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Aug 12, 2012 - Gavrilescu 2004; Volesky 2001). Biosorption ...... accumulation by rotating biological contactor (RBC) biofilms. J .... ron Sci Biotechnol 2:9â33.
workers and assess their efficiency for different rnetal bearing solutions and industrial efiluents .... whether some others, such as Al, Ag, Cd, Sn, Au, Sr Hg, Ti.
can remove heavy metals from aqueous solutions by biosorption. Although the complexity of the microor- ganism's structure implies that there are many ways for.
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Occurrence of 'overshoot's and impact on heavy metal removal has not been analyzed enough. .... their biosorption potential, and the vast majority of studies have been ..... let stream increases sharply and the effective life of the column is over ..
(incomplete metal removal, high reagent and energy requirements, generation of toxic sludge or other waste products). Most of these methods are often ineffective or uneconomical when heavy metal concentration is higher (10-100 mg/L) than permissible concentration less than 1 mg /L), which require a high cost when they used for disposal the heavy metals from aqueous effluents. Increasing environmental awareness and legal constraints being imposed on discharge of effluents are major factors for using cost–effective alternative technologies. In recent years, microbial biomass has emerged as an option for developing economic and eco-friendly wastewater treatment process., therefore, applying biotechnology in controlling and removing metal pollution has been paid much attention, and gradually becomes hot topic in the field of metal pollution control because of its potential application. Alternative process is a biosorption, which utilizes various certain natural materials of biological origin, including bacteria, fungi, yeast, algae, etc. . Biosorption can be defined as the ability of biological materials to accumulate heavy metals from wastewater through metabolically mediated or physico-chemical pathways of uptake . Biosorption, which is the ability of certain microbial biomaterials to bind and concentrate heavy metals from even the most dilute aqueous solutions, offers a technically feasible and economically attractive alternative . „Biosorption‟ has been defined as the property of certain biomolecules (or types of biomass) to bind and concentrate selected ions or other molecules from aqueous solutions . Algae, bacteria and fungi and yeasts have proved to be potential metal biosorbents . It is consider an ideal alternative method for removing contaminates from effluents Biosorption is a rapid phenomenon of passive metal sequestration by the non-growing biomass/adsorbents. It has advantages compared with conventional techniques , some of these are listed: (low cost; high efficiency; minimization of chemical and or biological sludge; no additional nutrient requirement; regeneration of biosorbent; and possibility of metal recovery). The biosorption process involves a solid phase (sorbent or biosorbent; adsorbent; biological material) and a liquid phase (solvent, normally water) containing a dissolved species to be sorbet (adsorbate, metal). Due to the higher affinity of the adsorbent for the adsorbate species, the latter is attracted and bound there by different mechanisms. The process continues till equilibrium is established between the amount of solid-bound adsorbate species and its portion remaining in the solution. The degree of adsorbent affinity for the adsorbate determines its distribution between the solid and liquid phases . Biosorption process, in which microorganisms are used to remove and recover heavy metals from aqueous solutions, have been known for few decades but have emerged as a low cost promising technology in the last decades. In this process, the uptake of heavy metals and radioactive compounds occurs as a result of physico-chemical interactions of metal ions with the cellular compounds of biological species . As a result, the idea of the use of biomaterial for the uptake of heavy metals has been extensively studied for the last two decades. Biotechnological approaches can succeed in those areas and are designed to cover such niches. Microorganisms have evolved various measures to respond to heavy-metal stress via processes such as transport across the cell membrane, biosorption to cell walls and entrapment in extracellular capsules, precipitation, complexation and oxidation– reduction reactions [9-16]. They have proven capability to take up heavy metals from aqueous solutions, especially when the metal concentrations in the effluent range from less than 1 to about 20 mg/L . Besides, flexibility to handle the range of physico-chemical parameters in effluents, selectivity to remove only the desired metals and the cost-effectiveness are some added advantages of biological metal cleanup techniques. These factors have promoted extensive research on the biological methods of metal removal. This paper reviews the use of different types of bacteria, algae fungi and yeasts and its wastes as biosorbents to remove heavy metals from wastewaters; these biological biosorbents have a highly effective as well as reliable in the removal of heavy metal ions from wastewater. Hence, this work attempts to summarize recent studies in the removal of heavy metals using biological biosorbents published between 2000 and 2013. Equilibrium studies in biosorption of heavy metals using various kinds of biosorbents are also reviewed. II.
