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 generated as a by-product of fermentative processes offers great potential for adopting an economical metal-recovery system
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 generated as a by-product of fermentative processes offers great potential for adopting an economical metal-recovery system
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 generated as a by-product of fermentative processes offers great potential for adopting an economical metal-recovery system
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 eects on the environment. Conventional treat- ment 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 alter- native 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 rmus 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 oers great potential for adopting an econom- ical metal-recovery system. The purpose of this paper is to review the available information on various attributes of utilization of micro- bial 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 indus- tries has resulted in generation of large quantities of eu- ent that contain high level of toxic heavy metals and their presence poses environmentaldisposal problems due to their non-degradable and persistence nature. In addition mining, mineral processing and extractive-metal- lurgical operations also generate toxic liquid wastes. Envi- ronmental engineers and scientists are faced with the challenging task to develop appropriate low cost tech- nologies for euent treatment. Conventional methods for removing metals from aqueous solutions include chem- ical precipitation, chemical oxidation or reduction, ion exchange, ltration, electrochemical treatment, reverse osmosis, membrane technologies and evaporation recov- ery. These processes may be ineective or extremely expen- sive especially when the metals in solution are in the range of 1100 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 aair and is not eco-friendly. Therefore, removal of toxic heavy metals to an environ- mentally safe level in a cost eective 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 eectively with heavy metals. Metabolically inactive dead biomass due to their unique chemical composition sequesters metal ions and metal complexes from solution, which obviates the neces- sity to maintain special growth-supporting conditions. Metal-sorption by various types of biomaterials can nd enormous applications for removing metals from solution and their recovery. 0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2005.12.006 * Corresponding author. E-mail address: d_goyal_2000@yahoo.com (D. Goyal). Bioresource Technology 98 (2007) 22432257 Rather than searching thousands of microbial species for particular metal sequestering features, it is benecial 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) micro- organisms 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. Dierent non-living bio- mass 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 dierent kinds of biomass, which have been tested for metal biosorption or removal (Volesky and Holan, 1995). 2. Metals in wastewater and their toxicity Euents from textile, leather, tannery, electroplating, galvanizing, pigment and dyes, metallurgical and paint industries and other metal processing and rening opera- tions 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 dis- comfort and sometimes life-threatening illness including irreversible damage to vital body system (Malik, 2004). From the eco-toxicological point of view, the most danger- ous metals are mercury, lead, cadmium and chromium(VI). In many instances the eect of heavy metals on human is not well understood. Metal ions in the environment bio- accumulate and are biomagnied along the food chain. Therefore, their toxic eect is more pronounced in animals at higher trophic levels. Mine tailing and euents 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 galvaniza- tion and production of alloys (Volesky and Schiewer, 2000). Cadmium has a half-life of 1030 years (Moore and Ramamoorthy, 1984) and its accumulation in human body aects kidney, bone and also causes cancer and its use is increasing in industrial applications such as electro- plating 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 euent treatment facil- ity within the industry discharging heavy metals contami- nated euent will be more ecient than treating large volumes of mixed wastewater in a general sewage treatment plant. Thus it is benecial to devise separate treatment pro- cedures for scavenging heavy metals from the industrial wastewater. Current research activity in this eld is focused on evaluating, whether biosorption may eventually provide such an eective and economic alternative treatment pro- cess, while biological treatment is reasonably eective in removing organic pollutants, heavy metals however tend to accumulate in biological sludge, which is unt as fertil- izers and require incineration for its disposal (Tien and Huang, 1991). 