hazards but also to another life forms. Toxic metal ions cause physical discomfort and sometimes life-threatening illness including irreversible damage to vital body system (Malik, 2004). From the eco-toxicological point of view, the most dangerous metals are mercury, lead, cadmium and chromium(VI). In many instances the effect of heavy metals on human is not well understood. Metal ions in the environment bioaccumulate and are biomagnified along the food chain. Therefore, their toxic effect is more pronounced in animals at higher trophic levels. Mine tailing and effluents from non-ferrous metals industry are the major sources of heavy metals in the environment (Moore and Ramamoorthy, 1984). Among commonly used heavy metals, Cr(III), Cu, Zn, Ni and V are comparatively less toxic then Fe and Al. Cu is mainly employed in electric goods industry and brass production. Major applications for Zn are galvanization and production of alloys (Volesky and Schiewer, 2000). Cadmium has a half-life of 10–30 years (Moore and Ramamoorthy, 1984) and its accumulation in human body affects kidney, bone and also causes cancer and its use is increasing in industrial applications such as electroplating and making pigments and batteries. Chromium compounds are nephrotoxic and carcinogenic in nature (Chen and Hao, 1998). As a result of increasing awareness about the toxicity of Hg and Pb, their large-scale use by various industries has been either curtailed or eliminated (Volesky and Schiewer, 2000). An effluent treatment facility within the industry discharging heavy metals contaminated effluent will be more efficient than treating large volumes of mixed wastewater in a general sewage treatment plant. Thus it is beneficial to devise separate treatment procedures for scavenging heavy metals from the industrial

3. Conventional methods for heavy metal removal from industrial effluents To mitigate the heavy metal pollution, many processes like adsorption, precipitation, coagulation, ion exchange, cementation, electro-dialysis, electro-winning, electro-coagulation and reverse osmosis have been developed.

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ions of opposite electrical charges provided by electrocoagulation system, they become destabilized and precipitate in a stable form. 5. Cementation is a type of another precipitation method implying an electrochemical mechanism in which a metal having a higher oxidation potential passes into solution e.g. oxidation of metallic iron, Fe(0) to ferrous iron(II) to replace a metal having a lower oxidation potential. Copper is most frequently separated by cementation along with noble metals such as Ag, Au and Pb as well as As, Cd, Ga, Pb, Sb and Sn can be recovered in this manner. 6. Reverse osmosis and electro-dialysis involves the use of semi-permeable membranes for the recovery of metal ions from dilute wastewater. In electro-dialysis, selective membranes (alternation of cation and anion membranes) are fitted between the electrodes in electrolytic cells, and under continuous electrical current the associated ion migrates, allowing the recovery of metals.

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• Metal can be desorbed readily and then recovered if the value and amount of metal recovered are significant and if the biomass is plentiful, metal-loaded biomass can be incinerated, thereby eliminating further treatment.

4.2. Disadvantages • Early saturation can be problem i.e. when metal interactive sites are occupied, metal desorption is necessary prior to further use, irrespective of the metal value. • The potential for biological process improvement (e.g. through genetic engineering of cells) is limited because cells are not metabolizing. Because production of the adsorptive agent occurs during pre-growth, there is no biological control over characteristic of biosorbent. This will be particularly true if waste biomass from a fermentation unit is being utilized. • There is no potential for biologically altering the metal valency state. For example less soluble forms or even for degradation of organometallic complexes.

4. Biosorption Biosorption is a property of certain types of inactive, non-living microbial biomass to bind and concentrate heavy metals from even very dilute aqueous solution. Biomass exhibits this property, acting just as chemical substance, as an ion exchanger of biological origin. It is particularly the cell wall structure of certain algae, fungi and bacteria, which was found responsible for this phenomenon (Volesky, 1990). Till now, research in the area of biosorption suggests it an ideal alternative for decontamination of metal containing effluents. Advantages and disadvantages of biosorption by non-living biomass are as follows (Modak and Natarajan, 1995). 4.1. Advantages • Growth-independent, non-living biomass is not subject to toxicity limitation of cells. No requirement of costly nutrients required for the growth of cells in feed solutions. Therefore, the problems of disposal of surplus nutrients or metabolic products are not present. • Biomass can be procured from the existing fermentation industries, which is essentially a waste after fermentation. • The process is not governed by the physiological constraint of living microbial cells. • Because of non-living biomass behave as an ion exchanger; the process is very rapid and takes place between few minutes to few hours. Metal loading on biomass is often very high, leading to very efficient metal uptake. • Because cells are non-living, processing conditions are not restricted to those conducive for the growth of cells. In other words, a wider range of operating conditions such as pH, temperature and metal concentration is possible. No aseptic conditions are required for this process.

Biosorption is a rapid phenomenon of passive metal uptake sequestration by non-growing biomass (Beveridge and Doyle, 1989). Results are convincing and binding capacity of certain biomass is comparable with the commercial synthetic cation exchange resins (Wase and Foster, 1997). Volesky and Holan (1995) have reviewed the exhaustive list of microbes and their metal binding capacities. Further, sorption capacity is evaluated by sorption isotherms described by Langmuir and Freundlich models. The uptake of metal by two biosorbents must be compared at the same equilibrium concentration. The adsorption is easy to understand when it refers to a single metal situation; however in a multi-ion situation, which is generally encountered in effluent, the assessment of sorption becomes complicated. Most of the work exists with single metal solution and realistic approach would be inferring results in mixed metal solution at extreme pH and variable metal concentration. Biosorption efficiency depends upon many factors, including the capacity, affinity and specificity of the biosorbents and their physical and chemical conditions in effluents. 5. Mechanism of metal uptake The understanding of the mechanism by which microorganisms accumulate metals is crucial to the development of microbial processes for concentration, removal and recovery of metals from aqueous solution. Metabolism-independent metal binding to the cell walls and external surfaces is the only mechanism present in the case of non-living biomass. Metabolism-independent uptake essentially involves adsorption process such as ionic, chemical and physical adsorption. A variety of ligands located on the fungal walls are known to be involved in metal chelation. These include carboxyl, amine, hydroxyl, phosphate and sulfhydryl

