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Introduction Water comprises over 70% of the Earth’s surface and it is undoubtedly the
most precious natural resource that exists on our planet (Krantz and Kifferstein, 1996). Without the seemingly invaluable compound comprised of hydrogen and oxygen, life on Earth would be non-existent (Krantz and Kifferstein, 1996). It is essential for everything on our planet to grow and prosper. Although we as humans recognize this fact, we disregard it by polluting our rivers, lakes, and oceans. Subsequently, we are slowly but surely harming our planet to the point where organisms are dying at a very alarming rate (Krantz and Kifferstein, 1996). In addition to innocent organisms dying off, our drinking water has become greatly affected as is our ability to use water for recreational purposes. In order to combat water pollution, we must understand the problems and become part of the solution (Krantz and Kifferstein, 1996). Water pollution is the contamination of water bodies such as lakes, rivers, oceans, and groundwater by anthropogenic activities, thereby harming the organisms and plants that live in these water bodies which occur when pollutants are discharged directly into water bodies without treating them first. Water pollution is a major problem in the global context. It has been suggested that it is the leading worldwide cause of deaths and diseases, and that it accounts for the deaths of more than 14,000 people daily. In addition to the acute problems of water pollution in developing countries, industrialized countries continue to struggle with pollution problems as well. In the most recent national report on water quality in the United States, 45
percent of assessed stream miles, 47 percent of assessed lake acres, and 32 percent of assessed bay and estuarine square miles were classified as polluted (U.S. EPA, 2002). Water is typically referred to as polluted when it is impaired by anthropogenic contaminants and either does not support a human use, like serving as drinking water, and/or undergoes a marked shift in its ability to support its constituent biotic communities, such as fish. Natural phenomena such as volcanoes, algae blooms, storms, and earthquakes also cause major changes in water quality and the ecological status of water. Water can be polluted from many sources. Faecal contamination from sewage makes water unpleasant and unsafe for recreational activities such as swimming, boating or fishing. Many organic pollutants, including sewage effluent and farm and food-processing wastes consume oxygen, suffocating fish and other aquatic life. Nutrients such as nitrates and phosphates, from everything from farm fertilizers to household detergents, can 'overfertilize' the water causing the growth of large mats of algae, some of which are directly toxic. When the algae die, they sink to the water bottom, decomposing, consuming oxygen and damaging ecosystems. Chemical contaminants including heavy metals, pesticides and some industrial chemicals can threaten wildlife and human health. Sediment run-off from the land can make water muddy, blocking sunlight and, as a result, killing wildlife. Irrigation also, especially when used improperly, can bring flows of salts, nutrients and other pollutants from soils into water. Heavy metals such as Pb and Cd are pollutants of very high priority concern in the scientific community because apart from being toxic to the entire ecosystem, they are non-biodegradable and have ability to bioaccumulate in biological species even at very low concentrations (Yurtsever and Sengil, 2009). Exposures to Lead and cadmium has been reported to have deleterious health effects on humans including
damage to liver, kidney and a painful disease called “itai-itai” (Yurtsever and Sengil, 2009; Forstner and Wittman, 1979). These metals get into natural surface and ground waters from industrial effluents such as those from the oil and gas, plastic, pharmaceutical, storage-battery manufacture, paper and pulp, mining, electroplating, lead smelting, other metallurgical finishing, automobile industry, agricultural run-off, chemical spills and municipal wastewaters (Yurtsever and Sengil, 2009). Various traditional methods of removing heavy metals from wastewaters have been reported including the use of precipitation and coagulation, chemical oxidation, sedimentation, filtration, osmosis, ion exchange, etc.(Aziz et al., 2009). Adsorption technology is currently being used extensively for the removal of heavy metals from aqueous solutions because it is a cleaner, more efficient and cheaper technology. A review of some recent low cost adsorbents material has been done by (Yurtsever and Sengil, 2009). With the vast array of biosorbents currently available for removal of metal ions, there is the dearth of information on the adsorptive potential of C. papaya seeds In this project work, Carica Papaya seeds (common name: Pawpaw Seeds) was used as a adsorbent for the removal of metal ions (Pb2+ and Cd2+) from an aqueous solution containing metal ions. The seeds were defatted before they were used in other to remove all the fat and oil present in the seed because the adsorbent was expected to be a waste material and an undefatted C. papaya seed is still a useful material because of its oil content which is valuable to man.
1. readily available and also an effective new adsorbent to the adsorption scientific community for the removal of lead. As humans developed new technologies. lead. the magnitude and severity of pollution increased. clothing. 1. Many historians speculate that the extensive use of lead plumbing for drinking water in Rome caused chronic lead poisoning in those who could afford such plumbing.2 Importance of this Project This research work has introduced a cheap. there will be portable water supply to every home. Samples of hair from historical figures such as Newton and 4 .1. This is in line with the Federal Government of Nigeria’s vision 2020.1 Aims/Objectives (i) Defatted C. a new biosorbent was used to remove Pb2+ and Cd2+ from aqueous solution. papaya seeds (DPS).3 Brief History of Pollution Much of what we know of ancient civilizations comes from the wastes they left behind. tool usage. copper. (ii) Study of the Sorption parameters such as contact time. The mining and smelting of ores that accompanied the transition from the Stone Age to the Metal Age resulted in piles of mining wastes that spread potentially toxic elements such as mercury. equilibrium. and the Middle East have helped to reveal hunting techniques. pH and temperature on the adsorbent (Carica papaya) were investigated. diet. and nickel throughout the environment. which says that by year 2020. and the use of fire for cooking that was carried out by people of old. Evidence of pollution during the early Industrial Revolution is widespread. China. cadmium and other heavy metals from polluted waste water. Refuse such as animal skeletons and implements from Stone Age cave dwellings in Europe.