The use of natural materials for heavy metals removal is becoming a concern in all countries. Heavy metals have been excessively released into the environment due to rapid industrialization and have created a major global concern. Heavy metal ions have great effects on all forms of life. Heavy metal pollution is one of the most important environmental problems today because of their toxicity, bio-accumulation tendency, threat to human life and the environment . Heavy metals are presented in nature and industrial waste water, so the presence of heavy metals in surface and ground water pose a contamination problem. Large number of industries can produce and discharge wastes containing different heavy metals into the environment. The main source of heavy metal pollution are metal plating, mining, smelting, battery manufacturing, tanneries, petroleum refining, pigment manufacture, printing paint manufacture, pesticides, etc. The term “heavy metal” is entirely applied to a group of metals (and metal-like elements) with density greater than 5 g/cm³, atomic number above 20 and is toxic or poisonous at low concentrations .
The main elements that considered as a heavy metals are chromium(Cr), manganese(Mn), cobalt (Co), copper(Cu), zinc(Zn), molybdenum(Mo), mercury(Hg), nickel(Ni), tin(Sn), lead(Pb), cadmium(Cd), antimony(Sb), etc. Three kinds of heavy metals are of concern, including toxic metals (such as Hg, Cr, Pb, Zn, Cu, Ni, Cd, As, Co, Sn, etc.), precious metals (such as Pd, Pt, Ag, Au, Ru etc.) and radionuclides such as U, Th, Ra, Am, etc. [1, 20]. Lead, mercury, cadmium and chromium (VI) are at the top on the toxicity list from among various metal ions, the first three, called “the big three”, are in the limelight due to their major impact on the environment . Heavy metals are natural components from the earth‟s crust. They cannot be destroyed or degraded. However, most of these heavy metals become toxic at high concentrations due to their ability to accumulate in living tissues. Removal of heavy metals from industrial wastewater is of primary importance. Cadmium, zinc, copper, nickel, lead, mercury and chromium are often detected in industrial wastewaters. Table 1 gives the main sources of heavy metal pollutants and its effects on human lives. A.
Copper, one of the most widely used heavy mental, is mainly employed in, electrical, electroplating industries, and in larger amounts is extremely toxic to living organisms. The presence of copper (II) ions causes serious toxicological concerns, it is usually known to deposit in brain, skin, liver, pancreas and myocardium . Copper usually occurs in nature as oxides and sulphides. Copper is an essential substance to human life. Copper is found in a variety of enzymes and is used for biological electron transport. Like all heavy metals, it is potentially toxic, especially at high concentrations. Thirty grams of copper sulfate is potentially lethal in humans. In high doses, it can cause anemia, liver and kidney damage, and stomach and intestinal irritation. Wilson‟s disease, a disease that causes the body to retain copper can lead to brain and liver damage if untreated. Inhalation of copper produces symptoms similar to those of silicosis and allergic contact dermatitis. Copper normally occurs in drinking water from copper pipes, as well as from additives designed to control algal growth. The suggested safe level of copper in drinking water for humans varies depending on the source, but tends to be pegged at 1.3 mg/L according to the US Environmental Protection Agency. Too much copper in water has also been found to damage marine life. The observed effect of these higher concentrations on fish and other creatures is damage to gills, liver, kidneys, and the nervous system. Common oxidation states of copper include the less stable copper (I) state, Cu+, and the more stable copper (II) Cu2+ . Environmental contamination due to copper is caused by mining, printed circuits, metallurgical, fiber production, pipe corrosion and metal plating industries  the other major industries discharging copper in their effluents are paper and pulp, petroleum refining and wood preserving. Agricultural sources such as fertilizers, fungicidal sprays and animal wastes also lead to water pollution due to copper. Copper may be found as a contaminant in food, especially shell fish, liver, mushrooms, nuts and chocolates. Any packaging container using copper material may contaminate the product such as food, water and drink . In some instances, exposure to copper has resulted in jaundice and enlarged liver. It is suspected to be responsible for one form of metal fume fever . Containing is linked to an increase in lung cancer among exposed workers . B.
There are two stable oxidation states of chromium found in the environment, Cr (III) and Cr (VI) which have contrasting toxicities, mobility and bioavailability. Chromium compounds of oxidation state Cr6+ are powerful oxidants. Chromium hexavalent (VI) compounds are used as pigments for Photography, and in pyrotechnics, dyes, paints, inks, and plastics. They can also be used for stainless steel production, textile dyes, wood preservation, leather tanning, and as anti-corrosion coatings. While Cr (III) is relatively innocuous and immobile, Cr (VI) moves readily through soils and aquatic environments and is a strong oxidizing agent capable of being absorbed through the skin. Trivalent chromium, Cr (III), is an essential element required for normal carbohydrate and lipid metabolism. C.
