Bioremediation of Aquatic Environments Polluted With Heavy Metals

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Contents

Title Page

Acknowledgement 3

Abstract 4

Introduction 5

Part one: Definition of bioremediation

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Part two: Heavy metals and its hazards effect in aquatic environment

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Part three: Methods & mechanisms of heavy metal removal

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Part four : Mechanisms of microbial removal of heavy metals 24

Arabic abstract 27

References 28

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Acknowledgement

First and above of all , thanks to Allah , without his grace and help this study would have been unable to be completed . I would like to express my sincere and my deep gratitude and appreciation to my supervisor Dr. Sahar El-Shatoury , associate professor of Microbiology , Botany Department , Faculty of science , Suez Canal University , for her keen supervision , guidance , encouragement during the course of study . I would like to thank Dr. Samira Resk

Mansour , professor of Microbiology , Head of Botany Department and all the staff members of Botany Department , Faculty of science , Suez Canal University for their encouragement .

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Abstract

The aquatic environment with its water quality is considered the main factor controlling the state of health and disease. Pollution of the aquatic environment by inorganic and organic chemicals is a major factors posing serious threat to health, this report focuses on the pollution caused by heavy metals as mercury (Hg), cadmium (Cd), arsenic (As), chromium (Cr), thallium (Tl), and lead (Pb) which are very dangerous because they tend to bioaccumulate in the body result in many diseases. Also, this report focuses on the different methods of heavy metals removal and bioremediation. Actinomycetes ,in particular, show many mechanisms of heavy metal removal as biosorption, metal reduction and produce siderophores .

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Introduction

Water is essential to humans and other lifeforms. Thus any pollution in the water or in the aquatic environment has great effects on human health, animals and fishes. One of the dangerous pollutants is the heavy metals. Heavy metals can enter a water supply by industrial and consumer waste, or even from acidic rain breaking down soils and releasing heavy metals into streams, lakes, rivers, and groundwater. Metal ions can be incorporated into food chains and concentrated in aquatic organisms to a level that affects their physiological state. Of the effective pollutants are the heavy metals which have drastic environmental impact on all organisms. Trace metals such as Zn, Cu and Fe play a biochemical role in the life processes of all aquatic plants and animals; therefore, they are essential in the aquatic environment in trace amounts. In the Egyptian irrigation system, Cu, Pb and Cd are serious polluting metals. The main source of Cu and Pb are industrial wastes as well as algaecides (for Cu), while that of Cd is the phosphatic fertilizers used in crop farms (Mason, 2002).

There are various methods of heavy metals removal; those are categorized as chemical, physical and biological. This report focus on the biological removal of heavy metals by actinomycetes . Actinomycetes are a group of Gram-positive bacteria with high guanine and cytosine content and they include some of the most common soil life, freshwater life, and marine life, playing an important role in decomposition of organic materials, such as cellulose and chitin, Thereby, they are playing a vital part in organic matter turnover and carbon cycle. This replenishes the supply of nutrients in the soil and is an important part of humus formation.

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1.Definition of bioremediation :

Bioremediation can be defined as any process that uses microorganisms, fungi, green plants or their enzymes to return the natural environment altered by contaminants to its original condition.

Generally, bioremediation technologies can be classified as in situ or ex situ. In situ bioremediation involves treating the contaminated material at the site while ex situ involves the removal of the contaminated material to be treated elsewhere. Some examples of bioremediation technologies are bioventing, land farming, bioreactor, composting, bioaugmentation and biostimulation.

Bioremediation can occur on its own (natural attenuation or intrinsic bioremediation) or can be spurred on via the addition of fertilizers to increase the bioavailability within the medium (biostimulation). Recent advancements have also proven successful via the addition of matched microbe strains to the medium to enhance the resident microbe population's ability to break down contaminants. Microorganism whose perform the function of bioremediation is known as Bioremediators (bioaugmentation).

1.2 Examples of bioremediation cases :

1.2.1 Pesticides, San Francisco Bay Estuary

Pesticide contamination of rivers and streams is a matter of concern throughout the United States. Field and laboratory studies in the Sacramento River and San Francisco Bay have shown the effects of biological and non-biological processes in degrading commonly used pesticides, such as molinate, thiobencarb, carbofuran, and methyl parathion.

1.2.2 Agricultural chemicals in the Midcontinent

Agricultural chemicals affect the chemical quality of ground water in many Midwestern States. Studies in the Midcontinent have traced the fate of nitrogen fertilizers and pesticides in ground and surface waters. These studies have shown that many common contaminants, such as the herbicide atrazine, are degraded by biological (microbial degradation) and non-biological (photolytic degradation) processes.

1.2.3 Sewage effluent, Cape Cod, Massachusetts

Disposal of sewage effluent in septic drain fields is a common practice throughout the United States. Systematic studies of a sewage effluent plume at Massachusetts Military Reservation (formerly known as Otis Air Force Base) led to the first accurate field and laboratory measurements of how rapidly natural microbial populations degrade nitrate contamination (denitrification) in a shallow aquifer.

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1.2.4 Crude oil spill, Bemidji, Minnesota

In 1979, a pipeline carrying crude oil burst and contaminated the underlying aquifer. U.S. Geological Survey (USGS) scientists studying the site found that toxic chemicals leaching from the crude oil were rapidly degraded by natural microbial populations. Significantly, it was shown that the plume of contaminated ground water stopped enlarging after a few years as rates of microbial degradation came into balance with rates of contaminant leaching. This was the first and best-documented example of intrinsic bioremediation in which naturally occurring microbial processes remediates contaminated ground water without human intervention.

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2.1-Definition of heavy metals:

The term heavy metal refers to any metallic chemical element that has a relatively high density and is toxic or poisonous at low concentrations. Examples of heavy metals include mercury (Hg), cadmium (Cd), arsenic (As), chromium (Cr), thallium (Tl), and lead (Pb).

Heavy metals are natural components of the Earth's crust. They cannot be degraded or destroyed. To a small extent they enter our bodies via food, drinking water and air. As trace elements, some heavy metals (e.g. copper, selenium, zinc) are essential to maintain the metabolism of the human body. However, at higher concentrations they can lead to poisoning. Heavy metal poisoning could result, for instance, from drinking-water contamination (e.g. lead pipes), high ambient air concentrations near emission sources, or intake via the food chain.