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groups. Metal ions could be adsorbed by complexing with negatively charged reaction sites on the cell surface (Beveridge and Murray, 1980; Gupta et al., 2000). The relative importance of each functional group is often difficult to resolve (Strandberg et al., 1981). Microbial cell wall is rich in polysaccharide and glycoproteins such as glucans, chitin, mannans and phospho-mannans. These polymers form abundant source of metal binding ligands. Cell walls of fungi present a multi-laminate architecture where up to 90% of their dry mass consists of amino or non-amino polysaccharides (Farkas, 1980). In general, the fungal cell wall can be regarded as a two-phase system consisting of the chitin skeleton framework embedded in an amorphous polysaccharide matrix (Farkas, 1980). Up to 30% of Aspergillus niger biomass is comprised of an association of chitin and glucan (Muzzarelli and Tanfari, 1982). Chitin and chitosan components of the cell wall are suggested to be important for metal uptake (Tsezos and Volesky, 1981; Fourest and Roux, 1992). Muraleedharan and Venkobachar (1990) reported copper binding wood-rotting fungi Ganoderma lucidum was reduced only marginally when the biosorbent was devoid of chitin, indicating that chitin does not play a major role in the system. Electron paramagnetic-resonance spectra of biosorbent indicated the presence of a free radical (unidentified) in the cell wall matrix, which interacts with metal, resulting in metal binding by the cells. Mechanism of uranium binding Rhizopus arrhizus involves the amine nitrogen of chitin crystallites and takes place in a sequence of events (Tsezos and Volesky, 1982). Other studies in fungi have implicated the phosphate and carboxylate groups of the cell wall in primary binding (Akthar et al., 1996; Kapoor and Viraraghavan, 1997). Determination of the exact mechanism is further complicated by complex solution chemistry of the metals and the inability to determine the precise metal complex present in the solution (Tobin et al., 1984), which is not readily amenable to instrumental analysis (Kuyucak and Volesky, 1989). Differences in affinities between elements and their ionic species may exist for various ligands encountered in biological system. Cell wall of different fungi can vary considerably in their overall composition, which leads to varying adsorption capacity. However, localization of metal(s) has been carried out using electron microscopic and Xray energy dispersive analyses. X-ray photoelectron spectroscopy for chemical analysis is a relatively new technique for determination of binding energy of electrons in atoms/ molecules, which depends upon the distribution of valence charges and thus gives information about the oxidation state of an atom/ion (Gupta et al., 2000). Electron microscopic observation carried out by Mullen et al. (1989) revealed the presence of Ag2+ as discrete particles at or near the cell wall of both gram-positive and gram-negative bacteria. The presence of silver was also confirmed by energy dispersive X-ray analysis (EDAX). Figueira et al. (1999) using the X-ray photoelectron spectroscopy observed that iron was present in two oxidation states,

when the brown seaweed Sargassum fluitans was exposed to Fe2+, while only Fe3+ was present when biomass was exposed to ferric ions. Further, FTIR analysis has confirmed that both carboxyl groups were involved in the uptake of Fe2+ and Fe3+ and sulfonate groups were responsible for Fe3+ uptakes. 6. Removal of metal by non-living biomass of microbial and plant origin Removal of heavy metals from aqueous solution by using inactive and dead biomass is an innovative and alternative technology for removing these pollutants. Nonliving biomass of algae, aquatic ferns and seaweeds, waste biomass originated from plants and mycelial wastes (Tables 1a–1c and 1d) from fermentation industries are potential biosorbents for removal of heavy metals from aqueous solution and wastewater (Puranik and Paknikar, 1999; Ahluwalia and Goyal, 2005). Considerable potential exists for these naturally existing, abundant and cheap sources of biomass, for use as adsorbents. Their efficiency depends on the capacity, affinity and specificity including physico-chemical nature. Biomass related metal removal processes may not necessarily replace existing treatment processes but may complement them. 6.1. Removal of metals by fungal biomass Copper biosorption by non-living wood rotting fungus Ganoderma lucidum was studied and it was found that protein interaction with metals did not play a significant role in copper(II) uptake (Muraleedharan and Venkobachar, 1990). Waste mycelia of A. niger, Phanerochaete chrysogenum and Claviceps paspali from industrial fermentation plants were used as biosorbent for Zn from aqueous environments in batch as well as column modes. Under optimized conditions, A. niger and C. paspali were superior to P. chrysogenum (Luef et al., 1991). Biosorption of lead by P. chrysogenum biomass was strongly affected by pH. At pH 4–5, the saturated uptake capacity for lead sorption was higher than that of activated charcoal and that reported for some other organisms (Niu et al., 1993). Dead cells of Saccharomyces cerevisiae removed 40% more uranium or zinc than live cultures and biosorption rapidly reached 60% of the final uptake value within 15 min of contact and uranium was deposited as fine needle-like crystals inside the cells and on the outer cell surface (Volesky and May-Phillips, 1995). Non-living waste biomass of A. niger attached to wheat bran was used as a biosorbent for removal of Zn and Cu from aqueous solution and metal uptake was found to be a function of the initial metal concentration, biomass loading and pH. Metal uptake decreased in the presence of coions, which was dependent on the concentration of metal ions in two compounds in aqueous solution (Modak et al., 1996). Alkali treated biomass of A. niger referred to as Biosorb, was found to sequester Cd2+, Cu2+, Zn2+,