In 1976 an explosion at a chemical factory in Seveso. 5 . hatters became disoriented. pollution had evolved from a mainly localized problem to one of global consequences in which pollutants not only persisted in the environment. certain trades were associated with characteristic occupational diseases: Chimney sweeps contracted cancer of the scrotum (the external sac of skin enclosing the testes. The Minamata Bay disaster was the first major indication that humans would need to pay more attention to their waste products and waste disposal practices. released clouds of toxic dioxin into the area. uncontained disasters. in particular. and bootblacks suffered liver damage from boot polish solvents. Italy. or “mad. The Iraqi military intentionally released as much as 1 billion liters (336 million gallons) of crude oil into the Persian Gulf and set fire to more than 700 oil wells. The 1986 Chernobyl’ nuclear accident demonstrated dangerous contamination effects of large. hazardous waste disposal. but changed atmospheric and climatic conditions. black smoke into the atmosphere over the Middle East.Napoleon show the presence of toxic elements such as antimony and mercury. In an unprecedented action. sending thick. or reproductive glands) from hydrocarbons in chimney soot. pollution was used as a military tactic in 1991 during the conflict in the Persian Gulf.” from nerve-destroying mercury salts used to treat felt fabric. By the 1800s. exposing hundreds of residents and killing thousands reactor of animals that ate exposed the food. many more instances of neglect or carelessness resulted in dangerous levels of contamination. In the years that followed. By the 21st century.
It also accumulates in rivers and streams. Acid rain kills plants and trees and damages structures. 1990). land and water. This problem is not confined to developed countries only. a thick. smoke and industrial pollution claimed more and more lives (Leinwand and Gerald. 1990). All around the world.4.000 were hospitalized with respiratory problems (Asimov et al. Donora. 1990). malodorous fog enveloped the small industrial town.1. In October 26. and as coal became common in private residences all over the world. The use of leaded gasoline raised lead levels in populations around the world (Leinwand and Gerald. 1948. the advent of the internal combustion engine-powered vehicles compounded air pollution. In the United States. which are: air. 1991). but as the Industrial Revolution swept across countries.4 Types of Pollution There are three major types of Pollution.1 Air: The growth of population centers coupled with the switch from woodburning to coal-burning fires created clouds of smoke over cities as early as the eleventh century (Asimov et al. Smoke from coal-fired power plants creates the related problem of acid rain and gases (sulfur dioxide and nitrogen oxides) released by burning fossil fuels. 6 . Unlike usual fogs. adding particulate and gaseous contaminant to the air people breath. Pennsylvania. became famous for a tragedy that symbolized the dangers of industrial air pollution. it stayed on the ground for five days which resulted to the death of twenty people in Donora and about 7. and has resulted in lakes that are already devoid of life in areas where industrial processes abound (Leinwand and Gerald. 1. it did not burn off as the day progressed but instead.. making the rain more acidic and therefore corrosive. 1991)..
The pollution of water with raw sewage was the catalyst for many typhoid and cholera outbreaks throughout the centuries. without a thought to the possible risks or consequences of these actions. In the developed countries. leading to environmental disasters. the importance of clean water was not understood until the second half of the nineteenth century. however. or accessible.1. Historically. as the world becomes more of a global community. there has been little or no regulation of hazardous waste disposal in developing nations.4. a relatively recent development (Markham and Adam. this problem will no doubt haunt future generations. 1990). The practice of chemical dumping persisted for years in the early twentieth century. and not only were freshwater sources used as sewage dumps in most of the Western world. in many places. where disposal is more expensive. there will be crises of loss of life ( ebel et al.2. but industrial waste was also discarded in rivers and streams (Leinwand and Gerald. it will leach these toxins to several water bodies and if such waters are not treated properly before use. human wastes was carried in rivers for centuries. 2000). in numerous developing nations. Across the globe. Even today. Leather tanning waste and butchering waste were frequent early 7 . 1994). 1992). Water Pollution Water is essential to life and that is why most human settlements always began near a water source.. Land Pollution: This occurs as a result of chemical/ non chemical waste dumps on land surfaces by anthropogenic activities. to everyone (Ponting and Clive. this is because the buried waste over time will become toxic and when rain falls.5. cholera still kills tens of thousands each year because clean drinking water is not available. Unfortunately. 1. in many parts of the world. developing countries have been buying hazardous waste from developed nations.