3. Conventional methods for heavy metal removal from industrial euents To mitigate the heavy metal pollution, many processes like adsorption, precipitation, coagulation, ion exchange, cementation, electro-dialysis, electro-winning, electro-coagu- lation and reverse osmosis have been developed. 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 eective its eciency is aected by low pH and the presence of other salts (ions). The process requires addition of other chemicals, which nally 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 specicity and is ineective 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 euents. 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. Com- monly used matrices for ion exchange are synthetic organic ion exchange resins. The disadvantage of this method is that it cannot handle concentrated metal solu- tion as the matrix gets easily fouled by organics and other solids in the wastewater. Moreover ion exchange is non- selective and is highly sensitive to pH of the solution. 3. Electro-winning is widely used in the mining and metal- lurgical industrial operations for heap leaching and acid mine drainage. It is also used in the metal transforma- tion 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 euents can be recov- ered 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 eective 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 2244 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 ions of opposite electrical charges provided by electro- coagulation system, they become destabilized and pre- cipitate 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 mem- branes) are tted between the electrodes in electrolytic cells, and under continuous electrical current the associ- ated ion migrates, allowing the recovery of metals. 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 phe- nomenon (Volesky, 1990). Till now, research in the area of biosorption suggests it an ideal alternative for decon- tamination of metal containing euents. 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 solu- tions. 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 ferment- ation. The process is not governed by the physiological con- straint of living microbial cells. Because of non-living biomass behave as an ion exchan- ger; 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 ecient 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 pos- sible. No aseptic conditions are required for this process. Metal can be desorbed readily and then recovered if the value and amount of metal recovered are signicant 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 interac- tive 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 fermen- tation 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. 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 euent, 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 eciency depends upon many factors, including the capacity, anity and specicity of the biosorbents and their physical and chemical conditions in euents. 5. Mechanism of metal uptake The understanding of the mechanism by which microor- ganisms accumulate metals is crucial to the development of microbial processes for concentration, removal and recov- ery of metals from aqueous solution. Metabolism-indepen- dent metal binding to the cell walls and external surfaces is the only mechanism present in the case of non-living bio- mass. 