Heavy metals are dangerous because they tend to bioaccumulate. Bioaccumulation means an increase in the concentration of a chemical in a biological organism over time, compared to the chemical's concentration in the environment. Compounds accumulate in living things any time they are taken up and stored faster than they are broken down (metabolized) or excreted.

2.2-How metals get into freshwater :

Metals are introduced into aquatic systems as a result of a variety of human activities involving the mining, processing, or use of metals and/or substances that contain metal pollutants. The most common heavy metal pollutants are arsenic, cadmium, chromium, copper, nickel, lead and mercury. There are different types of sources of pollutants: point sources (localized pollution), where pollutants come from single, identifiable sources. The second type of pollutant sources are nonpoint sources, where pollutants come from dispersed (and often difficult to identify) sources. There are only a few examples of localized metal pollution, like the natural weathering of ore bodies and the little metal particles coming from coal-burning power plants via smokestacks in air, water and soils around the factory.

The most common metal pollution in freshwater comes from mining companies. They usually use an acid mine drainage system to release heavy metals from ores, because metals are very soluble in an acid solution. After the drainage process, they disperse the acid solution in the groundwater, containing high levels of metals.

2.3- What happens when an excess of metals enters freshwater ecosystems.

When the pH in water falls, metal solubility increases and the metal particles become more mobile. That is why metals are more toxic in soft waters. Metals can become ‘locked up’ in bottom sediments, where they remain for many years. Streams coming from draining mining areas are often very acidic and contain high concentrations of dissolved metals with little aquatic life. Both localized and dispersed metal pollution cause environmental damage because metals are non-biodegradable. Unlike some organic pesticides, metals cannot be broken down into less harmful components in the environment.

The ionic form of a metal is more toxic, because it can form toxic compounds with other ions. Electron transfer reactions that are connected with oxygen can lead to the production of toxic oxyradicals, a toxicity mechanism now known to be of considerable importance in both animals and plants. Some oxyradicals, such as superoxide anion (O2-) and the hydroxyl radical (OH-), can cause serious cellular damage.

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2.4-Metal tolerance

Some metals, such as manganese, iron, copper, and zinc are essential micronutrients. They are essential to life in the right concentrations, but in excess, these chemicals can be poisonous. At the same time, chronic low exposures to heavy metals can have serious health effects in the long run.

Tolerance to metals has also been recorded in invertebrates and in fish. After exposure for 24 hours to a copper concentration of 0.55 mg/l, rainbow trout showed a 55 per cent inhibition of sodium uptake and a 4 per cent reduction in affinity for sodium, which resulted in an overall decrease in total sodium concentration of sulphydryl-rich protein (Lauren and McDonald 1987a,b). The protein was considered to be a metallothionein. These low molecular weight proteins contain many sulphur-rich amino acids which bind and detoxify some metals. The pretreatment of an organism with low doses of a metal may stimulate metallothionein synthesis and provide tolerance during a subsequent exposure (Pascoe and Beattie, 1979).

2.5-Toxicity of metals .

For the protection of human health, the maximum permissible concentrations for metals in natural waters that are recommended by the Environmental Protection Agency (EPA), are listed below:

Table 1 : Maximum Permissible Concentrations (MPC) of Various Metals in Natural Waters For the Protection of Human Health

Metal Chemical Symbol mg m-3

Mercury Hg 0.144 Lead Pb 5 Cadmium Cd 10 Selenium Se 10 Thallium Tl 13 Nickel Ni 13.4 Silver Ag 50 Manganese Mn 50 Chromium Cr 50 Iron Fe 300 Barium Ba 1000

This table gives an idea of the relative toxicity of various metals. Mercury, lead and cadmium are

not required even in small amounts by any organism.

Because metals are rather insoluble in neutral or basic , pHs of 7 or above give a highly misleading picture of the degree of metal pollution. So in some cases it may underestimate significantly the total of metal concentrations in natural waters.

The three most pollutans heavy metals are Lead, Cadmium, and Mercury.

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Effects of heavy metals are summarized as following : 2.5.1 Effects of Chromium on the environment

Chromium is used in metal alloys and pigments for paints, cement, paper, rubber, and other materials. Low-level exposure can irritate the skin and cause ulceration. Long-term exposure can cause kidney and liver damage, and damage too circulatory and nerve tissue. Chromium often accumulates in aquatic life, adding to the danger of eating fish that may have been exposed to high levels of chromium.

2.5.2 Effects of Copper on the environment

Copper is an essential substance to human life, but in high doses it can cause anemia, liver and kidney damage, and stomach and intestinal irritation. People with Wilson's disease are at greater risk for health effects from overexposure to copper. Copper normally occurs in drinking water from copper pipes, as well as from additives designed to control algal growth.

2.5.3 Effects of Lead on the environment

In humans exposure to lead can result in a wide range of biological effects depending on the level and duration of exposure. Various effects occur over a broad range of doses, with the developing foetus and infant being more sensitive than the adult. High levels of exposure may result in toxic biochemical effects in humans which in turn cause problems in the synthesis of haemoglobin, effects on the kidneys, gastrointestinal tract, joints and reproductive system, and acute or chronic damage to the nervous system.

2.5.4 Effects of Mercury on the environment

Mercury is a toxic substance which has no known function in human biochemistry or physiology and does not occur naturally in living organisms. Inorganic mercury poisoning is associated with tremors, gingivitis and/or minor psychological changes, together with spontaneous abortion and congenital malformation.

Monomethylmercury causes damage to the brain and the central nervous system, while foetal and postnatal exposure have given rise to abortion, congenital malformation and development changes in young children.

2.5.5 Effects of Nickel on the environment

Small amounts of Nickel are needed by the human body to produce red blood cells, however, in excessive amounts, can become mildly toxic. Short-term overexposure to nickel is not known to cause any health problems, but long-term exposure can cause decreased body weight, heart and liver damage, and skin irritation. The EPA does not currently regulate nickel levels in drinking water. Nickel can accumulate in aquatic life, but its presence is not magnified along food chains.