and waste treatment plants and so on.1. factories and even bakeries. 1991). Direct sources include effluent outfalls from factories. 1. Atmospheric contaminants are also derived from human practices such as gaseous emissions from automobiles. spray painting. Recently. Indirect sources include contaminants that enter the water supply from soils/groundwater systems and from the atmosphere via rain water. water pollution became a major crisis (Leinwand and Gerald. Contaminants can be broadly classified into: • Organic pollutants which are by-products of auto mobile. or through leaching into groundwater from dumping sites. Sources of Water Pollution: There are many sources of water pollution but two general categories exist: direct and indirect contamination sources. birth defects. resulting into massive wildlife die-offs. refineries. especially rivers. many industrial waste byproducts find their way into the water. and the trend continued well into the twentieth century.5. emissions from waste incinerators. and are also blamed for elevated cancer rates. etc. dry-cleaning and other 8 . either through direct dumping by companies.. In the developed and some developing countries. pesticides.) and improperly disposed industrial wastes. although this does not mean that pollutants cannot be found in their waters. a convenient means of waste disposal. these practices are regulated. Factories found water sources. Soils and ground waters contain the residue of agricultural practices (fertilizers.polluters of water sources and as the Industrial Revolution progressed. petroleum and chemical industries. domestic solid fuel and gas combustion. that emit fluids of varying quality directly into urban water supplies. service stations. and a lower IQ in people who subsisted on water polluted by heavy industries (Asimov et al. 1990).
producing dangerous chemical by-products that include: sulphur dioxide. most sewage treatment does not remove phosphorus compounds. it is difficult to correct and spreads over wide areas. which occur wherever there are many cars and factories. toluene. zinc. and cigarette smoke. In many public water systems. Additionally. sewage carries industrial contaminants and a growing tonnage of paper and plastic refuse. ammonia. Towns and municipalities are also major sources of water pollution. xylene and formaldehyde. When contamination reaches underground water tables. and phosphate. nitrite. communities discharge untreated or only partially treated sewage into the waterways. These are toxic to humans and the entire ecosystem.S. carbon dioxide. nitrate. and • Acid/base pollutants. many U.solvent usage. phosphorous. pollution exceeds safe levels. Although thorough sewage treatment would destroy most disease-causing bacteria. In addition. • Inorganic pollutants which are of primary concern in urban storm water containing cadmium. the problem of the spread of viruses and viral illness remains. contributed principally by detergents. Along with domestic wastes. threatening the health of their own and neighbouring populations. and nitrogen oxides which are mixed with moisture in the air. lead. Excreted drugs and household chemicals also are not removed by present municipal treatment facilities. nitrogen. and these pollutants include: benzene. which cause Eutrophication of lakes and ponds. • Radioactive pollutants from natural sources of radiation are radon gas. and can be recycled into the drinking water 9 . copper. medical X-rays and nuclear medicine. One reason for this is that much groundwater has been contaminated by wastes pumped underground for disposal or by seepage from surface water.
secondary treatment or better) can remove 90 percent or more of these pollutants. and other chemicals used to raise livestock are components of such animal wastes. Some plants have additional subsystems to treat nutrients and pathogens. 2004).S.. increasing overall hydraulic capacity of the sewage collection system (often a very expensive option).2. Rain drainage is another major polluting agent because it carries such substances as highway debris (including oil and chemicals from automobile exhausts). a widespread source of pollutants impairing rivers and streams. including: Utilizing a green infrastructure approach to improve storm water management capacity throughout the system (U. Municipal treatment plants are designed to control conventional pollutants like BOD (Biochemical Oxygen Demand) and suspended solids.S. repair and replacement of leaking and malfunctioning equipment(U.S.5. and even some coastal waters. EPA. Most municipal plants are not designed to treat toxic pollutants found in industrial wastewater (U. most of these plants are operated by local government agencies.S. Pesticide and fertilizer residues from farms also contribute to water pollution via rain drainage. 10 . 1.supply. and acids and radioactive wastes from mining operations into freshwater systems as well as into the ocean. hormones. groundwater. Methods of Controlling / Treatment of Water Pollution Domestic Sewage Treatment: In urban areas. Antibiotics. domestic sewage is typically treated by centralized sewage treatment plants. 2004). Well-designed and operated systems (i. 2008). EPA. sediments from highway and building construction.. Cities with sanitary sewer overflows or combined sewer overflows employ one or more engineering approaches to reduce discharges of untreated sewage. Also transported by rain runoff and by irrigation return-flow are animal wastes from farms and feedlots. In the U.e. EPA.
g. or spraying of municipal or industrial wastewater (effluent) or sludge. oil and grease). EPA. Common techniques include contour plowing.S. Some industries have been successful at redesigning their manufacturing processes to reduce or eliminate pollutants. Nutrients may also enter runoff from crop residues. Nutrients (nitrogen and phosphorus) are typically applied to farmland as commercial fertilizer. Farmers can develop and implement nutrient management plans to reduce excess application of nutrients (U. a process where waste heat is recycled for domestic and/or industrial heating purposes. Industries generating large volumes of wastewater typically operate their own complete on-site treatment systems. 11 . irrigation water. EPA. 2003).S. which transfer waste heat to the atmosphere through evaporation and/or heat transfer. and then send the partiallytreated wastewater to the municipal system.( U. convection. Heated water generated by power plants or manufacturing plants may be controlled with: Cooling ponds. Some of these facilities can install a pre-treatment system to remove the toxic components.S. planting perennial crops and installing riparian buffers.conventional pollutants such as ammonia. 2003). crop mulching. crop rotation. 2003). man-made bodies of water designed for cooling by evaporation.g. heavy metals. and atmospheric deposition(U. wildlife. cogeneration. EPA. animal manure.Industrial Wastewater Treatment: Industries that generate wastewater with high concentrations of conventional pollutants (e. cooling towers. Agricultural Wastewater Treatment on point Source Control: Farmers utilize erosion controls to reduce runoff flows and retain soil on their fields. need specialized treatment systems. volatile organic compounds) or other non . through a process called pollution prevention. and radiation. toxic pollutants (e.