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 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 2245 groups. Metal ions could be adsorbed by complexing with negatively charged reaction sites on the cell surface (Beve- ridge and Murray, 1980; Gupta et al., 2000). The relative importance of each functional group is often dicult 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 Asper- gillus 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 cop- per 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 (unidentied) 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 com- plicated 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). Dierences in anities between elements and their ionic species may exist for various ligands encountered in biological system. Cell wall of dierent fungi can vary con- siderably in their overall composition, which leads to vary- ing adsorption capacity. However, localization of metal(s) has been carried out using electron microscopic and X- ray energy dispersive analyses. X-ray photoelectron spec- troscopy 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 micro- scopic observation carried out by Mullen et al. (1989) revealed the presence of Ag 2+ as discrete particles at or near the cell wall of both gram-positive and gram-negative bacteria. The presence of silver was also conrmed 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 uitans was exposed to Fe 2+ , while only Fe 3+ was present when biomass was exposed to ferric ions. Further, FTIR analysis has con- rmed that both carboxyl groups were involved in the uptake of Fe 2+ and Fe 3+ and sulfonate groups were responsible for Fe 3+ 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 alter- native technology for removing these pollutants. Non- living biomass of algae, aquatic ferns and seaweeds, waste biomass originated from plants and mycelial wastes (Tables 1a1c 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 eciency depends on the capacity, anity and specicity 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 pro- tein interaction with metals did not play a signicant role in copper(II) uptake (Muraleedharan and Venkobachar, 1990). Waste mycelia of A. niger, Phanerochaete chryso- genum and Claviceps paspali from industrial fermentation plants were used as biosorbent for Zn from aqueous envi- ronments in batch as well as column modes. Under opti- mized conditions, A. niger and C. paspali were superior to P. chrysogenum (Luef et al., 1991). Biosorption of lead by P. chrysogenum biomass was strongly aected by pH. At pH 45, 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 ura- nium or zinc than live cultures and biosorption rapidly reached 60% of the nal uptake value within 15 min of con- tact and uranium was deposited as ne 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 load- ing and pH. Metal uptake decreased in the presence of co- ions, 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 Cd 2+ , Cu 2+ , Zn 2+ , 2246 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 Table 1a Fungal biomass for removal of heavy metals from aqueous solution Biosorbent Metals Adsorption capacity (mg g 1 ) References Aspergillus foetidus Cr(VI) 2 Prasanjit and Sumathi (2005) Aspergillus niger Cu 5 Townsley and Ross (1986) Modak et al. (1996) Co 95 Kuyucak and Volesky (1989) Au 200 Kuyucak and Volesky (1989) Co 2.4 Sakaguchi and Nakajima (1991) Cr, Fe Goyal et al. (2003) Pb 30 Kim et al. (1995) Th 22 Tsezos and Volesky (1981) 162 Gadd (1988) U 29 Sakaguchi and Nakajima (1991) 27 Kuyucak and Volesky (1989) Zn Luef et al. (1991),Modak et al. (1996), Muter et al. (2002) Aspergillus terreus Th, U 60, 10 Tsezos and Volesky (1981) Aureobasidium pullulans Cu 6 Gadd and Mowll (1995) Pb 56.9 Suh et al. (1998) Ahluwalia and Goyal (2003) Cladosporium resinae Cu 18 Gadd (1988) de Rome and Gadd (1987) Pb Ahluwalia and Goyal (2003) Candida utilis Cr, Cu, Pb Muter et al. (2002) Ganoderma lucidum Cu 24 Muraleedharan and Venkobachar (1990) Mucor meihi Cr Tobin and Roux (1998) Mucor rouxii Pb, Zn, Cd, Ni 17, 4.89, 6.94, 5.24 Yan and Viraraghavan (2003) Pb 769 Lo et al. (1999) Penicillium chrysogenum Cd, Cu, Pb 11, 9, 116 Niu et al. (1993) Cd 56 Holan and Volesky (1995) 39 Fourest et al. (1994) Th 142 Tsezos and Volesky (1981) Gadd and White (1992) U 70 Tsezos and Volesky (1981) Zn 6.5 Niu et al. (1993) Luef et al. (1991) Cd, Zn, Cu, Pb Skowron ski et al. (2001) Pleurotus sapidus Cd, Hg 127, 287 Yalcinkaya et al. (2002) Streptoverticillium cinnamoneum Pb, Zn 57.7, 21.3 Puranik and Paknikar (1997) Penicillium italicum Cu de Rome and Gadd (1987) Th Gadd and White (1989) Penicillium spinulosum Cu, Zn 0.42, 0.2 Townsley and Ross (1985) Phanerochaete chrysosporium Cd 84.5 Gabriel et al. (1996) Pb 2 Say et al. (2001) Cu Yetis et al. (2000) Rhodotorula glutinis Pb 73.5 Cho and Kim (2003) Rhizopus nigricans Cr, Pb 47 Bai and Abraham (2001) Zn 14 Zhang et al. (1998) Cd, Ni, Pb 19, 5, 166 Fourest and Roux (1992) Holan and Volesky (1995) R. oligosporus Cr 126 Ari et al. (1999) Cd 17.09 Aloysius et al. (1999) R. arrhizus Ni, Cd, Zn, Pb, Cu 18, 27, 14, 56, 9.5 Fourest and Roux (1992) Cd 30 Holan and Volesky (1995) Cr 11 Bai and Abraham (1998) 36 Nourbakhsh et al. (1994) Co 2.9 Sakaguchi and Nakajima (1991) Niyogi et al. (1998) Sag and Kutsal (1998) Prakasham et al. (1999) Cu 10 Gadd (1988) de Rome and Gadd (1987), Sag and Kutsal (1998), Zhou and Ki (1991) (continued on next page) S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 2247 Ni 2+ and Co 2+ eciently 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 7080% 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 capa- city were obtained at initial metal concentration up to 100 mg l 1 in a batch reactor. Cd(II) biosorption to non- living biomass of fungus R. arrhizus and green alga Schi- zomeris 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 100150 mg l 1 . Adsorption by R. arrhizus was much higher than S. leiblenii (Ozer et al., 1997). Dried, non-liv- ing, granulated biomass of Streptoverticillium cinnamoneum was used for recovery of Pb and Zn at optimum pH 5.06.0 and 3.54.5, 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 eectively 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 1437% 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-trea- ted and untreated biomass showed that adsorption took 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 (2.08.0), initial metal ion concentration (100 500 mg l 1 ), contact time (224 h) and varying biomass concentration (0.53.0 g) were optimized. R. nigricans and R. arrhizus possessed good specic uptake of 11 mg Cr(VI) g 1 of biomass at the pH range of 2.07.0. Metal uptake capacity was in the order of Rhizopus nigri- cans > Rhizopus arrhizus > Aspergillus oryzae > Aspergillus niger (Bai and Abraham, 1998). Mucor meihi, a fermenta- tion industry waste was found to be an eective biosorbent for the removal of hexavalent chromium from leather industry euent. In comparative studies with ion-exchange resins, Mucor biomass showed biosorption levels corre- sponding 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 con- ditions over immobilized state. Stirred tank reactor studies indicated maximum chromium biosorption at 100 rpm and 1:10 biomassliquid ratio. The uidized bed reactor was more ecient in chromium removal than the stirred tank reactor (Prakasham et al., 1999). The inuences of co-cations (cadmium, copper, cobalt and nickel) on lead and zinc biosorption by S. cinnamo- neum and Penicillium chrysogenum in binary and multi- metal systems was studied (Puranik and Paknikar, 1999). Metal sorption capacity of S. cinnamoneum was observed Table 1a (continued) Biosorbent Metals Adsorption capacity (mg g 1 ) References Th 185 Tsezos and Volesky (1981) 97 Gadd et al. (1988) Gadd and White (1992) U 220 Tsezos and Volesky (1981) Tsezos et al. (1989) Tsezos and Deutschmann (1990) Saccharomyces cerevisiae Cd Volesky et al. (1993) Cr Nourbakhsh et al. (1994) 11.4 Omar et al. (1996) Co 5.8 Sakaguchi and Nakajima (1991) Pb Suh et al. (1998) Th 119 Gadd (1988) Cu 1740 Volesky and May-Phillips (1995) U 55140 Cu 10 Mattuschka et al. (1993) 0.4 Huang et al. (1990) Zn 1440 Volesky and May-Phillips (1995) Trametes versicolor Cr Bayramoglu et al. (2003) Cd 109 Gabriel et al. (1996) 2248 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 to be higher than P. chrysogenum for all metals. The extent of metal sorption depended on metal chemistry, anity for binding sites and type of metal. The order of metal biosorp- tion 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 (Ari et al., 1999). At an initial lead concentration ranging from 50 to 200 mg l 1 , pH 5.0 and optimum biomass concen- tration (0.5 g l 1 ) the maximum lead adsorption was 750 mg g 1 with lead uptake capacity of 126 mg g 1 . Chro- mium 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 articial wastewater in the concentration range of 5500 mg l 1 (Say et al., 2001). Maximum bio- sorption of dierent 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. Table 1b Algal biomass for removal of heavy metals from aqueous solution Biosorbent Metals Adsorption capacity (mg g 1 ) References Ascophyllum nodosum Cd 215 Holan et al. (1993) Co 156, 100 Kuyucak and Volesky (1988, 1989) Ni, Pb 30, 270360 Holan and Volesky (1995) Cd 30 Volesky and Prasetyo (1994) Aphanothece halophytica Zn 133 Incharoensakdi and Kitjaharn (2002) Chlorella vulgaris Ag Harris and Ramelow (1990) Cd 111 Aksu (2001) Cu 43 Aksu et al. (1992) Cr 3.5 Nourbakhsh et al. (1994) Cr, Cu, Ni Donmez et al. (1999) U 3.95 Sakaguchi and Nakajima (1991) Greene et al. (1986) Chlorella fusca Pb 293 Wehreim