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2.5.6 Effects of Selenium on the environment

Selenium is needed by humans and other animals in small amounts, but in larger amounts can cause damage to the nervous system, fatigue, and irritability. Selenium accumulates in living tissue, causing high selenium content in fish and other organisms, and causing greater health problems in human over a lifetime of overexposure. These health problems include hair and fingernail loss, damage to kidney and liver tissue, damage to circulatory tissue, and more severe damage to the nervous system.

2.5.7 Effects of Antimony on the environment

Antimony is a metal used in the compound antimony trioxide, a flame retardant. It can also be found in batteries, pigments, and ceramics and glass. Exposure to high levels of antimony for short periods of time causes nausea, vomiting, and diarrhea. There is little information on the effects of long-term antimony exposure, but it is a suspected human carcinogen. Most antimony compounds do not bioaccumulate in aquatic life.

2.5.8 Effects of Cadmium on the environment

Cadmium derives its toxicological properties from its chemical similarity to zinc an essential micronutrient for plants, animals and humans. Cadmium is biopersistent and, once absorbed by an organism, remains resident for many years (over decades for humans) although it is eventually excreted.

In humans, long-term exposure is associated with renal disfunction. High exposure can lead to obstructive lung disease and has been linked to lung cancer, although data concerning the latter are difficult to interpret due to compounding factors. Cadmium may also produce bone defects (osteomalacia, osteoporosis) in humans and animals. In addition, the metal can be linked to increased blood pressure and effects on the myocardium in animals, although most human data do not support these findings.

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Methods of heavy metals removal are divided into three classes according to the

nature of the process :

3.1Chemical methods:

3.1.1 Carbamates

Carbamates are chemical reducing agents that can be obtained as either sodium dimethyldithiocarbamate or sodium diethyldithiocarbamate. Carbamate precipitation is again an equilibrium reaction that does not go to completion. Metal residuals of 1.0 - 1.5 mg/l can usually be obtained. Carbamates are not effective at acidic pH levels and are not always effective at treating chelated wastes.

3.1.2 Selective heavy metals removal from waters by amorphous zirconium phosphate

Uptake of heavy metals including lead, cadmium, and zinc onto ZrP was studied by using a polystyrene sulfonic-acid exchanger D-001 as a reference sorbent and Ca2+ as a competing cation due to its ubiquity in natural or industrial waters. The results indicated that the uptake of heavy metals onto ZrP is essentially an ion-exchange process and dependent upon solution pH. In comparison with D-001, ZrP exhibited more favorable sorption of heavy metals particularly in terms of high selectivity, as indicated by the distribution coefficients of ZrP even several orders higher than D-001 towards heavy metals when calcium ion coexisted at a high level in solution.( Bingcai Pan, Qingrui Zhang, Wei Du, Weiming Zhang, Bingjun Pan, Qingjian Zhang, Zhengwen Xu, Quanxing Zhang ) .

3.1.3 Organometallic Precipitation

In 1991 Steve Holtzman, pioneered a new more environmentally responsible method of removing heavy metals. This process revolves around the formation of insoluble organometallic compounds formed by reacting metal bearing wastes with a proprietary organic agent.

3.1.4 Chemical precipitation

Precipitation of metals is achieved by the addition of coagulants such as alum, lime, iron salts and other organic polymers. The large amount of sludge containing toxic compounds produced during the process is the main disadvantage.

• Hydroxide precipitation : Chemical precipitation of heavy metals as their hydroxides using lime or sodium hydroxide is widely used. Lime is generally favoured for precipitation purposes due to the low cost of precipitant, ease of pH control in the range of 8.0 –10.0 and the excess of lime also serves as an adsorbent for the removal of metal ions. The efficiency of the process depends on a number of factors, which include the ease of hydrolysis of the metal ion, nature of the oxidation state, pH, presence of complex forming ions, standing time, degree of agitation and settling and filtering and characteristics of the precipitate. The limitations of this method include difference between metals in the optimum pH for hydroxide formation may lead to the problems in the treatment of effluents containing combined metal ions. Variability in metal hydroxide solubility at a fixed pH is another drawback.

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• Carbonate precipitation : Carbonate precipitation of metals using calcium or sodium carbonate is very limited. Patterson et al., 1997 reported improved results using carbonate precipitate for Cd (II) and Pb (II) from electroplating effluents. When the pH was brought to 7.5, residual concentration of Pb (II) and Cd (II) were 0.60 and 0.25 mg/L respectively.

• Sulphide precipitation : Since most of the heavy metals form stable sulphides, excellent metal removal can be obtained by sulphide precipitation. Treatment with sulphides is most advantageous when used as a polishing step after conventional hydroxide precipitation or when very high metal removals are required.

3.1.5 Chemical reduction

Reduction of hexavalent chromium can also be accomplished with electro-chemical units. The electrochemical chromium reduction process uses consumable iron electrodes and an electric current to generate ferrous ions that react with hexavalent chromium to give trivalent chromium as follows United States Environmental Protection Agency (USEPA, 1979).

3Fe2+ + CrO42- + 4H2O 3Fe3+ + Cr 3+ + 8OH-

Another application of reduction process is the use of sodium borohydride, which has been considered effective for the removal of mercury, cadmium, lead, silver and gold (Kiff, 1987).

3.1.6 Xanthate process

Insoluble starch xanthate (ISX) is made from commercial cross linked starch by reacting it with sodium hydroxide and carbon disulphide. To give the product stability and to improve the sludge settling rate, magnesium sulphate is also added. ISX works like an ion exchanger, removing the heavy metals from the wastewater and replacing them with sodium and magnesium. Average capacity is 1.1-1.5 meq of metal ion per gram of ISX (Anon, 1978).