Pollution prevention practices include low impact development techniques. Discharge of toxic chemicals such as motor fuels and concrete washout is prevented by use of: spill prevention and control plans. Local governments use a variety of stormwater management techniques to reduce the effects of urban runoff.S. 2008). management of motor fuels & oil.S. 2008). Construction Site Storm Water Sediment from construction sites is managed by installation of: erosion controls.g. such as factory farms. Animal slurries are usually treated by containment in lagoons before disposal by spray or trickle application to grassland. EPA. and sediment controls.g. and specially-designed containers (e.S. as well as reducing pollutant discharges. are called concentrated animal feeding operations or confined animal feeding operations in the U. EPA. EPA. 2006). installation of green roofs and improved chemical handling (e. and are being subject to increasing government regulation( U. 12 Runoff mitigation systems include . Urban runoff (storm water) Effective control of urban runoff involves reducing the velocity and flow of stormwater.Point Source Wastewater Control: Farms with large livestock and poultry operations. Constructed wetlands are sometimes used to facilitate treatment of animal wastes. fertilizers and pesticides)( U. such as mulching and hydro seeding. as are anaerobic lagoons.S. Some animal slurries are treated by mixing with straw and composted at high temperature to produce a bacteriologically sterile and friable manure for soil improvement. for concrete washout) and structures such as overflow controls and diversion beams (U. such as sediment basins and silt fences.
Interestingly. For some heavy metals. lead. and multiple sclerosis. cerium. and other vital organs (International Occupational Safety and Health Information Centre 1999). Heavy Metals There are 35 metals that concern us because of occupational or residential exposure. bioretention systems. 1. 1999). 23 of these are the heavy elements or "heavy metals": antimony. gold. cadmium. muscular dystrophy. liver. silver. retention basins and similar devices. nickel. tellurium. and damage to blood composition. vanadium.6. iron. Therefore. bismuth. thallium. and neurological degenerative processes that mimic Alzheimer's disease. however. tin. toxic levels can be just above the background concentrations naturally found in nature. lower energy levels. In most parts of the world. but large amounts of any of them may cause acute or chronic toxicity (Glanze. mercury. If unrecognized or inappropriately treated. Parkinson's disease. uranium. muscular. kidneys. copper. and zinc (Glanze. chromium. Heavy metal toxicity can result in damaged or reduced mental and central nervous function. 1996). 1996). gallium. platinum. arsenic. Allergies are not uncommon and repeated long-term contact with some metals or their compounds may even cause cancer (IOSHIC. toxicity can result in significant illness and 13 . it is important for us to inform ourselves about the heavy metals and to take protective measures against excessive exposure. lungs. Long-term exposure may result in slowly progressing physical. cobalt. manganese.infiltration basins. it is a clinically significant condition when it does occur. heavy metal toxicity is an uncommon medical condition. constructed wetlands. small amounts of these elements are common in our environment and diet and are actually necessary for good health.
iron. 1992). and insomnia. and language skills. specific gravity is a measure of density of a given amount of a solid substance when it is compared to an equal amount of water. sweating. Simply stated.6. nausea.546 (Lide. thinking the symptoms are related to something else. 2001). Symptoms of chronic exposure are very similar to symptoms of other health conditions and often develop slowly over months or even years.reduced quality of life (Ferner. The association of symptoms indicative of acute toxicity is not difficult to recognize because the symptoms are usually severe. however.7. Sometimes the symptoms of chronic exposure actually abate from time to time. 13. 11. The symptoms of toxicity resulting from chronic exposure (impaired cognitive. testing is essential. For persons who suspect that they or someone in their household might have heavy metal toxicity. nausea. and language skills. difficulty breathing. and mercury. pain. lead. rapid in onset. Heavy metals could also be defined generally as collective term which 14 . cadmium.1. Definition of Heavy Metals Heavy metals are chemical elements with a specific gravity that is at least 5 times the specific gravity of water (Lide. 2001): cramping. and feeling ill) are also easily recognized. they are much more difficult to associate with their cause. 1992). Some wellknown toxic metallic elements with a specific gravity that is 5 or more times that of water are arsenic. motor. leading the person to postpone seeking treatment. learning difficulties. headaches. The specific gravity of water is 1 at 4°C (39°F). motor. and vomiting. 7. nervousness and emotional instability. and convulsions. mania. 1.9. 2001).65. Appropriate conventional and natural medical procedures may need to be pursued (Dupler.34. and associated with a known exposure or ingestion (Ferner. 5. 8. lethargy. impaired cognitive.