and Wettern (1994) Chlorella sorokiniana Cd Akhtar et al. (2003) Cladophora crispate Cr 3 Nourbakhsh et al. (1994) Caulerpa lentillifera Cu, Cd, Pb, Zn Apiratikul et al. (2004) Dunaliella sp. Cr 58.3 Donmez and Aksu (2002) Fucus vesiculosus Cd 73 Holan et al. (1993) Ni, Pb 17, 220371 Holan and Volesky (1995) Fucus spiralis Cd 64 Cordeo et al. (2004) Ecklonia maxima Cd Stirk and Staden (2002) Laminaria japonica Cd Yun et al. (2001) Laurencia obtuse Cr Hamdy (2000) Lyngbya taylorii Cd, Pb, Ni, Zn Klimmek et al. (2001) Phormidium laminosum Cu, Ni, Zn Blanco et al. (1998) Pilayella littoralis Al, Cd, Co, Cr, Ni, Zn Carrilho and Gilbert (2000) Pachymeniopis sp. Cr(VI) 225 Lee et al. (2000) Oscillatoria anguistissima Zn 641 Ahuja et al. (1999) Zn, Cu, Co Mohapatra and Gupta (2005) Spirogyra sp. Cr Gupta et al. (2001) Scenedesmus quadricula Cd, Cu, Zn Harris and Ramelow (1990) Scenedesmus obliquus Cr, Cu, Ni Donmez et al. (1999) Scenedesmus abundans Cd, Cu Terry and Stone (2002) Scenedesmus incrassatulus Cr, Cd, Cu Pena-Castro et al. (2004) Sargassum uiyans Cu Schiwer and Volesky (1996) 51 Kratochvil et al. (1997) Sargassum natans U Kuyucak and Volesky (1989) Cd 135 Holan et al. (1993) Ni, Pb 2444, 220270 Holan and Volesky (1995) Sargassum sp. Zn da Cotsa et al. (2001) Sargassum sp. Cu 38, Volesky et al. (2003),Padilha et al. (2005) Cd, Zn, Cu 157, 118, 77 Valdman and Leite (2000) Cd 120 Cruz et al. (2004) Tetraselmis suecica Cd Perez-Rama et al. (2002) Ulothrix zonata Cu Nuhoglu et al. (2002) Ulva lactuca Hg Zeroual et al. (2003) S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 2249 niger, R. oryzae and Mucor rouxii was studied (Baik et al., 2002). Binding of copper, cadmium, nickel and zinc was considerably improved by treating the cell wall fraction with 4 M NaOH at 121 C. Table 1c Bacterial biomass used for metal removal Biosorbent Metals Adsorption capacity (mg g 1 ) References Pseudomonas uorescens Th, U 15, 6 Tsezos and Volesky (1981) Pseudomonas sp. U Pons and Fuste (1993) Ochrobactrum anthropi Cr, Cd, Cu Ozdemir et al. (2003) Thiobacillus ferrooxidans Zn 82 Baillet et al. (1998) Cr Celaya et al. (2000) Rhodococcus erythropolis Cd, Zn Plette et al. (1996) Ocimum basilicium Cr Melo and DSouza (2004) Sphingomonas paucimobilis Cd Tangaromsuk et al. (2002) Bacillus rmus Pb, Cu, Zn 467, 381, 418 Salehizadeh and Shojaosadati (2003) B. coagulans Cr(VI) 39.9 Srinath et al. (2002) B. megaterium Cr(VI) 30.7 Srinath et al. (2002) Zoogloea ramigera Cr(VI) 2 Nourbakhsh et al. (1994) Cu 29 Aksu et al. (1992) Streptomyces noursei Cd, Cu, Ni 3.4, 9, 0.8 Mattuschka and Straube (1993) Pb, Zn, Ag, Co 36, 1.6, 38 Mattuschka and Straube (1993) Cr, Pb 1.2 Mattuschka and Straube (1993) 1.8, 55 Mattuschka et al. (1993) S. longwoodensis Pb, U 100, 440 Friis and Myers-Keith (1986) S. rimosus Zn 30 Mameri et al. (1999) Table 1d Plant derived biomass used for metal removal Biosorbent Metals Adsorption capacity (mg g 1 ) References Activated baggase carbon Cr Mor et al. (2002) Alfalfa Cu, Pb 20, 43 Tiemann et al. (1999) Artocarpus heterphyllus Cd Inbaraj and Sulochana (2004) Azolla liculoides Pb 93 Sanyhumbi et al. (1998) Banana pith (Musacea zingiberales) Pb, Cu, Ni, Cr, Zn Low et al. (1995) Hydrilla verticillata casp. and Salvinia sp. Cu Elankumaran et al. (2003) Carrot pulp Pb, Ni, Zn, Fe Joshi et al. (2003) Ceratophyllum demersum Cu, Pb, Zn 6.17, 45, 14 Keskinkan et al. (2004) Cupressus Female Cone Cr(VI) 119 Murugan and Subramanian (2003) Eucalyptus wood powder Pb, Ni, Zn, Fe Joshi et al. (2003) Eucalyptus bark Cr(VI) Sarin and Pant (2006) Ground corncobs Cd, Cu, Pb Vaughan et al. (2001) Ni, Zn Hydrilla verticillata casp. Cu Elankumaran et al. (2003) Larrea tridenta Cu 24 Gardea-Torresdey et al. (2004a,b) Olive mill solid residue Hg, Pb, Cu Pagnanelli et al. (2002) Zn, Cd Paper mill sludge Pb, Cu, Ag Calace et al. (2003) Cd Pb, Ni, Zn, Fe Joshi et al. (2003),Ahluwalia and Goyal (2004) Sago processing waste Cu, Pb 12.4, 46.6 Quek et al. (1998) Sawdust Zn, Ni, Cd, Cu, Pb Marin and Ayele (2002) Cr(VI) Acar and Malkoc (2004) Wheat stem and Spent Babul Bark Ni Verma and Shukla (2000) Oryza sativa L. hush Pb Zulkali et al. (2006) Waste tea-leaves Pb, Ni, Zn, Fe Joshi et al. (2003),Ahluwalia and Goyal (2005) Wola globosa Cd, Cr Upatham et al. (2002) Water hyacinth roots Cr Low et al. (1997) Helianthus annuus L. (Sunower) Cu Lin et al. (2003) Allium sativum L. (Garlic) Cd Jiang et al. (2001) Grape stalk waste Cu, Ni 15.9, 18.1 Villaescusa et al. (2004) Hemidesmus indicus Pb Chandrasekhar