ISX is most commonly used by adding to it the wastewater as slurry for continuous flow operations or in the solid form for batch treatments. It should be added to the effluent at pH ≥ 3. Then the pH should be allowed to rise above 7 for optimum metal removal (Wing, 1978). Residual metal ion level below 50 µg/L has been reported (Hanway et al., 1978, Wing et al., 1978). The effectiveness of soluble starch xanthate (SSX) for removal of Cd (II), Cr (VI) and Cu (II) and insoluble starch xanthate (ISX) for Cr (VI) and Cu (II) have been evaluated under different aqueous phase conditions. Insoluble starch xanthate had better binding capacity for metals. The binding capacity of SSX and ISX respectively for different metal ions follows the sequence of Cr (VI)> Cu (II)> Cd(II) and Cr (VI)> Cu (II) (Tare et al., 1988).

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3.1.7 Solvent extraction

Liquid-liquid extraction (also frequently referred as solvent extraction) of metals from solutions on a large scale has experienced a phenomenal growth in recent years due to the introduction of selective complexing agents (Beszedits, 1988). In addition to hydrometallurgical applications, solvent extraction has gained widespread usage for waste reprocessing and effluent treatment.

Solvent extraction involves an organic and an aqueous phase. The aqueous solution containing the metal or metals of interest is mixed with the appropriate organic solvent and the metal passes into the organic phase. In order to recover the extracted metal, the organic solvent is contacted with an aqueous solution whose composition is such that the metal is stripped from the organic phase and is reextracted into the stripping solution. The concentration of the metal in the strip liquor may be increased, often 110 to 100 times over that of the original feed solution. Once the metal of interest has been removed, the organic solvent is recycled either directly or after a fraction of it has been treated to remove the impurities.

3.2- Physical methods :

3.2.1 Membrane process

Important examples of membrane process applicable to inorganic wastewater treatment include reverse osmosis and eletrodialysis (Environmental Protection Agency EPA, 1980). These processes involve ionic concentration by the use of selective membrane with a specific driving force. For reverse osmosis, pressure difference is employed to initiate the transport of solvent across a semipermeable membrane and electro dialysis relies on ion migration through selective permeable membranes in response to a current applied to electrodes. The application of the membrane process described is limited due to pretreatment requirements, primarily, for the removal of suspended solids. The methods are expensive and sophisticated, requiring a higher level of technical expertise to operate.

A liquid membrane is a thin film that selectively permits the passage of a specific constituent from a mixture (Beszedits, 1988). Unlike solid membranes, however liquid membranes separate by chemistry rather than size, and thus in many ways liquid membrane technology is similar to solvent extraction. Since liquid membrane technology is a fairly recent development, a number of problems remain to be solved. A major issue with the use of supported membranes is the long term stability of the membranes, whereas the efficient breakup of microspheres for product recovery is one of the difficulties encountered frequently with emulsion membranes.

3.2.2 Evaporators

In the electroplating industry, evaporators are used chiefly to concentrate and recover valuable plating chemicals. Recovery is accomplished by boiling sufficient water from the collected rinse stream to allow the concentrate to be returned to the plating bath. Many of the evaporators in use also permit the recovery of the condensed steam for recycle as rinse water. Four types of evaporators are used throughout the elctroplating industry (USEPA, 1979a) (I) Rising film evaporators; (ii) Flash evaporators using waste heat; (iii) submerged tube evaporators; (iv) Atmospheric evaporators. Both capital and operational costs for evaporative recovery systems are high. Chemical and water reuse values must offset these costs for evaporative recovery to become economically feasible.

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3.2.3 Cementation

Cementation is the displacement of a metal from solution by a metal higher in the electromotive series. It offers an attractive possibility for treating any wastewater containing reducible metallic ions. In practice, a considerable spread in the electromotive force between metals is necessary to ensure adequate cementation capability. Due to its low cost and ready availability, scrap iron is the metal used often. Cementation is especially suitable for small wastewater flow because a long contact time is required. Some common examples of cementation in wastewater treatment include the precipitation of copper from printed etching solutions and the reduction of Cr (VI) in chromium plating and chromate-inhibited cooling water discharges (Case, 1974). Removal and recovery of lead ion by cementation on iron sphere packed bed has been reported (Angelidis et al., 1988, 1989). Lead was replaced by a less toxic metal in a harmless and reusable form.

3.2.4 Ion exchange

Ion exchange resins are available selectively for certain metal ions. The cations are exchanged for H+ or Na+. The cation exchange resins are mostly synthetic polymers containing an active ion group such as SO3H. The natural materials such as zeolites can be used as ion exchange media (Van der Heen, 1977). The modified zeolites like zeocarb and chalcarb have greater affinity for metals like Ni and Pb (Groffman et al., 1992). The limitations on the use of ion exchange for inorganic effluent treatment are primarily high cost and the requirements for appropriate pretreatment systems. Ion exchange is capable of providing metal ion concentrations to parts per million levels. However, in the presence of large quantities of competing mono-and divalent ions such as Na and Ca, ion exchange is almost totally ineffective.

3.2.5 Electrodeposition

Some metals found in waste solution can be recovered by electrodeposition using insoluble anodes. For example, spent solutions resulting from sulphuric acid cleaning of Cu may be saturated with copper sulphate in the presence of residual acid. These are ideal for electro-winning where the high quality cathode copper can be electrolytically deposited while free sulphuric acid is regenerated.

3.2.6 Adsorption

Since activated carbon also possesses an affinity for heavy metals, considerable attention has been focussed on the use of carbon for the adsorption of hexavalent chromium, complexed cyanides and metals present in various other forms from wastewaters. Watonabe and Ogawa (1929) first presented the use of activated carbon for the adsorption of heavy metals. The mechanism of removal of hexavalent and trivalent chromium from synthetic solutions and electroplating effluents has been extensively studied by a number of researchers. According to some investigators, the removal of Cr (VI) occurs through several steps of interfacial reactions (Huang and Bowers, 1979).

� The direct adsorption of Cr6+ onto carbon surface. � The reduction of Cr6+ species to Cr3+ by carbon on the surface. � The adsorption of the Cr3+ species produced, which occurs to a much lesser extent than the adsorption of the Cr6+ species.

Adsorption of Cr (III) and Cr (VI) on activated carbon from aqueous solutions has been studied (Toledo, 1994). Granular activated carbon columns have been used to treat wastewaters containing lead and cadmium (Reed and Arunachalam, 1994, Reed et al., 1994). Granular activated carbon was used for the removal of Pb (II) from aqueous solutions (Cheng et al., 1993). The adsorption process was inhibited by the presence of humic acid, iron (III), aluminum (III) and calcium (II).