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Table 1a Fungal biomass for removal of heavy metals from aqueous solution Biosorbent

Metals

Adsorption capacity (mg g 1)

References

Aspergillus foetidus Aspergillus niger

Cr(VI) Cu

2 5 – 95 200 2.4 – 30 22 162 29 27 –

Prasanjit and Sumathi (2005) Townsley and Ross (1986) Modak et al. (1996) Kuyucak and Volesky (1989) Kuyucak and Volesky (1989) Sakaguchi and Nakajima (1991) Goyal et al. (2003) Kim et al. (1995) Tsezos and Volesky (1981) Gadd (1988) Sakaguchi and Nakajima (1991) Kuyucak and Volesky (1989) Luef et al. (1991),Modak et al. (1996), Muter et al. (2002) Tsezos and Volesky (1981) Gadd and Mowll (1995) Suh et al. (1998) Ahluwalia and Goyal (2003) Gadd (1988) de Rome and Gadd (1987) Ahluwalia and Goyal (2003) Muter et al. (2002) Muraleedharan and Venkobachar (1990) Tobin and Roux (1998) Yan and Viraraghavan (2003) Lo et al. (1999) Niu et al. (1993) Holan and Volesky (1995) Fourest et al. (1994) Tsezos and Volesky (1981) Gadd and White (1992) Tsezos and Volesky (1981) Niu et al. (1993) Luef et al. (1991) Skowron˜ski et al. (2001) Yalcinkaya et al. (2002) Puranik and Paknikar (1997) de Rome and Gadd (1987) Gadd and White (1989) Townsley and Ross (1985) Gabriel et al. (1996) Say et al. (2001) Yetis et al. (2000) Cho and Kim (2003) Bai and Abraham (2001) Zhang et al. (1998) Fourest and Roux (1992) Holan and Volesky (1995) Ariff et al. (1999) Aloysius et al. (1999) Fourest and Roux (1992) Holan and Volesky (1995) Bai and Abraham (1998) Nourbakhsh et al. (1994) Sakaguchi and Nakajima (1991) Niyogi et al. (1998) Sag and Kutsal (1998) Prakasham et al. (1999) Gadd (1988) de Rome and Gadd (1987), Sag and Kutsal (1998), Zhou and Kiff (1991) (continued on next page)

Co Au Co Cr, Fe Pb Th U Zn Aspergillus terreus Aureobasidium pullulans

Th, U Cu Pb

Cladosporium resinae

Cu

Candida utilis Ganoderma lucidum Mucor meihi Mucor rouxii Penicillium chrysogenum

Pb Cr, Cu, Pb Cu Cr Pb, Zn, Cd, Ni Pb Cd, Cu, Pb Cd Th U Zn

Pleurotus sapidus Streptoverticillium cinnamoneum Penicillium italicum Penicillium spinulosum Phanerochaete chrysosporium

Rhodotorula glutinis Rhizopus nigricans

R. oligosporus R. arrhizus

Cd, Zn, Cu, Pb Cd, Hg Pb, Zn Cu Th Cu, Zn Cd Pb Cu Pb Cr, Pb Zn Cd, Ni, Pb Cr Cd Ni, Cd, Zn, Pb, Cu Cd Cr Co

Cu

60, 10 6 56.9 – 18 – – 24 – 17, 4.89, 6.94, 5.24 769 11, 9, 116 56 39 142 70 6.5 – – 127, 287 57.7, 21.3 – – 0.4–2, 0.2 84.5 2 – 73.5 47 14 19, 5, 166 126 17.09 18, 27, 14, 56, 9.5 30 11 36 2.9 – – – 10 –

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Table 1a (continued) Biosorbent

Saccharomyces cerevisiae

Metals

Adsorption capacity (mg g 1)

References

Th

185 97 Gadd and White (1992) 220 Tsezos et al. (1989) Tsezos and Deutschmann (1990) – – 11.4 5.8 – 119 17–40 55–140 10 0.4 14–40 – 109

Tsezos and Volesky (1981) Gadd et al. (1988)

– U – – Cd Cr Co Pb Th Cu U Cu

Trametes versicolor

Zn Cr Cd

Ni2+ and Co2+ efficiently up to 10% of its weight (w/w) and exhibited higher metal binding capacity as compared to Neurospora, Fusarium and Penicillium (Akthar et al., 1996). The kinetics of metal binding by Biosorb indicated that it is a rapid process and about 70–80% of the metal is removed from solution in 5 min followed by slower rate. Dry cells of R. arrhizus were used for removal of Fe(II), Pb(II) and Cd(II) ions from industrial wastewater (Ozer et al., 1997). Higher adsorption rate and adsorption capacity were obtained at initial metal concentration up to 100 mg l 1 in a batch reactor. Cd(II) biosorption to nonliving biomass of fungus R. arrhizus and green alga Schizomeris leiblenii showed that maximum adsorption rate of Cd(II) ions to microbial biomass was at 30 C and pH 5.0, which increased with increasing Cd(II) concentration up to 100–150 mg l 1. Adsorption by R. arrhizus was much higher than S. leiblenii (Ozer et al., 1997). Dried, non-living, granulated biomass of Streptoverticillium cinnamoneum was used for recovery of Pb and Zn at optimum pH 5.0–6.0 and 3.5–4.5, respectively. Maximum loading capacity of S. cinnamoneum biomass pre-treated with boiling water was 57.7 mg g 1 for Pb and 21.3 mg g 1 for Zn. The metals were effectively desorbed with dilute HCl, nitric acid and 0.1 M EDTA (Ethylene diamine tetra acetic acid). Treatment with 0.1 M sodium carbonate permitted reuse of desorbed biomass, which decreased loading capacity by 14–37% in subsequent cycles (Puranik and Paknikar, 1997). Waste mycelial biomass comprising of Rhizopus nigricans from the pharmaceutical fermentation industry, was used for adsorption of lead over a range of metal ion concentrations, adsorption times, pH and co-ions. Uptake process followed Langmuir and Freundlich adsorption isotherms. Comparison of the uptake between NaOH-treated and untreated biomass showed that adsorption took