et al. (2003) Myriophyllum spicatum Pb, Cu, Cd Keskinkan et al. (2003) 2250 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 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 aected metal uptake capacity (Nourbakhsh et al., 1994). Maxi- mum adsorption was observed at a temperature range of 2535 C, which increased with increasing metal concen- trations 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, chro- mate 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, 9095% 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 non- viable biomass of the cyanobacterium Phormidium lamino- sum 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 eect on the binding of Cu(II). Washing with dilute acids was much faster and eective than NaOH, NaCl, CaCl 2 and ultra pure water reaching equilibrium within 30 min and the eciency was independent of the concentra- tion 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 inuence of algal biomass concentration on metal uptake by all species and both Fre- undlich and Langmuir adsorption models described the short-term biosorption. Out of 48 dierent 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 exhib- ited a typical Langmuir isotherm with q max of 225 mg g 1 and K 1106 mg ml 1 (Lee et al., 2000). Biosorption of tri- valent chromium by protonated brown algal biomass of Eklonia revealed three types of functional groups. The car- boxyl group was the chromium-binding site within the pH range of 15 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- tion level was found to be a function of contact time at dif- ferent 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 (Api- ratikul 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-har- vested water bloom cyanobacterium Microcystis aeruginosa (Li et al., 2004) was optimum at 4.08.0 pH. The batch sorption reached the equilibrium within 1 h and followed the Freundlich isotherm model. Uranium was eectively desorbed with 0.01 N HCl. This naturally abundant bio- mass otherwise nuisance cyanobacterium exhibited good potential for application in removal of uranium from aque- ous solution. The waste biomass of Sargassum sp. for the recovery of ionic copper from simulated semiconductor euents was investigated (Padilha et al., 2005) using con- tinuous system comprising of four column reactors lled 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 con- taining 500 mg l 1 copper. Copper concentration was found to be less than 0.5 mg l 1 in the euent from the outlet of the reactor. Five dierent brown seaweeds, Bifur- caria bifurcata, Saccorhiza polyschides, Ascophyllum nodo- sum, 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 signicant 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 140250 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 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 2251 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 inuence 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 dierent biosorbents like dried mycelium of some species of fungi, baggase, rice husk and fermented baggase was examined to remove cyanide from industrial euent (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 ow conditions. The sorption was observed to be both pH and concentration dependent with pH 45 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 euent of an electroplating industry (Verma and Shukla, 2000). The removal of nickel was 210% 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 capa- city of dierent 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 Na 4 EDTA was eective and there existed the possibility of recycling the phytomass. Biosorption capacity of plant biomass of Indian Sarapa- rilla (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 eect the Pb removal but Zn and Cr uptake decreased. Metal loaded biomass was regenerated with HNO 3 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 solu- tion 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. bio- mass 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-rst order, Ritchie second order and modied Ritchie second order models showed better ts with modied Ritchie second order model. The LangmuirFreundlich (Sips equations) model best denes the experimental equilibrium data among the three isotherm models (Freundlich, Lang- muir and LangmuirFreundlich) used. A complete recov- ery of the adsorbed metals ions from the spent adsorbent was achieved by using 0.01 M HCl. The adsorption of activated carbon prepared from apri- cot 