1999). 1999). copper. and zinc). it is widely recognized and usually applies to the widespread contaminants of terrestrial and freshwater ecosystems. or some form of them. such as organochlorines. 15 . copper. zinc. certain heavy metals are nutritionally essential for a healthy life.g. arsenic. They are therefore found naturally in soils and rocks with a subsequent range of natural background concentrations in soils. Osmium. Many of these products are in our homes and actually add to our quality of life when properly used. Rhodium. are commonly found naturally in foodstuffs. Although it is a loosely defined term (Duffus. textile dyes. and in commercially available multivitamin products (IOSHIC. alloys. waters and organisms. These elements. Unlike almost all organic pollutants. 2002). Palladium. lead. and so forth (IOSHIC. iron. The heavy metals which are included in Apis are cadmium. Heavy metals are also common in industrial applications such as in the manufacture of pesticides. manganese. Diagnostic medical applications include direct injection of gallium during radiological procedures. Ruthenium. and the use of lead as a radiation shield around x-ray equipment (Roberts. in fruits and vegetables. steel. Anthropogenic releases can give rise to higher concentrations of the metals relative to the normal background values. which comprises Platinum. 1999). batteries. sediments. mercury.. 1. Some of these are referred to as the trace elements (e. and Iridium. heavy metals are elements which occur naturally in the Earth’s crust.2. dosing with chromium in parental nutrition mixtures.applies to the group of metals and metalloids with an atomic density greater than 4 g/cm³.6. electroplated metal parts. boron and the platinum group metals. chromium. Beneficial Heavy Metals In small quantities.
industrial.S. 2001). or from a suicide or homicide attempt (Lupton et al. water.. As a rule. from inappropriate dosing or monitoring during intravenous (parental) nutrition. Ingestion is the most common route of exposure in children (Roberts. air. The Agency for Toxic Substances and Disease Registry (ATSDR) in Atlanta. 16 .6.1. lesser levels of contamination may occur in residential settings. response to emergency release situations. acute poisoning is more likely to result from inhalation or skin contact of dust. or materials in the workplace. 1999). 1985). Industrial exposure accounts for a common route of exposure for adults. and education and training concerning hazardous substances (ATSDR. or absorption through the skin when they come in contact with humans in agriculture and in manufacturing. 2001). Department of Health and Human Services) was established by congressional mandate to perform specific functions concerning adverse human health effects and diminished quality of life associated with exposure to hazardous substances. The ATSDR is responsible for assessment of waste sites and providing health information concerning hazardous substances. Toxic Heavy Metals Heavy metals become toxic when they are not metabolized by the body and accumulate in the soft tissues. fumes or vapors. However.3. 1997).. particularly in older homes with lead paint or old plumbing (International Occupational Safety and Health Information Centre 1999). Less common routes of exposure are during a radiological procedure. (a part of the U. Georgia. Heavy metals may enter the human body through food. from a broken thermometer (Smith et al. pharmaceutical. Children may develop toxic levels from the normal hand-to-mouth activity of small children who come in contact with contaminated soil or by actually eating objects that are not food (dirt or paint chips) (Dupler. or residential settings.
Cd. Unlike organic pollutants. Broadly. Hg. Cr). Co. Cu.g. Cu.g. e. Cr. Some treatment of mining tailings has occurred were the vegetation is then incinerated to recover the heavy metals. Arsenic may pollute catalysts). some are harmful in other ways (e. plants or microorganisms are tentatively used to remove some heavy metals such as mercury. Cd.g. Mn. Cr). Cu) or skin.4. Sn and Tl. heavy metal pollutants can localize and lay dormant. the emissions of which are regulated in waste incinerators. As). Pb. heavy metals can be considered to come from two sources. As. among others. Cd.g. heavy metals do not decay and thus pose a different kind of challenge for remediation. the smelting of copper and the preparation of nuclear fuels. Plants which exhibit hyper accumulation can be used to remove heavy metals from soils by concentrating them in their bio mater. These are: 17 . Hg. Some of these elements are actually necessary for humans in minute amounts (Co.1. Cu.6. Pb. Zn. Sources of Heavy Metal Motivations for controlling heavy metal concentrations in gas streams are diverse. bones or teeth (Ni. Pb). the central nervous system (Hg. Currently. Pb. Cd. affecting. the kidneys or liver (Hg. Heavy metal pollution can arise from many sources but most commonly arises from the purification of metals. Some may cause corrosion (e. Ni.. Within European community the 13 elements of highest concern are As. Cr. Pb. Some of them are dangerous to health or to the environment (e. Through precipitation of their compounds or by ion exchange into soils and muds. Electroplating is the primary source of chromium and cadmium. Ni) whilst others are carcinogenic or toxic.
Metals such as lead. mercury cadmium are cumulative poisons. contaminated sediments and mines wastes. The effects of heavy metals can be grouped into four broad categories. battery manufacture etc. Lead is known to cause impaired motor skill development. fertilizers and other chemicals. 18 delay growth and affect . The introduction of lead and copper into food chain affect human health and studies concerning their accumulation vegetables is of increasing importance. Effects of Heavy Metals It is difficult to summarize all the adverse effects due to heavy metals because of their large number and the fact that each element can cause a number of different problems.atural Sources: These are as a result of natural processes such as weathering of heavy metal.5. fuels. Anthropogenic Sources: These are sources of heavy metals linked with man’s activities such as mining. municipal wastes and industrial big-products. farming. these are: Human Health Hazards: The primary results of exposure of humans to heavy metals is through inhalation of dust. smelting processes. and metal processing which is the main source of heavy metal contamination. fuels. use of chemicals such as pesticides. copper. Chronic low-level intakes of heavy metals have damaging effect on humans as there is no good mechanism for their elimination. accidental spills.6. 1.containing rocks and those that are found as constituents of soil parent materials and aquatic environment. paints. consumption of food grown on contaminated soils or through direct ingestion of soil.