Tsezos and Volesky (1981)

Volesky et al. (1993) Nourbakhsh et al. (1994) Omar et al. (1996) Sakaguchi and Nakajima (1991) Suh et al. (1998) Gadd (1988) Volesky and May-Phillips (1995) Mattuschka et al. (1993) Huang et al. (1990) Volesky and May-Phillips (1995) Bayramoglu et al. (2003) Gabriel et al. (1996)

place in the chitin structure of the cell wall (Zhang et al., 1998). Removal of Cr(VI) from aqueous solution was carried out in batch mode using dead biomass of fungal strains A. niger NCIM-501, A. oryzae NCIM-637, R. arrhizus NCIM-997 and R. nigricans NCIM-880. Basic parameters such pH (2.0–8.0), initial metal ion concentration (100– 500 mg l 1), contact time (2–24 h) and varying biomass concentration (0.5–3.0 g) were optimized. R. nigricans and R. arrhizus possessed good specific uptake of 11 mg Cr(VI) g 1 of biomass at the pH range of 2.0–7.0. Metal uptake capacity was in the order of Rhizopus nigricans > Rhizopus arrhizus > Aspergillus oryzae > Aspergillus niger (Bai and Abraham, 1998). Mucor meihi, a fermentation industry waste was found to be an effective biosorbent for the removal of hexavalent chromium from leather industry effluent. In comparative studies with ion-exchange resins, Mucor biomass showed biosorption levels corresponding to the strongly acidic commercial resins. Response to pH was similar to the weakly acidic resins in solution and chromium elution characteristics were similar to both weakly and strongly acidic resins (Tobin and Roux, 1998). Non-living free and immobilized biomass of R. arrhizus were used to study biosorption of chromium(VI). The removal rates were slightly more in free biomass conditions over immobilized state. Stirred tank reactor studies indicated maximum chromium biosorption at 100 rpm and 1:10 biomass–liquid ratio. The fluidized bed reactor was more efficient in chromium removal than the stirred tank reactor (Prakasham et al., 1999). The influences of co-cations (cadmium, copper, cobalt and nickel) on lead and zinc biosorption by S. cinnamoneum and Penicillium chrysogenum in binary and multimetal systems was studied (Puranik and Paknikar, 1999). Metal sorption capacity of S. cinnamoneum was observed

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Table 1b Algal biomass for removal of heavy metals from aqueous solution Biosorbent

Metals

Adsorption capacity (mg g 1)

References

Ascophyllum nodosum

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

215 156, 100 30, 270–360 30 133 – 111 43 3.5

Holan et al. (1993) Kuyucak and Volesky (1988, 1989) Holan and Volesky (1995) Volesky and Prasetyo (1994) Incharoensakdi and Kitjaharn (2002) Harris and Ramelow (1990) Aksu (2001) Aksu et al. (1992) Nourbakhsh et al. (1994) Donmez et al. (1999) Sakaguchi and Nakajima (1991) Greene et al. (1986) Wehreim and Wettern (1994) Akhtar et al. (2003) Nourbakhsh et al. (1994) Apiratikul et al. (2004) Donmez and Aksu (2002) Holan et al. (1993) Holan and Volesky (1995) Cordeo et al. (2004) Stirk and Staden (2002) Yun et al. (2001) Hamdy (2000) Klimmek et al. (2001) Blanco et al. (1998) Carrilho and Gilbert (2000) Lee et al. (2000) Ahuja et al. (1999) Mohapatra and Gupta (2005) Gupta et al. (2001) Harris and Ramelow (1990) Donmez et al. (1999) Terry and Stone (2002) Pena-Castro et al. (2004) Schiwer and Volesky (1996) Kratochvil et al. (1997) Kuyucak and Volesky (1989) Holan et al. (1993) Holan and Volesky (1995) da Cotsa et al. (2001) Volesky et al. (2003),Padilha et al. (2005) Valdman and Leite (2000) Cruz et al. (2004) Perez-Rama et al. (2002) Nuhoglu et al. (2002) Zeroual et al. (2003)

Aphanothece halophytica Chlorella vulgaris

Chlorella fusca Chlorella sorokiniana Cladophora crispate Caulerpa lentillifera Dunaliella sp. Fucus vesiculosus Fucus spiralis Ecklonia maxima Laminaria japonica Laurencia obtuse Lyngbya taylorii Phormidium laminosum Pilayella littoralis Pachymeniopis sp. Oscillatoria anguistissima Spirogyra sp. Scenedesmus quadricula Scenedesmus obliquus Scenedesmus abundans Scenedesmus incrassatulus Sargassum fluiyans Sargassum natans

Sargassum sp. Sargassum sp.