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Disadvantages of conventional chemical & physical methods for treatment of wastewater containing heavy metals

Precipitation, by adjusting the pH value is not selective and any iron (ferric ion) present in the liquid effluent will be precipitated initially followed by other metals. Consequently precipitation produces large quantities of solid sludge for disposal, for example precipitation as hydroxides of 100 mg/l of copper (II), cadmium (II) or mercury (II) produces as much as 10-, 9- and 5 fold mg/l of sludges respectively. The metal hydroxide sludge resulting from treatment of electroplating wastewater has been classified as a hazardous waste. The performance characteristics of heavy metal waste water treatment technologies are identified in the table below. The versatility, simplicity and other technology characteristics will contribute to the overall process costs, both capital and operational. At present many of these technologies such as ion exchange represent significant capital investments by industry.

Table 2: Performance characteristics of various heavy metal removal

/recovery technologies

Technology pH

change

Metal

selectivity

Influence

of

Suspended

solids

Tolerance

of

organic

molecules

Working

level for

appropriate

metal

(mg/I) Adsorption, e.g.

Granulated

Activated

carbon

Limited

tolerance

Moderate Fouled Can be

poisoned

<10

Electro

chemical

Tolerant Moderate Can be

engineered

to tolerate

Can be

accommodated

>10

Ion exchange Limited

tolerance

Chelate -

resins can

be selective

Fouled Can be

poisoned

<100

Membrane Limited

tolerance

Moderate Fouled Intolerant >10

Precipitation (a) Hydroxide Tolerant Non-selective Tolerant Tolerant >10

(b) Sulphide Limited

tolerance

Limited

selective

pH dependent

Tolerant Tolerant >10

Solvent

extraction

Some

systems

Metal

selective

Fouled Intolerant >100

pH

tolerant

extractants

available

As seen from the table above, conventional methods are ineffective in the removal of low concentrations of heavy metals and they are non-selective. Moreover, it is not possible to recover the heavy metals by the above mentioned methods.

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3.3- Biological methods :

3.3.1 Biosorption

During the 1970’s increasing environmental awareness and concern led to a search for new techniques capable of inexpensive treatment of polluted wastewaters with metals. The search for new technologies involving the removal of toxic metals from wastewaters has directed attention to biosorption, based on binding capacities of various biological materials.

Till date, research in the area of biosorption suggests it to be an ideal alternative for decontamination of metal containing effluents. Biosorbents are attractive since naturally occurring biomass/adsorbents or spent biomass can be effectively used. Biosorption is a rapid phenomenon of passive metal sequestration by the non-growing biomass/adsorbents. Results are convincing and binding capacities of certain biomass/adsorbents are comparable with the commercial synthetic cation exchange resins.

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 sorbed (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.

There are many types of adsorbents; Earth’s forests and plants, ocean and freshwater plankton, algae and fish, all living creatures, that including animals are all “biomass/ adsorbents”. The renewable character of biomass that grows, fuelled directly or indirectly by sunshine, makes it an inexhaustible pool of chemicals of all kinds.

Biosorption has advantages compared with conventional techniques (Volesky, 1999). Some of these are listed below:

• Cheap: the cost of the biosorbent is low since they often are made from abundant or waste material.

• Metal selective: the metalsorbing performance of different types of biomass can

be more or less selective on different metals. This depends on various factors such as type of biomass, mixture in the solution, type of biomass preparation and physico-chemical treatment.

• Regenerative: biosorbents can be reused, after the metal is recycled. • No sludge generation: no secondary problems with sludge occur with

biosorption, as is the case with many other techniques, for example, precipitation.

• Metal recovery possible: In case of metals, it can be recovered after being

sorbed from the solution.

• Competitive performance: biosorption is capable of a performance comparable to the most similar technique, ion exchange treatment. Ion exchange is, as mentioned above, rather costly, making the low cost of biosorption a major factor.

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Biosorbents intended for bioremediation environmental applications are waste biomass of crops, algae, fungi, bacteria, etc., which are the naturally abundant. Numerous chemical groups have been suggested to contribute to biosorption. A review of biosorption of heavy metals by microorganisms is presented below. Biosorption by microorganisms have various disadvantages, and hence many low cost adsorbents (industrial/agricultural waste products/byproducts) are increasingly used as biosorbents. This chapter also provides review of the low cost adsorbents used for removal of heavy metals (Ahalya et al., 2004).

- Biosorption of heavy metals by microorganisms

A large number of microorganisms belonging to various groups, viz. bacteria, fungi, yeasts, cyanobacteria and algae have been reported to bind a variety of heavy metals to different extents (table 3 ). The role of various microorganisms by biosorption in the removal and recovery of heavy metal(s) has been well reviewed and documented (Stratton, 1987; Gadd and Griffiths, 1978; Volesky, 1990; Wase and Foster, 1997; Greene and Darnall, 1990; Gadd 1988). Most of the biosorption studies reported in literatures have been carried out with living microorganisms. However due to certain inherent disadvantages, use of living microorganisms for metal removal and recovery is not generally feasible in all situations. For example, industrial effluents contain high concentrations of toxic metals under widely varying pH conditions. These conditions are not always conducive to the growth and maintenance of an active microbial population. There are several advantages of biosorption of using non living biomass and they are as follows:

1. Growth independent nonliving biomass is not subject to toxicity limitation by cells. 2. The biomass from an existing fermentation industry, which essentially is a waste after

fermentation, can be a cheap source of biomass. 3. The process is not governed by physiological constraints of microbial cells. 4. Because nonliving biomass behaves as an ion exchanger, the process is very rapid,

requiring anywhere between few minutes to few hours. Metal loading is very high on the surface of the biomass leading to very efficient metal uptake.

5. Because cells are non-living processing conditions are not restricted to those conducive for the growth of the cells. Hence, a wider range of operating conditions such as pH, temperature and metal concentrations are possible. Also aseptic operating conditions are not essential.

6. Metals can be desorbed readily and then recovered. If the value and the amount of metal recovered are insignificant and if the biomass is plentiful, the metal loaded biomass can be incinerated, eliminating further treatment.