Symptoms of heavy metal induced phytoxicities include stunting. necrosis and death of the plant. the reduction in soil quality included by elevated heavy metal concentrations can reduce both the quantity and quality of the food produced from that soil. 2004). 2005). necrosis. In humans.neurotransmission in children. the disease is named “itai-itai disease” ( ordberg.. wind and water erosion occurs uninhabited. Animal Health: Animal health effects include domestic animals and wildlife. fatigue.. although this is very uncommon in young children. a Mo – Induced Cu deficiency Selemium and other metal toxicity are harmful to animals if consumed regularly. Ni and Zn Phytixicity problems are of concern for two primary reasons. Chronic lead poisoning can produce a lead hue of the skin with a lividity and pallor (James et al. lack of calmness. chlorosis. Phytotoxicities: Phytotoxicity refers to reduce yields or death of plants in the soil. First. Heavy metals often associated with phytoxiaties include stunting. lead toxicity sometimes causes the formation of a bluish line along the gums. which is known as the “Burton line” or "lead line" (James et al. in areas where irrigation is spare due to heavy metal toxicitives. Mercury is known to cause irritability. arthritis. 19 . chlorisis. and inflammation while. Heavy metals often associated with physotoxicities include Cu. causing severe pains in the joints and spine. memory loss. secondly. and death of the plant. 2005). Ruminant animals are the most susceptible to Molybdenosis. learning disorders. Toxicities of Molybdenum in livestock (molybdenosis) and Selenium in livestock and wildlife (selenosis) are common having metal animal health problems. cadmium poisoning causes softening of the bones and kidney failure.
dialysis. Where an exceptionally high quality effluent is required. The effluent is continuously pumped through the two columns in a series to yield the treated effluent.6. commercially available resins and activated carbons can be expensive. Conventional physical and chemical treatment of low-concentration. adsorption and co-precipitation. Attention has thus been focused on non-consumptive methods that include ion-exchange and other sorption process. reverse osmosis. Discharge of metals to aquatic environment is of major concern and treatment of industrial effluents has consequently attracted considerable attention. hence: the need to development other methods that are relatively cheap. a cation exchange resin. Ion Exchange: An ion-exchange system consists of a pair of column or pressure vessel.6. Common methods of metal removal from industrial effluents include chemicals precipitation. Methods of Heavy Metal Removal from Industrial Effluents. productivity and density of aquatic organisms. ion exchange. Consumptive process such as chemical precipitation entails large capital and operating cost. the other. one containing an anion exchange resin. membrane filtration. The effects of heavy metals in aquatic environment are generally to reduce diversity. Soil erosion and industrial effluent discharge are the main source of heavy metals in aquatic environments. solvent extraction. 1. electrolytic extraction.Aquatic Environment: Effect of elevated concentrations of heavy metals in aquatic environment are difficult to assess due in part to the mobility of some of the species and the difficulty in separating out the effect of contaminated sediments. cementation. a third 20 . Even then. large volume wastes tend to be very costly.
The disadvantage is the formation of metal hydroxides. The cost of this process is very dependent on dissolved solids concentration. Because of the alternate spacing of cation and anion permeable membranes. It does not find common use in effluent treatment but may be appropriate in certain 21 . It is particularly suitable where low metal concentration is present. the ionic components (heavy metals) are separated through the use of semi-permeable ion-selective membranes. cells of concentrated and dilute salts are formed. it finds only little application in this sphere largely because of cost of solvent loss. The process requires high pressure (up to 100 atmospheres) and is thus fairly costly in terms of energy. At present. it is still at infancy. The delicacy of the membrane is restrictive with regard to solid content and pH of the material being treated.mixer-bed exchange column can be placed after the cation exchange resin. Application of an electrical potential between the two electrodes causes a migration of cations and anions towards respective electrodes. Solvent Extraction: This involves separation of components of a liquid mixture by treatment with a solvent in which one or more of the desired component is preferentially soluble. It is a process widely used in the petroleum and chemical industry but which has only recently been adopted for recovery of metals from aqueous solutions. Electrodialysis: In this process. However. Reverse Osmosis: On a practical scale. which clog the membrane. the process has been used on effluents from electroplating in the electronic component industry.
iron salts and other organic polymers. Phytoremediation: Phytoremediation is the use of certain plants to clean up soil. The large amount of sludge containing toxic compounds produced during the process is the main disadvantage. 22 . The main disadvantage of this process is the generation of sludge. and water contaminated with metals. the concentration of static rinses from electroplating processes especially chromium. The disadvantages include that it takes a long time for removal of metals and the regeneration of the plant for further biosorption is difficult. A recent development is the rotatory electrode. Chemical Precipitation: Precipitation of metals is achieved by the addition of coagulants such as alum. lime.g. Evaporation: This is one of the most common methods used in industry for concentrating aqueous solution. Ultrafiltration: They are pressure driven membrane operations that use porous membranes for the removal of heavy metals.circumstances where the concentrate is of high value. sediment. Nevertheless use of this method as a means of effluents treatment is rare and occurs only under special circumstances where effluents contains a high concentrations of valuable material e.