Tetraselmis suecica Ulothrix zonata Ulva lactuca

Pb Cd Cr Cu, Cd, Pb, Zn Cr Cd Ni, Pb Cd Cd Cd Cr Cd, Pb, Ni, Zn Cu, Ni, Zn Al, Cd, Co, Cr, Ni, Zn Cr(VI) Zn Zn, Cu, Co Cr Cd, Cu, Zn Cr, Cu, Ni Cd, Cu Cr, Cd, Cu Cu U Cd Ni, Pb Zn Cu Cd, Zn, Cu Cd Cd Cu Hg

3.95 – 293 – 3 – 58.3 73 17, 220–371 64 – – – – – – 225 641 – – – – – – – 51 – 135 24–44, 220–270 – 38, – 157, 118, 77 120 – – –

to be higher than P. chrysogenum for all metals. The extent of metal sorption depended on metal chemistry, affinity for binding sites and type of metal. The order of metal biosorption in a multi-metal system could be predicted well based on Langmuir parameters evaluated in binary metal system. The kinetics and mechanisms of lead(II) biosorption by pulverized R. oligosporus were studied in batch mode (Ariff et al., 1999). At an initial lead concentration ranging from 50 to 200 mg l 1, pH 5.0 and optimum biomass concentration (0.5 g l 1) the maximum lead adsorption was 750 mg g 1 with lead uptake capacity of 126 mg g 1. Chromium sorption by powdered biomass of R. nigricans was optimum at pH 2, an agitation rate of 120 rpm, a temper-

ature of 45 C, a contact time of 30 min and a dosage of 0.5% (w/v) with a biomass particle size of 90 lm. High adsorption was observed at lower initial concentration of Cr ions (Bai and Abraham, 2001). The biosorption of Cd(II), Pb(II) and Cu(II) onto the dry fungal biomass of Phanerochaete chrysosporium was investigated from artificial wastewater in the concentration range of 5–500 mg l 1 (Say et al., 2001). Maximum biosorption of different heavy metal ions was obtained at pH 6.0 and biosorption equilibrium was established after about 6 h and experimental biosorption data followed the Langmuir adsorption model. The biosorption of heavy metals by whole mycelia and selected components of A.

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Table 1c Bacterial biomass used for metal removal Biosorbent

Metals

Adsorption capacity (mg g 1)

References

Pseudomonas fluorescens Pseudomonas sp. Ochrobactrum anthropi Thiobacillus ferrooxidans

Th, U U Cr, Cd, Cu Zn Cr Cd, Zn Cr Cd Pb, Cu, Zn Cr(VI) Cr(VI) Cr(VI) Cu Cd, Cu, Ni Pb, Zn, Ag, Co Cr, Pb

15, 6 – – 82 – – – – 467, 381, 418 39.9 30.7 2 29 3.4, 9, 0.8 36, 1.6, 38 1.2 1.8, 55 100, 440 30

Tsezos and Volesky (1981) Pons and Fuste (1993) Ozdemir et al. (2003) Baillet et al. (1998) Celaya et al. (2000) Plette et al. (1996) Melo and D’Souza (2004) Tangaromsuk et al. (2002) Salehizadeh and Shojaosadati (2003) Srinath et al. (2002) Srinath et al. (2002) Nourbakhsh et al. (1994) Aksu et al. (1992) Mattuschka and Straube (1993) Mattuschka and Straube (1993) Mattuschka and Straube (1993) Mattuschka et al. (1993) Friis and Myers-Keith (1986) Mameri et al. (1999)

Rhodococcus erythropolis Ocimum basilicium Sphingomonas paucimobilis Bacillus firmus B. coagulans B. megaterium Zoogloea ramigera Streptomyces noursei

S. longwoodensis S. rimosus

Pb, U Zn

Table 1d Plant derived biomass used for metal removal Biosorbent

Metals

Adsorption capacity (mg g 1)

References

Activated baggase carbon Alfalfa Artocarpus heterphyllus Azolla filiculoides Banana pith (Musacea zingiberales) Hydrilla verticillata casp. and Salvinia sp. Carrot pulp Ceratophyllum demersum Cupressus Female Cone Eucalyptus wood powder Eucalyptus bark Ground corncobs

Cr Cu, Pb Cd Pb Pb, Cu, Ni, Cr, Zn Cu Pb, Ni, Zn, Fe Cu, Pb, Zn Cr(VI) Pb, Ni, Zn, Fe Cr(VI) Cd, Cu, Pb Ni, Zn Cu Cu Hg, Pb, Cu Zn, Cd Pb, Cu, Ag Cd Pb, Ni, Zn, Fe Cu, Pb Zn, Ni, Cd, Cu, Pb Cr(VI) Ni Pb Pb, Ni, Zn, Fe Cd, Cr Cr Cu Cd Cu, Ni Pb Pb, Cu, Cd

– 20, 43 – 93 – – – 6.17, 45, 14 119 – – – – – 24 – – – – – 12.4, 46.6 – – – – – – – – – 15.9, 18.1 – –

Mor et al. (2002) Tiemann et al. (1999) Inbaraj and Sulochana (2004) Sanyhumbi et al. (1998) Low et al. (1995) Elankumaran et al. (2003) Joshi et al. (2003) Keskinkan et al. (2004) Murugan and Subramanian (2003) Joshi et al. (2003) Sarin and Pant (2006) Vaughan et al. (2001)

Hydrilla verticillata casp. Larrea tridenta Olive mill solid residue Paper mill sludge

Sago processing waste Sawdust Wheat stem and Spent Babul Bark Oryza sativa L. hush Waste tea-leaves Wolffia globosa Water hyacinth roots Helianthus annuus L. (Sunflower) Allium sativum L. (Garlic) Grape stalk waste Hemidesmus indicus Myriophyllum spicatum

niger, R. oryzae and Mucor rouxii was studied (Baik et al., 2002). Binding of copper, cadmium, nickel and zinc was

Elankumaran et al. (2003) Gardea-Torresdey et al. (2004a,b) Pagnanelli et al. (2002) – Calace et al. (2003) – Joshi et al. (2003),Ahluwalia and Goyal (2004) Quek et al. (1998) Marin and Ayele (2002) Acar and Malkoc (2004) Verma and Shukla (2000) Zulkali et al. (2006) Joshi et al. (2003),Ahluwalia and Goyal (2005) Upatham et al. (2002) Low et al. (1997) Lin et al. (2003) Jiang et al. (2001) Villaescusa et al. (2004) Chandrasekhar et al. (2003) Keskinkan et al. (2003)

considerably improved by treating the cell wall fraction with 4 M NaOH at 121 C.