Lead is a heavy metal poison which forms complexes with Oxo-groups in enzymes to affect virtually all steps in the process of hemoglobin synthesis and porphyria metabolism . Toxic levels of lead in human have been associated with encephalopathy, seizures and mental retardation . D.
The most severe form of Cd toxicity in humans is “itai-itai”, a disease characterized by excruciating pain in the bone [29, 30]. Other health implications of Cd in humans include kidney dysfunction, hepatic damage and hypertension . However, it has been suggested that overall nutritional status (rather than mere Cd content of food) is a more critical factor in determining Cd exposure. Table 1 shows the sources and toxicity of certain metal ions.
• Greatly improved recovery of bound heavy metals from the biomass; • Greatly reduced volume of hazardous waste produced. B.
Biosorption depends on many factors that can effect on it. Some of these factors are related to the biomass and metal and the others are related to environmental conditions. The major factors that affect the biosorption process are: 1) Temperature: In contrast to bioaccumulation process, biosorption efficiency remains unaffected within the range 20-35 ᵒC, although high temperatures, e.g. 50 ᵒC, may increase biosorption in some cases, but these high temperatures may cause permanent damage to microbial living cells and then decreasing metal uptake [7, 48]. Adsorption reactions are generally exothermic and the extent of adsorption increases with decreasing temperature. The maximum biosorption capacity for Ni and Pb by S. cerevisiae was obtained at 25 ᵒC and found to decrease as the temperature was increased to 40 ◦C . 2) Characteristics of Biomass: The nature of the biomass or derived product may be considered one of the important factors, including the nature of its application such as: freely-suspended cells, immobilized preparations, living biofilms etc. Physical treatments such as boiling, drying, autoclaving and mechanical disruption will all affect binding properties while chemical treatments such as alkali treatment often improve biosorption capacity, especially evident in some fungal systems because of DE acetylation of chitin to form chitosan-glycan complexes with higher metal affinities . Growth and nutrition on the biomass, and age can also influence biosorption due to changes in cell size, wall composition, extracellular product formation, etc. 3) The Surface Area to Volume Ratio: It may be important for individual cells or particles, as well as the available surface area of immobilized biofilms. In addition, the biomass concentration may also affect biosorption efficiency with a reduction in sorption per unit weight occurring with increasing biomass concentration . 4) Acidity: pH seems to be the most important parameter in the biosorption processes. Biosorption is similar to an ion-exchange process, i.e. biomass can be considered as natural ion-exchange materials which mainly contain weakly acidic and basic groups. Therefore, pH of solution influences the nature of biomass binding sites and metal solubility; it affects the solution chemistry of the metals, the activity of the functional groups in the biomass and the competition of metallic ions. Metal biosorption has frequently been shown to be strongly pH dependent in almost all systems examined, including bacteria, cyanobacteria, algae, and fungi. Competition between cations and protons for binding sites means that biosorption of metals like Cu, Cd, Ni, Co and Zn is often reduced at low pH values [51, 52]. Generally, the heavy metal uptake for most of the biomass types decline significantly when pH of the metal solutions is decreased from pH 6.0 to 2.5. At pH less than 2, there are minimum or negligible removal metal ions from solutions. The metal uptake increases when pH increases from 3.0 to 5.0. Optimum value of pH is very important to get a highest metal sorption, and this capacity will decrease with further increase in pH value. 5) Biomass Concentration: Concentration of biomass in solution affects the specific uptake . At a given equilibrium concentration, the biomass adsorbs more metal ions at low cell densities than at high densities . So electrostatics interaction between the cells plays an important role in metal uptake. At lower biomass concentration, the specific uptake of metals is increased because an increase in biosorbent concentration leads to interference between the bindings sits . High biomass concentration restricts the access of metal ions to the binding sites . 6) Initial Metal Ion Concentration: The initial concentration provides an important driving force to overcome all mass transfer resistance of metal between the aqueous and solid phases . Increasing amount of metal adsorbed by the biomass will be increased with initial concentration of metals. Optimum percentage of metal removal can be taken at low initial metal concentration. Thus, at a given concentration of biomass, the metal uptake increases with increase in initial concentration. 7) Metal Affinity to the Biosorbent: Physical/chemical pretreatment affects permeability and surface charges of the biomass and makes metal binding groups accessible for binding. It can be manipulated by pretreating the biomass with alkalis, acids detergents and heat, which may increase the amount of metal uptake .