It is different from absorption. and water purification. In a bulk material. or metallic) of the constituent atoms of the material are filled by other atoms in the material. atoms on the surface of the adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. 23 . Adsorption. The use of adsorption as a method of removal of heavy metals from industrial effluent is the focus of this project work. but the adsorption process is generally classified as physisorption (characteristic of weak van der Waals forces) or chemisorption (characteristic of covalent bonding).1. However. Adsorption is present in many natural physical. synthetic resins. Adsorption is the accumulation of atoms or molecules on the surface of a material. all the bonding requirements (be they ionic. and chromatography are sorption processes in which certain adsorbates are selectively transferred from the fluid phase to the surface of insoluble. while desorption is the reverse process. in which a substance diffuses into a liquid or solid to form a solution. The exact nature of the bonding depends on the details of the species involved. and is widely used in industrial applications such as activated charcoal. ion exchange. Adsorption This process can be cheap. relatively simple and effective if a suitable adsorbent is found. and chemical systems. The term sorption encompasses both processes. This process creates a film of the adsorbate (the molecules or atoms being accumulated) on the adsorbent's surface. Similar to surface tension. adsorption is a consequence of surface energy. covalent.7. biological. rigid particles suspended in a vessel or packed in a column.
As the temperature increases. (ii) Adsorbed molecules do not interact. The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials. which retained his name. (iv)At the maximum adsorption.8. 24 . the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (if liquid) at constant temperature. already adsorbed. P is the pressure of adsorbate and k and n are empirical constants for each adsorbent-adsorbate pair at a given temperature. all the adsorption sites are equivalent. the constants k and n change to reflect the empirical observation that the quantity adsorbed rises more slowly and higher pressures are required to saturate the surface. It is a semi-empirical isotherm derived from a proposed kinetic mechanism. molecules of adsorbate. In 1916. m is the mass of the adsorbent. only on the free surface of the adsorbent. only a monolayer is formed: molecules of adsorbate do not deposit on other.1. Isotherms Adsorption is usually described through isotherms. Irving Langmuir published a new model isotherm for gases adsorbed on solids. The function has an asymptotic maximum as pressure increases without bound. that is. It is based on four assumptions: (i) The surface of the adsorbent is uniform. (iii) All adsorption occurs through the same mechanism. The first mathematical fit to an isotherm was published by Freundlich and Küster (1894) and is a purely empirical formula for gaseous adsorbates: x = kP 1 / n m where x is the quantity adsorbed. that is.
For very low pressures θ ≈ KP and for high pressures. If we define surface coverage. as the fraction of the adsorption sites occupied. adsorbed molecules are not necessarily inert. The Langmuir isotherm is nonetheless the first choice for most models of adsorption. as frequently more molecules will adsorb on the monolayer.These four assumptions are seldom all true: there are always imperfections on the surface. or gas volumes at standard temperature and pressure (STP) per gram of adsorbent. in the equilibrium we have K= K θ KP = orθ = K − 1 (1 − θ ) P 1 + KP Where P is the partial pressure (gas) or the molar concentration of the solution (gas). θ = 1 1 1 1 = + v Kv mon P 1 + v mon v v mon and we obtain an expression for a straight line: Through its slope and y-intercept we can obtain vmon and K. and has many applications in surface kinetics (usually called LangmuirHinshelwood kinetics) and thermodynamics. usually. θ is difficult to measure experimentally. this problem is addressed by the BET isotherm for relatively flat (non-microporous) surfaces. The direct and inverse rate constants are k and k-1. vmon is related to the number of 25 . grams. the adsorbate is a gas and the quantity adsorbed is given in moles. If we call vmon the STP volume of adsorbate required to form a monolayer on the adsorbent (per gram of adsorbent). which are constants for each adsorbent/adsorbate pair at a given temperature. and the mechanism is clearly not the same for the very first molecules to adsorb as for the last. The fourth condition is the most troublesome. θ. θ ≈ 1 . Langmuir suggested that adsorption takes place through this mechanism: Ag + S ⇔ AS Where Ag is a gas molecule and S is an adsorption site.
Preetha and Viruthagiri (2005) applied the BET model to describe biosorption of Zn2+ by Rhizopus arrhizus. Pseudo-First-Order Equation: The pseudo-first-order kinetic equation or the socalled Lagergren equation has the following formulation: 26 . B is a constant relating to the energy of interaction with the surface and Cs is the saturation concentration of the solute. the more pores it has.. Types of Isotherms Bet Isotherm Equation: Brunauer et al. we can easily calculate the surface area of the adsorbent. the greater the area. If we assume that the number of sites is just the whole area of the solid divided into the cross section of the adsorbate molecules.8. The surface area of an adsorbent depends on its structure. so-called the BET equation: BC e Q 0 Qe = (C S − C e )[1 + ( B − 1)C e / C s Where. which has a big influence on reactions on surfaces.1. Q0 is the amount of solute adsorbed per unit weight of adsorbent in forming a complete monolayer on the surface.adsorption sites through the ideal gas law. If more than one gas adsorbs on the surface. (1938) developed an equation for multimolecular adsorption. we define θE as the fraction of empty sites and we have θj = K j Pj 1 + ∑ K i Pi i =1 n and θE = 1 1 + ∑ K i Pi i =1 n where i is each one of the gases that adsorb. 1.