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6.2. Removal of metals by algal biomass Chromium sorption by non-living biomass of Chlorella vulgaris and Cladophora crispata along with bacteria and fungi was studied and it was observed that pH affected metal uptake capacity (Nourbakhsh et al., 1994). Maximum adsorption was observed at a temperature range of 25–35 C, which increased with increasing metal concentrations up to 200 mg l 1. The short-term accumulation of chromate by Anabaena sp. and Synechococcus sp. PCC6301 was rapid with relatively low level of sorption to the cell wall. The process was not energy dependent but was regulated bychromate concentration described by Freundlich adsorption isotherm. On decreasing pH, chromate accumulation increased in both the species. Over a longer growth period Anabaena variabilis was capable of reducing chromate(VI) to chromium(III) and accumulating it. Synechococcus PCC 6301 showed no further interaction with chromate concentration over the same period after an initial biosorption (Garnham and Green, 1995). In brown seaweeds, 90–95% removal of Hg and Cd from industrial wastewater was observed (Wilson and Edween, 1995). Biosorption of Cu(II), Fe(II), Ni(II) and Zn(II) by nonviable biomass of the cyanobacterium Phormidium laminosum from single and binary metal solution was extremely rapid and consisted of a single phase (Blanco et al., 1998). The presence of a second metal in solution decreased the binding of Fe(II), Ni(II) and Zn(II) due to chemical blocking of the carboxyl groups of biomass but this had no effect on the binding of Cu(II). Washing with dilute acids was much faster and effective than NaOH, NaCl, CaCl2 and ultra pure water reaching equilibrium within 30 min and the efficiency was independent of the concentration of desorbent. Biosorption of Cu(II), Ni(II) and Cr(VI) from aqueous solution by dried algae Chlorella vulgaris, Scenedesmus obliquus and Synechocystis sp. was tested under laboratory conditions as a function of pH, initial metal ion and biomass concentration (Donmez et al., 1999). Results showed the influence of algal biomass concentration on metal uptake by all species and both Freundlich and Langmuir adsorption models described the short-term biosorption. Out of 48 different species of red, brown and green algae examined for chromate adsorption, excellent adsorption was observed by Pachymeniopsis sp., which had high selectivity for chromate among other heavy metals ions such as cadmium and manganese. It also exhibited a typical Langmuir isotherm with qmax of 225 mg g 1 and K 1106 mg ml 1 (Lee et al., 2000). Biosorption of trivalent chromium by protonated brown algal biomass of Eklonia revealed three types of functional groups. The carboxyl group was the chromium-binding site within the pH range of 1–5 at which chromium does not precipitate. The pK value and number of carboxyl groups were estimated to be 4.6 ± 0.1 and 2.2 ± 0.1 mmol g 1, respectively (Yun et al., 2001). Adsorption of Cu(II) from aqueous solution by Ulothrix zonata was studied using batch adsorption technique (Nuhoglu et al., 2002). The equilibrium biosorp-

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tion level was found to be a function of contact time at different initial metal ion concentration and the adsorption data showed the Langmuir adsorption model. The free energy change for the adsorption process was found to be 12.60 kJ mol 1. Dried Caulerpa lentillifera was shown to have adsorption potential for Cu, Cd, Pb and Zn (Apiratikul et al., 2004). The adsorption equilibrium followed the Freundlich isotherm. The adsorption of metals from binary mixture of heavy metal was competitive and the adsorption capacity of any single metal decreased by 10– 40% in the presence of the other metallic species and the overall adsorption capacity of the algae decreased by 30– 50%. Uranium biosorption by powered biomass of lake-harvested water bloom cyanobacterium Microcystis aeruginosa (Li et al., 2004) was optimum at 4.0–8.0 pH. The batch sorption reached the equilibrium within 1 h and followed the Freundlich isotherm model. Uranium was effectively desorbed with 0.01 N HCl. This naturally abundant biomass otherwise nuisance cyanobacterium exhibited good potential for application in removal of uranium from aqueous solution. The waste biomass of Sargassum sp. for the recovery of ionic copper from simulated semiconductor effluents was investigated (Padilha et al., 2005) using continuous system comprising of four column reactors filled with the biomass which showed high operation stability and completely biosorbed the ionic copper from 63 l of copper sulphate solution, 72 l of copper chloride solution and 72 l of copper nitrate solution, all the solutions containing 500 mg l 1 copper. Copper concentration was found to be less than 0.5 mg l 1 in the effluent from the outlet of the reactor. Five different brown seaweeds, Bifurcaria bifurcata, Saccorhiza polyschides, Ascophyllum nodosum, Laminaria ochroleuca and Pelvetia caniculata were studied for their ability to remove cadmium from aqueous solution (Lodeiro et al., 2005). Kinetics of cadmium adsorption by all algae was relatively fast with 90% of total adsorption occurring in less than 1 h. 6.3. Removal of metals by bacterial biomass Bacteria may uptake and accumulate a significant amount of metal ions, resulting in the transfer of metals to a contaminated matrix of biomass (Smith et al., 1994). When suspension of dead biomass of actinomycetes from industrial fermentation, was mixed with wastewater, the biosorption of cadmium cations occurred due to negatively charged sites on bacterial cell wall (Butter et al., 1996). Zinc biosorption capacity of Streptomyces rimosus biomass was studied in batch mode and after heat treatment (Mameri et al., 1999). The optimum conditions of biosorption were a contact time of 4 h, biomass particle size 140–250 lm, ambient temperature, a stirring speed of 250 rpm and pH 7.5. The biosorption capacity was 30 mg of Zn g 1 of biomass, which increased up to 80 mg following chemical treatment by NaOH. The removal of chromium, cadmium and copper from dilute aqueous solution using dead