Biosorption essentially involves adsorption processes such as ionic, chemical and physical adsorption. A variety of ligands located on the fungal cell walls are known to be involved in metal chelation. These include carboxyl, amine, hydroxyl, phosphate and sulphydryl groups. Metal ions could be adsorbed by complexing with negatively charged reactions sites on the cell surface. In the table below presents an exhaustive list of microrganisms used for the uptake of heavy metals.

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Table 3 : Biosorbent uptake of metals by Microbial Biomass

Metal Biomass Type Biomass class Metal uptake

(mg/g) Freshwater alga Biosorbent 86-94

Fungal biomass Biosorbent 65

Rhizopus arrhizus Fungus 54

Streptomyces noursei Filamentous bacter 38.4

Ag

Sacchromyces cerevisiae Yeast 4.7

Sargassum natans Brown alga 400

176 Aspergillus niger Fungus

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Palmaria tevera Marine alga 164

Palmaria palmata Marine alga 124

Chlorella pyrenoidosa Freshwater alga 98

Cyanidium caldarium Alga 84

Chlorella vulgaris Freshwater alga 80

Bacillus subtilis Bacteria Cell wall 79

Chondrus crispus Marine alga 76

Bacillus subtilis Bacterium 70

71 Spirulina platensis Freshwater alga

58

Rhodymenia palmata Marine alga 40

Au

Ascophyllum nodosum Brown marine alga 24

Ascophyllum nodosum Brown markertman

ine alga

215

Sargassum natans Brown marine alga 135

Fucus vesiculosus Brown marine alga 73

Candida tropicalis Yeast 60

56 Pencillium chrysogenum Fungus

11


Sacchromyces cervisiae Yeast 20-40


Rhizopus nigricans Fungus 19

Pencillium spinulosum Fungus 0.4

Pantoea sp. TEM 18 Bacteria 204.1

Chlamydomonas reinhardtii Alga 42.6

Spirulina sp. Blue green algae 1.77 meq/g

Enterobacter cloaceae

(Exopolysaccharide)

Marine bacterium 16

Padina sp. Brown seaweed 0.75

Sargassum sp. Brown seaweed 0.76

Ulva sp. Green seaweed 0.58

Gracillaria sp. Red seaweed 0.30

Cd

Gloeothece magna Cyanobacteria 115–425 µg mg−1

Ascophyllum nodosum Brown marine algae 100

Sacchromyces cerevisiae Yeast 4.7

Co

Ulva reticulata Marine green algae 46.1

20

Enterobacter cloaceae Marine bacterium 4.38

Bacillus biomass Bacterium 118 Cr3+

60 Cr 6+


Candida tropicalis Yeast 4.6

Streptomyces nouresei Bacteria 1.8


Spirulina sp. Cyanobacteria 10.7 meq/g

Cr

Spirogyra sp. Filamentous algae 4.7

Bacillus subtilis Biosorbent 152


Manganese oxidising bacteria MK-2 50

Cladosporium resinae Fungus 18


Saccharomyces crevisae Yeast 17-40; 10; 6.3

Pichia guilliermondii Yeast 11

Scenedesmus obliquus Freshwater algae 10


Pencillium chrysogenum Fungus 9

Streptomyces noursei sp. Filamentous bacteria 5

Bacillus sp Bacterium 5

Pencillium spinulosum Fungus 0.4-2

Aspergillus niger Fungus 1.7

Trichoderma viride Fungus 1.2

Pencillium chrysogenum Fungus 0.75


Ulva reticulata Marine green alga 56.3

Spirulina sp. Blue green algae 6.17 meq/g

Enterobacter cloaceae

(Exopolysaccharide)

Marine bacterium 6.60





Thiobacillus thiooxidans Bacteria 38.54

Cu

Ulothrix zonata Algae 176.20

Bacillus subtillis Bacterial cell wall

preparation

201

Bacillus biomass Bacterium 107

Fe

Sargassum fluitans Brown alga 60


Pencillium chrysogenum

(biomass not necessarily in its

natural state)

Fungus 20

Cystoseira baccata Marine alga 178

Hg

Chlamydomonas reinhardtii Algae 72.2

Fucus vesiculosus Brown marine algae 40

Ascophylum nodosum Brown marine algae 30

Sargassum natans Brown marine algae 24-44

Ni

Bacillus licheniformis Bacterial cell wall

preparation

29

21



Bacillus subtillis Bacterial cell wall

preparation

6


Absidia orchidis Fungus 5

Ulva reticulata Marine green algae 46.5





Polyporous versicolor White rot fungus 57

Bacillus subtilis(biomass not

necessarily in its natural

state)

Biosorbent 601

Absidia orchidis Fungus 351

Fucus vesiculosus Brown marine algae 220-370

Ascophyllum nodosum Brown marine algae 270-360

Sargassum natans Brown marine algae 220-270

Bacillis subtilis(biomass not


state)

Biosorbent 189

Pencillium chrysogenum Fungus 122; 93


Streptomyces longwoodensis Filamentous bacteria 100

Rhizopus arrhizus Fungus 91; 55

Streptomyces noursei Filamentous bacteria 55

Chlamydomonas reinhardtii Algae 96.3





Pb

Ecklonia radiata Marine alga 282

Freshwater alga(biomass not


state)

Biosorbent 436 Pd

Fungal biomass Biosorbent 65

Pt Freshwater alga (biomass not


state)

Biosorbent 53

Sargassum fluitans Brown algae 520

Streptomyces longwoodensis Filamentous bacteria 440


Sacchromyces crevisae Yeast 55-140

U

Bacillus sp. Bacterium 38

22

Chaetomium distortum Fungus 27

Trichoderma harzianum Fungus 26

Pencillium chrysogenum

(biomass not necessarily in its

natural state)

Fungus 25

Alternaria tenulis

Rhizopus arrhizus Fungus 160; 93 Th

Sacchromyces cerevisae Yeast 70

Bacillus subtilis(biomass not


state)

Biosorbent 137

Sargassa sp.