Examples Gram-positive bacteria (Bacillus sp., Corynebacterium sp., etc.). Gram-negative bacteria (Eschrichia sp., Pseudomonas sp., etc.). and Cyanobacteria (Anabaena sp., Synechocystis sp., etc.) Molds (Aspergillus sp., Rhizopus sp., etc.) Mushrooms (Agaricus sp., Trichaptum sp., etc.). and Yeast (Scaccharomyces sp., Candida sp., etc.) Micro-algae (clorella sp. Chamydomonas sp., etc.) and Macro-algae (green seaweed (Enteromorpha sp.,Codium sp.,etc.), brown seaweed(Sargassum sp., Ecklonia sp., etc., and red seaweed(geildium sp., Porphyra sp., etc.)) Fermentation wastes, food/beverage wastes, activated sludges, anaerobic sludge, etc. Fruit/Vegetable wastes, rice straws, wheat bran, soybean halts, etc. Plant residues, sawdust, tree barks, weeds, etc. Chitosan-driven materials, cellulose-driven materials, etc.
B. Factors Affecting Biomass Choice When choosing biomass, for large-scale industrial uses, the main factor to be taken into account is its availability and cheapness [5, 6, 67]. Considering these factors, native biomass can come from: (i) Industrial wastes, which should be available free of charge; (ii) Organisms easily obtainable in large amounts in nature; and (iii) Organisms that can be grown quickly or specially cultivated or propagated for biosorption purposes [6, 67]. Adsorptive pollutants like metals can be removed by living microorganisms, but can also be removed by dead biological material .
Bacillus sp. Pseudomonas sp. Micrococcus sp.
3) Fungi: Fungi are one of the industrial fermentation waste biomass which is really excellent metal sorbets. So, fungi including yeasts have received increased attention. Fungi gives good efficient and economical for sequestering heavy toxic metals from dilute aqueous solutions by biosorption because: (i) It offers the advantage of having a high percentage of cell wall materials; (ii) It shows excellent metal binding properties; (iii) It is available in large quantities from the antibiotic and food industries; (iv) It provides an eco-friendly environment. Three groups of fungi have a major practical importance: the molds, yeasts and mushrooms. Filamentous fungi and yeasts have been used in many wastewater treatments to bind metallic elements. Fungi are found entirely in natural environments and important in industrial processes. The structure of fungi has a wide range of morphologies from unicellular yeasts to polymorphic and filamentous fungi; many of them have complex macroscopic fruiting bodies.
Environmental conditions such as pH, temperature, etc.
Based on location where biosorption occurs: in these criteria, biosorption mechanisms are classified as extra cellular accumulation/precipitation, cell surface sorption /precipitation and intra cellular accumulation.
Biosorption of metals occurs mainly through several interactions such as physical adsorption, ion exchange, complexation, precipitation and entrapment in inner space . In the biosorption process, two types of biological cells (living and dead cells) as well as chemical pretreated biomass can be used. The metal ion uptake by living and dead cells can consist of two different modes. The mechanisms of uptake by living materials (bioaccumulation) and removal by dead ones (biosorption) are entirely different.
PS: polysaccharides, UA: uronic acids, SPS: sulfated PS, AA: amino acids, Cto: chitosan, Cti: chitin, PG: peptidoglycan, PL: phospholipids, TA: teichoic acid, LPS: lipo, PS.
VI. EQUILIBRIUM AND KINETIC STUDIES A. Biosorption Isotherms Biosorption is usually described through isotherm. Adsorption isotherm is relatively simple method for determining the feasibility of using a certain adsorbent material for a particular application. It is represented the equilibrium relationship between the adsorbate concentration in the fluid phase and the adsorbate concentration in the adsorbent particles at a given temperature. It is a plot of the amount of adsorbate per unit weight of adsorbent qe against the equilibrium concentration of the adsorbate remaining in solution Ce The quantity described is nearly always normalized by the mass of adsorbent to allow comparison of different materials . By knowing the adsorption isotherm, the affinity of the adsorbate for an adsorbent is quantified. For most applications in wastewater treatment, the amount of adsorbate adsorbed is usually a function of the aqueous-phase concentration . Some typical isotherm shapes are shown as arithmetic graphs as shown in Fig. 3 . From the above curves, it will be noted that the adsorption is specific property related to the nature of the adsorbate-adsorbent system .
The application of the Elovich equation in liquid phase adsorption is gaining in popularity . Pseudo-second order kinetic model was applied on biosorption of lead onto dried activated sludge with correlation coefficient of 0.994 . It was found that pseudo-second order model could be represent the adsorption of lead onto GAC better than Elovich model with correlation coefficient of 0.994,0.726 respectively . Some researchers applied first and second-order-pseudo models in GAC adsorption of phenol. Pseudo-second order model fit the data with 0.998 correlation coefficient for the concentration of 1000 mg/L, and pseudo-first order model fit the data with 0.900 correlation coefficient for 100 mg/l concentration . VII.
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Report "Biosorption of Heavy Metals: A Review"

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