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polysaccharide producing Ochrobactrum anthropi, isolated from activated sludge (Ozdemir et al., 2003). Optimum adsorption pH values of Cr(VI), Cd(II) and Cu(II) were 2.0, 8.0 and 3.0, respectively. Experimental showed the influence of initial metal concentration on the metal uptake for dried biomass. Both the Langmuir and Freundlich adsorption were suitable for describing the short term biosorption of Cr(VI), Cd(II) and Cu(II) by O. anthropi. 6.4. Removal of metals by plant derived biomass The sorption capacity of different biosorbents like dried mycelium of some species of fungi, baggase, rice husk and fermented baggase was examined to remove cyanide from industrial effluent (Azab et al., 1995). Banana pith (Musacea zingiberales) was evaluated for its ability to sorb metal ions from electroplating waste and synthetic solutions under both batch and continuous flow conditions. The sorption was observed to be both pH and concentration dependent with pH 4–5 being optimum. The equilibrium data followed the Langmuir isotherm model with maximum capacity of 8.55 and 13.46 mg g 1 of Cu in electroplating waste and synthetic solution, respectively (Low et al., 1995). Waste biomass such as wheat stem and babul bark was used to remove nickel from effluent of an electroplating industry (Verma and Shukla, 2000). The removal of nickel was 2–10% less as compared to synthetic solution under similar conditions. Wheat straw activated carbon could remove 100% Ni(II) from initial nickel concentration of 25 mg l 1 at pH 4.0 in 4 h at 36 ± 2 C. The uptake capacity of different metals by Quercus ilex phytomass (root, stem and leaf) was found to be in the order of roots Ni > Cd > Pb > Cu > Cr; stem Ni > Pb > Cu > Cd > Cr; and leaf Ni > Cd > Cu > Pb > Cr (Prasad and Freitas, 2000). Desorption with 10 mM Na4 EDTA was effective and there existed the possibility of recycling the phytomass. Biosorption capacity of plant biomass of Indian Saraparilla (Hemidesmus indicus) was studied with toxic heavy metals like As, Se, Zn, Fe, Ni, Co, Pb, Mn, Hg, Cr and Cu. Lead was preferentially removed followed by Cr and Zn at concentration less than 250 mg l 1 and with biomass quantity above 2 g. Presence of co-ions (As, Se and Hg) did not effect the Pb removal but Zn and Cr uptake decreased. Metal loaded biomass was regenerated with HNO3 and reused for three cycles without any loss in metal retention capacity (Chandrasekhar et al., 2003). Adsorption of Cd(II) and Ni(II) was found to be higher than Cr(VI) and Zn(II) when phosphate treated rice husk was used as an adsorbent (Ajmal et al., 2003). Sorption of Cd(II) was dependent on contact time, concentration, temperature, adsorbent doses and pH of the solution and follows the Langmuir constant. Recovery of Cd(II) from aqueous solution by column operation was found to be higher than batch process. Adsorption of Cr(VI) with activated rice husk carbon and activated alumina (Bishnoi et al., 2004) and with formaldehyde treated saw dust and sulphuric acid treated saw dust carbon (Garg et al., 2004) was investi-

gated. The amount of Cr(VI) adsorbed increased with increase in dose of these adsorbents and their contact time. Reduction rate of Cr(VI) to Cr(III) by Ecklonia sp. biomass increased with decreasing pH, which appeared in the solution phase or was partly bound to the biomass (Park et al., 2004). The jack fruit peel (Artocarpus heterophyllus) was treated with sulphuric acid to produce a carbonaceous product, which was used as an adsorbent for the removal of Cd(II) from aqueous solution (Inbaraj and Sulochana, 2004). Kinetic analysis made with Lagergren pseudo-first order, Ritchie second order and modified Ritchie second order models showed better fits with modified Ritchie second order model. The Langmuir–Freundlich (Sips equations) model best defines the experimental equilibrium data among the three isotherm models (Freundlich, Langmuir and Langmuir–Freundlich) used. A complete recovery of the adsorbed metals ions from the spent adsorbent was achieved by using 0.01 M HCl. The adsorption of activated carbon prepared from apricot stones, to remove Ni(II), Co(II), Cd(II), Cu(II), Pb(II), Cr(III) and Cr(VI) ions from the aqueous solution was studied (Kobya et al., 2005). Highest adsorption occurred at pH 1–2 for Cr(VI) and at pH 3–6 for the remaining metal ions. Further, adsorption capacities for these metals were found to in the order of Cr(VI) > Cd(II) > Co(II) > Cr(III) > Ni(II) > Cu(II) > Pb(II), respectively. Potential of modified lignocellulosic fibre/jute was assessed for adsorption of heavy metal ions like Cu(II), Ni(II) and Zn(II) from aqueous solution (Shukla and Pai, 2005). The dye loaded jute fibre showed adsorption capacity of 8.4, 5.26 and 5.95 mg g 1 for Cu(II), Ni(II) and Zn(II), respectively, whereas oxidized jute fibre showed 7.73, 5.57 and 8.02 mg g 1 against 4.23, 3.37 and 3.55 mg g 1 for unmodified jute fibre which followed Langmuir adsorption model. Desorption efficiency, regenerative and reuse capacity of these adsorbent were also assessed for three successive adsorption–desorption cycles. The sorption of lead by tree fern, an agricultural by product was carried out using agitated and baffled system (Ho, 2005). The optimum pH for lead removal was 4.9. Also pseudo-second-order kinetics analysis was performed to determine the rate constant of sorption, the equilibrium sorption capacity, and the initial sorption rate. Removal of cadmium from aqueous solution by Moringa oleifera seed was studied in batch sorption experiments as a function of biomass dosage, contact time, metal concentration, particle size and pH (Sharma et al., 2006). Fourier transform infrared spectroscopy indicated the amino-Cd interaction responsible for this sorption. These finding opens up new avenues in the removal of toxic metals by shelled M. oleifera seeds from water bodies as low cost, domestic and environment friendly safe technology. 7. Development of biosorbent Biosorption is a complex process, mainly comprising of ion exchange, chelation and adsorption by physical forces