Brown algae 70

Manganese oxidising bacteria (MK-2) 39

Sacchromyces cerevisae Yeast 14-40



Pencillium chrysogenum Fungus 6.5

Bacillus sp. Bacterium 3.4

Pencillium spinulosum Fungus 0.2





Zn

Thiobacillus thiooxidans Bacteria 43.29

Among micro-organisms, fungal biomass offers the advantages of having high percentage of cell wall material, which shows excellent metal binding properties (Gadd, 1990; Rosenberger, 1975; Paknikar, Palnitkar and Puranik, 1993). Many fungi and yeast have shown an excellent potential of metal biosorption, particularly the genera Rhizopus,Aspergillus, Streptoverticullum and Sacchromyces (Volesky and Tsezos, 1981; Galun et al., 1984; de Rome and Gadd, 1987; Siegel et al., 1986; Luef et al., 1991, Brady and Duncan, 1993 Puranik and Paknikar, 1997).

23

3.3.2 Phytoremediation

Phytoremediation is the use of certain plants to clean up soil, sediment, and water contaminated with metals. The disadvantages include that it takes a long time for removal of metals and the regeneration of the plant for further biosorption is difficult.

3.3.3 Complexation

The metal removal from solution may also take place by complex formation on the cell surface after the interaction between the metal and the active groups. Aksu et al. 1992 hypothesized that biosorption of copper by C. vulgaris and Z. ramigera takes place through both adsorption and formation of coordination bonds between metals and amino and carboxyl groups of cell wall polysaccharides. Complexation was found to be the only mechanism responsible for calcium, magnesium, cadmium, zinc, copper and mercury accumulation by Pseudomonas syringae. Micro-organisms may also produce organic acids (e.g., citric, oxalic, gluonic, fumaric, lactic and malic acids), which may chelate toxic metals resulting in the formation of metallo-organic molecules. These organic acids help in the solubilisation of metal compounds and their leaching from their surfaces. Metals may be biosorbed or complexed by carboxyl groups found in microbial polysaccharides and other polymers.

3.3.4 Removal of heavy metals using waste eggshell

When calcined eggshell was applied in the treatment of synthetic wastewater containing heavy metals, a complete removal of Cd as well as above 99% removal of Cr was observed after 10 min.

Although the natural eggshell had some removal capacity of Cd and Cr, a complete removal was not accomplished even after 60 min due to quite slower removal rate. However, in contrast to Cd and Cr, an efficient removal of Pb was observed with the natural eggshell rather than the calcined eggshell. From the application of the calcined eggshell in the treatment of real electroplating wastewater, the calcined eggshell showed a promising removal capacity of heavy metal ions as well as had a good neutralization capacity in the treatment of strong acidic wastewater. (PARK Heung Jai, JEONG Seong Wook, YANG Jae Kyu, KIM Boo Gil, LEE Seung Mok) .

24

4- Mechanisms of microbial removal of heavy metals:

4.1 Metal reduction

Bacterial reduction of metallic ions has been shown to occur for U(VI), Se(VI), Cr(VI), Mo(VI), Se(IV),

Hg(II), Ag(I) and others (Bradley and Obraztsova, 1998). Three Cr(VI) reduction mechanisms have been described (Cervantes and Campos, 2007): (i) In aerobic conditions, chromate reduction has been commonly associated with soluble chromate reductases that use NADH or NADPH as cofactors. (ii) Under anaerobiosis, some bacteria, can use Cr(VI) as an electron acceptor in the electron transport chain (Bopp and Ehrlich, 1988). (iii) Reduction of Cr(VI) may also be carried out by chemical reactions associated with compounds such as amino acids, nucleotides, sugars, vitamins, organic acids or glutathione. For instance, ascorbate is capable of reducing Cr(VI), and riboflavin derivatives FAD and FMN are essential coenzymes for chromate reducing flavoenzymes (Masayasu, 1991).

Example � Biological reduction of chromate by Streptomyces griseus (Ashwini C. Poopal, R. Seeta

Laxman)

The most toxic form of chromium Cr(VI) can be converted to less toxic Cr(III) by reduction. Among the actinomycetes tested for chromate reduction, thirteen strains reduced Cr(VI) to Cr(III), of which one strain of Streptomyces griseus (NCIM 2020) was most efficient showing complete reduction within 24 h. Chromate reduction was associated with the bacterial cells and sonication was the best method of cell breakage to release the enzyme. The enzyme was constitutive and did not require presence of chromate during growth for expression of activity. Chromate reduction with cell free extract (CFE) was observed without added NADH. However, addition of NAD(P)H resulted in 2–3-fold increase in activity. Chromate reductase showed optimum activity at 28◦ C and pH 7.

� CHROMIUM REMOVAL FROM TANNERY WASTEWATER USING CHEMICAL AND BIOLOGICAL

TECHNIQUES AIMING ZERO DISCHARGE OF POLLUTION (Hesham M. Abdulla , Engy M. Kamal

, Amr H. Mohamed , Ahmed D. El-Bassuony , Suez Canal University, Ismailia )

Tannery effluent containing chromium is one of the most obvious problems in leather industry. In Egypt, the tannery wastewater is discharged directly to the main domestic sewage pipeline which adds difficulties to the sewer system and to the wastewater treatment plants , Therefore, the removal and reuse of the chromium content of these wastewaters is necessary for environmental protection and economic reasons. In this study, the recovery of chromium (III) was carried out by using precipitation process , To this purpose, two common precipitating agents lime and cement dust were used.

For biological removal of Cr(VI), thirty four actinomycete isolates were found to tolerate up to

100 mg/l Cr(VI), five of these isolates could tolerate Cr(VI) at concentration up to 2500 mg/l and have abilities to produce chromate reductas .

25

4.2 Biosorption

Biosorption is a rapid phenomenon of passive metal sequestration by the non-growing biomass (Gourdon, et al., 1990). Biosorption mainly involves cell surface complexation, ion exchange and microprecipitation (Gadd, 1990). Different microbes have been found to vary in their affinity for different heavy metal(s) and hence differ in their metal binding capacities. Some biomass(es) exhibit preference for certain heavy metal(s) whereas others do not show any specific binding and have a broad range (Greene and Darnall, 1990 ). The bacterial cell wall is the first component that comes into contact with metal ions, where the solutes can be deposited on the surface or within the cell wall structure (Doyle et al., 1980). Since the mode of solute uptake by dead/inactive cells is extracellular, the chemical functional groups of the cell wall play vital roles in biosorption. Due to the nature of the cellular components, several functional groups are present on the bacterial cell wall, including carboxyl, phosphonate, amine and hydroxyl groups (Van der wal et al., 1997) .