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 12 for Cr(VI) and at pH 36 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 modied lignocellulosic bre/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 bre 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 bre showed 7.73, 5.57 and 8.02 mg g 1 against 4.23, 3.37 and 3.55 mg g 1 for unmodied jute bre which followed Langmuir adsorption model. Desorption eciency, regenerative and reuse capa- city of these adsorbent were also assessed for three succes- sive adsorptiondesorption cycles. The sorption of lead by tree fern, an agricultural by product was carried out using agitated and baed system (Ho, 2005). The optimum pH for lead removal was 4.9. Also pseudo-second-order kinet- ics analysis was performed to determine the rate constant of sorption, the equilibrium sorption capacity, and the ini- tial 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 spectro- scopy indicated the amino-Cd interaction responsible for this sorption. These nding 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 2252 S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 and entrapment in inter and intra-brillar capillaries and space of the structural polysaccharide network as a result of the concentration gradient and diusion. There are sev- eral 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 guar- antees biosorption, perhaps due to steric, conformational or other eects. Several proprietory biosorption processes were devel- oped and commercialized in the early 1990s using Alga- SORB TM (Brierley et al., 1986) and AMT-Bioclaim TM (Darnall, 1991) but did not attract widespread adoption due to a lack of understanding of the underlying mech- anism of metal-sorption, proper selection of industrial euents for pilot testing and scaling up of the process (Kratochvil and Volesky, 1998). Routinely most prospec- tive biosorbents are discovered by trial and experimenta- tion. Many microorganisms can be used as biosorbents. Fungi in particular have unique metal adsorption charac- teristics and are easy to cultivate (Gadd, 1988). They can successfully absorb toxic metal ions Zn 2+ , Cu 2+ , Cd 2+ , Pb 2+ , Ni 2+ , Fe 2+ , Mn 2+ and Cr 6+ from aqueous solution. But the process is susceptible to complexation or precipita- tion 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 specic activity, while others are specic 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 Pak- nikar, 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 adsorp- tion 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. Pagna- nelli 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 range of 5.013.5 mg g 1 under dierent operating condi- tions. The biosorption capacity of copper, cadmium and zinc on dried activated sludge was 0.32 m mol g 1 for metal systems such as CuCd; 0.29 m mol g 1 for CuZn and 0.32 m mol g 1 for CdZn. 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 up- take 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 bio- logical uptake of heavy metal cations. Biosorption oers an economically feasible technology for ecient removal and recovery of metal(s) from aqueous solution. The pro- cess 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 anities that can remove a variety of metal cations. These will be particularly useful for industrial euents, 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, ecacy and cost eectivity. Biosorption processes are applicable to euents con- taining low concentrations of heavy metals for an extended period. This aspect makes it even more attractive for treat- ment of dilute euent that originates either from an indus- trial plant or from the primary wastewater treatment facility. Thus biomass-based technologies need not neces- sarily replace the conventional treatment routes but may complement them. At present, information on dierent biosorbent materials is inadequate to accurately dene 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 identied. To predict the dierence between the uptake capacities of the biomass, the experimental results should be tested against an adsorption model. The development of a packed bed or uidized-bed biosorption model would be helpful for evaluating industrial-scale biosorption S.S. Ahluwalia, D. Goyal / Bioresource Technology 98 (2007) 22432257 2253 column performance, based on laboratory scale experi- ments and to understand the basic mechanism involved in order to develop better and eective biosorbent. 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