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and entrapment in inter and intra-fibrillar capillaries and space of the structural polysaccharide network as a result of the concentration gradient and diffusion. There are several chemical groups that would attract and sequester the metals in biomass. Acetamide groups of chitin, structural polysaccharides of fungi, amino and phosphate groups of nucleic acids, amide, amine, sulfhydryl and carboxyl groups in the proteins and hydroxyls in polysaccharide of marine algae belonging to Phaeophyceae, Rhodophyceae and Chlorophyceae are some of the examples. It does not necessarily mean that presence of functional groups guarantees biosorption, perhaps due to steric, conformational or other effects. Several proprietory biosorption processes were developed and commercialized in the early 1990s using AlgaSORBTM (Brierley et al., 1986) and AMT-BioclaimTM (Darnall, 1991) but did not attract widespread adoption due to a lack of understanding of the underlying mechanism of metal-sorption, proper selection of industrial effluents for pilot testing and scaling up of the process (Kratochvil and Volesky, 1998). Routinely most prospective biosorbents are discovered by trial and experimentation. Many microorganisms can be used as biosorbents. Fungi in particular have unique metal adsorption characteristics and are easy to cultivate (Gadd, 1988). They can successfully absorb toxic metal ions Zn2+, Cu2+, Cd2+, Pb2+, Ni2+, Fe2+, Mn2+ and Cr6+ from aqueous solution. But the process is susceptible to complexation or precipitation of the metal, making it unavailable for binding due to the presence of anions such as phosphate. Some biosorbent have broad range, which bind the majority of heavy metals with no specific activity, while others are specific for certain metals. Biosorption studies have been carried out using easily available biomass in their native state or after simple processing. Among a variety of biomaterials, the majority has been focused on bio-waste generated as a by-product of large-scale industrial fermentation (Puranik and Paknikar, 1999), olive mill solid residues (Pagnanelli et al., 2002), activated sludge from sewage treatment plants (Hammaini et al., 2003; Sag et al., 2003), biosolids (Norton et al., 2003), aquatic macrophytes (Keskinkan et al., 2003) and other plant derived materials (Gardea-Torresdey et al., 2004a,b). Norton et al. (2003) used dewatered activated sludge from a sewage treatment plant for removing zinc from aqueous solution and recorded adsorption capacity of 0.56 mM g 1 of biosolids. Use of biosolids for zinc adsorption was favorable compared to the bio-adsorption rate of 0.3 mmol g 1 by seaweed Durvillea potatorum (Aderhold et al., 1996). Keskinkan et al. (2003) studied adsorption characteristics of copper, zinc and lead on submerged aquatic plant, Myriophyllum spicatum and found the adsorption capacities to be 46.60 mg l 1 for lead, 15.59 mg g 1 for zinc and 10.37 mg g 1 for copper. Pagnanelli et al. (2002) carried out a preliminary study on the use of olive mill residue as a heavy metal sorbent material. They found that copper was maximally adsorbed in the

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range of 5.0–13.5 mg g 1 under different operating conditions. The biosorption capacity of copper, cadmium and zinc on dried activated sludge was 0.32 m mol g 1 for metal systems such as Cu–Cd; 0.29 m mol g 1 for Cu–Zn and 0.32 m mol g 1 for Cd–Zn. Results showed that biomass had a preference for copper followed by cadmium and zinc (Hammaini et al., 2003). Another inexpensive source of biomass is seaweeds comprising mainly the marine macro-algae. However, most of the studies on the uptake of toxic metals by marine algae and to some extent by freshwater algae are focused on toxicological aspects, metal accumulation and pollution indicators. There has been no focus on the technological aspects of metal removal by algal biomass. 8. Conclusion Metabolic independent processes can mediate the biological uptake of heavy metal cations. Biosorption offers an economically feasible technology for efficient removal and recovery of metal(s) from aqueous solution. The process of biosorption has many attractive features including the selective removal of metals over a broad range of pH and temperature, its rapid kinetics of adsorption and desorption and low capital and operation cost. Biosorbent can easily be produced using inexpensive growth media or obtained as a by-product from industry. It is desirable to develop biosorbents with a wide range of metal affinities that can remove a variety of metal cations. These will be particularly useful for industrial effluents, which carry more than one type of metals. Alternatively a mixture of non-living biomass consisting of more than one type of microorganisms can be employed as biosorbents. Such ‘‘Combo’’ biosorbents have to be tested for commercial applications. The use of immobilized biomass rather than native biomass has been recommended for large-scale application but various immobilization techniques have yet to be thoroughly investigated for ease, efficacy and cost effectivity. Biosorption processes are applicable to effluents containing low concentrations of heavy metals for an extended period. This aspect makes it even more attractive for treatment of dilute effluent that originates either from an industrial plant or from the primary wastewater treatment facility. Thus biomass-based technologies need not necessarily replace the conventional treatment routes but may complement them. At present, information on different biosorbent materials is inadequate to accurately define the parameters for process scale up and design perfection including reliability and economic feasibility. To provide an economically viable treatment, the appropriate choice of biomass and proper operational conditions has to be identified. To predict the difference between the uptake capacities of the biomass, the experimental results should be tested against an adsorption model. The development of a packed bed or fluidized-bed biosorption model would be helpful for evaluating industrial-scale biosorption

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