Example

� Biosorption of cadmium ions by Actinomycetes and separation by flotation (M.I. Kefala, A.I. Zouboulis, K.A. Matis)

The removal of cadmium, a toxic metal of high environmental priority due to its toxicity, from dilute aqueous solutions has been studied , applying microorganisms and using living, as well as non-living bacterial biomass of two specially isolated Actinomycetes strains, AK61 and JL322. The main parameters influencing this treatment process, namely contact time, pH of the solution, temperature and toxic metal and biomass concentrations have been examined and Langmuir isotherms have been depicted. Dispersed-air flotation was applied as the subsequent separation method for harvesting the suspended metal-laden microorganisms, following the biosorption of cadmium. The investigated parameters (in batch mode, laboratory scale) were in this case the dispersion pH, the flotation time, the air flow rate and the surfactant concentration. Electrokinetic measurements have been also performed for the biomass dispersions, under similar conditions with biosorption, providing useful information for the process mechanisms. Applying the optimum defined conditions, over 95% removal of cadmium has been achieved in one stage and simultaneously, quantitative separation of the used (metal-loaded) biomass has been obtained.

� Bioremediation of Zinc by Streptomyces aureofacienes (Osama H. EL Sayed, Hala M. Refaat, Mahmoud A. Swellam, Mahmoud M. Amer, Aziza I. Attwa and Mohamed E. El Awady Benha university , benha, Egypt)

In this study, twelve Streptomyces species isolated from Egyptian soil and identified by using physiological tests as Bergey’s manual was assessed quantitatively to the effects of zinc using plate diffusion method. Biosorption of zinc by biomass microorganisms is an innovative and alternative technology for removal of these pollutants due to their good performance, low cost and large available quantities. Experiments in liquid culture were used to determine concentration ranges of the metals at which the most tolerant species could grow showed that Streptomyces aureofacienes had maximum uptake of zinc (734.8 µg g-1 biomass).

26

4.3 Siderophores

Siderophores are small organic molecules with strong affinity for ferric iron and are primarily

produced to mediate iron acquisition, but they are also able to bind other metals (Hu and Boyer,

1996) or in rare cases protect against metal toxicity (Cortese et al., 2002). Despite many

different structures of the siderophores, they are usually classified according to the type of the

binding ligand (Boukhalfa and Crumbliss, 2002). Ferrioxamines and ferrichromes were the first

siderophores recognized as iron transport agents produced by bacteria and fungi

(Budzikiewicz, 1997). Only few siderophores using carboxylate ligands are known, for example

staphyloferrin. Pyridine-2,6- bis(thiocarboxylic acid) (Pdtc) is an example of a siderophore using

sulfer as ligand donor atoms (Cornelis and Matthijs, 2002). Pdtc was identified as a

siderophore having such multiple properties, beside carbon tetrachloride degradation (Lee et al.,

1999). Pdtc forms soluble stable complexes with many transition metals such as iron, cobalt,

chromium and copper (Stolworthy et al., 2001). Many heavy metals and metalloids have been

found to form insoluble precipitates with pdtc, and pdtc was effective in protecting some bacteria

against metal toxicity (Cortese et al., 2002). Pdtc was found to reduce Cr(VI) to Cr(III) in

bacterial cultures and in abiotic reactions with chemically synthesized pdtc; Cr(III) subsequently

formed complexes with pdtc were found to slowly release Cr(III) as chromium sulfide and

possibly Cr(III) oxides and hydroxides (Chirwa and Wang, 2000). The properties of pdtc make it

a good candidate for heavy metal remediation by metal reduction and complexation, selective

precipitation of heavy metals from solution, and also solubilization of metal and mixed metal-

carbon tetrachloride contaminated wastes (Gadd,2004). .

27

CDEFGا IJKLGا MNNء هQNNLGا RG STUNNVGQD ةQNNXYGا ENNZQV[ \NNأه E^QUNNGن وQUNNa

ن MNNNKn \oNNNpث هlNNNا أوlNNNGا gNNNh iNNNajk اMNNNfJGرة QNNNcLDن ، اQNNNV^QcGت EqNNVFGأم ا SpMsNN[ tNNaQاء أآMNNv تQNNwMKLGاع اMNNaأ CoyNND مQNNzGا

SpMs[EX{SKX|}Gدن اQFLGت اQwMKLGا �lه Efأ� gh �FG و .

|}Gدن اQNNFLGا QNNzoK}hأ gNNhو SpMsNN[ ENNX{ ENNZQV[ CNNه SNNKX�gNh Qz ، ا�T^�G ،ا�Gر�Xa ، اQcGدMXhم ، اEcGومpEqNn \oNp CNoGوا

SKUNKUGا CNk ��n CGQoGQDو �QXLGدر اQqh CGا �Dا�LGو ا �aQqLGا SNNXYGم اQUNNا�� NNاآ\ دا�ENNon QNNzaأ CNNk QNNznرMf� gNNLcnو SNNX^اl�Gا

آ{ENXة �N}h و�p CGQoGQDداد Enآ�XهCNk Q اUN�G\ و�Nnدي �ENhاض ��y اMKcGي و ا�GهELpQ و}EXهgh Q ا�Ehاض Gا.

هQVك اE� gh EX}cGق إزاSG اQFLGدن اgNh SKX|}G اQqNLGدر

SX�MGMXTGو ا SX^Qp�X�Gو ا SX^QXLXcGق اEfGا QzVLk SX^QLGآ� ، اEpو �Kn SZQ� و SKX|}Gدن اQFLKG SX�MGMXTGا S�GQFLGا CK[ لQ|LGا اlه

. Sfv اQV^QcGت اS|X��GاMD \on CoGا

28

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