. Sips proposed an empirical isotherm equation which is often expressed as: 27 . The pseudo-firs torder Lagergren equation is indeed in line with the concept of linear driving force. Obviously. Qe is its value at equilibrium and k1 is a constant. Toth Isotherm Equation: This isotherm equation was derived from the potential theory.dQe = K (Qe − Qt ) dt in which Qt is the amount of adsorbate adsorbed at time t. but the T´oth isotherm equation could not reflect the feature of the Freundlich-type biosorption. and since then it has been frequently employed to analyze biosorption data obtained from various experiments using different adsorbates and biosorbents as reviewed by Ho et al.. (2000): dQt = K ' 2 (Qe − Qt ) 2 dt in which k’2 is a constant. the equation reduces to the Langmuir-type isotherm equation. 2006). and has been widely employed to describe biosorption on heterogeneous biosorbent surface: Qe = Qmax bTC e 1 [1 + (bTC e ) ]nT n in which bT and nT are two constants. It has been reported that the above equation could reasonably describe the Ni2+ biosorption by Sargassum wihtii (Vijayaraghavan et al. Sips Isotherm Equation: In study of the distribution of adsorption energies of the sites of a catalyst surface. Pseudo-Second-Order Equation: The pseudo-second-order kinetic equation was first proposed by Blanchard et al. if nT =1.
Freundlich Isotherm Equation: Freundlich proposed an empirical isotherm equation: Qe = kFEe 1 / nF in which kF and nF are Freundlich constants. and considered sorption as a chemical phenomenon.Qe = Qeth K eq Cn 5 e 1 + K eq Cnse in which ns is the Sips constant. Kumar and Porkodi concluded that the Sips isotherm provided the best fitting of experimental data. Based on a comparison study of a number of isotherm equations applied to the sorption of methylene blue on lemon peel. At the time of proposing the above empirical isotherm. Langmuir Isotherm Equation: Langmuir theoretically examined the adsorption of gases on solid surfaces. Similar to the Langmuir isotherm the equation. two approaches were developed for derivation of the empirical Sips equation. the Langmuir isotherm equation has a hyperbolic form: Qe = Qeth K eq C e 1 + K eq C e 28 . it can only be reasonably applied in the low to intermediate concentration ranges. has also been widely employed in biosorption research. Basically. followed by the Langmuir and the Redlich– Peterson isotherm equations. In the following sections. As the Freundlich isotherm equation is exponential. Sips noted that “we do not know whether or not this form of isotherm actually represents any experimental results”.
and Possibility of metal recovery. based on metal binding capacities of various biological materials. Biosorption The search for new technologies involving the removal of toxic metals from wastewaters has directed attention to biosorption.in which Qe is the adsorption capacity by weight at equilibrium. The degree of 29 . High efficiency. normally water) containing a dissolved species to be sorbed (sorbate. biological material) and a liquid phase (solvent. No additional nutrient requirement. The biosorption process involves a solid phase (sorbent or biosorbent. This isotherm equation has been most frequently applied in equilibrium study of biosorption. Minimisation of chemical and/or biological sludge. 1. The major advantages of biosorption over conventional treatment methods include (Kratochvil and Volesky. while Ce is concentration of adsorbate at equilibrium. Qeth is the theoretical maximum adsorption capacity by weight. The process continues till equilibrium is established between the amount of solid-bound sorbate species and its portion remaining in the solution. however. Regeneration of biosorbent. it should be realized that the Langmuir isotherm offers no insights into the mechanism aspects of biosorption. 1986). 1992). Due to higher affinity of the sorbent for the sorbate species. and Keq represents the equilibrium constant of adsorption reaction.9. the latter is attracted and bound there by different mechanisms. Algae. 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 (Fourest and Roux. bacteria and fungi and yeasts have proved to be potential metal biosorbents (Volesky. 1998): Low cost. metal ions).
(2003) used dewatered waste activated sludge from a sewage treatment plant for the biosorption of zinc from aqueous solutions.. zinc and lead on submerged aquatic plant Myriophyllum spicatum.1. which are by-products or the waste materials from large-scale industrial operations. biosolids ( orton et al.69 mg/g for lead. 2003). Some laboratories have used easily available biomass whereas others have isolated specific strains of microorganisms and some have also processed the existing raw biomass to a certain degree to improve their biosorption properties. For e. 15..9.. etc. Recent biosorption experiments have focused attention on waste materials.. The adsorption capacities were 46. Some types of biosorbents would be broad range. olive mill solid residues (Pagnanelli et al. (2003) studied the adsorption characteristics of copper. 2002).sorbent affinity for the sorbate determines its distribution between the solid and liquid phases.37 mg/g for copper. The use of biosolids for zinc adsorption was favourable compared to the biosorption rate of 0. 1996).59 mg/g for zinc and 10.299 mm/g by the seaweed Durvillea potatorum (Aderhold et al.. Keskinkan et al. orton et al. binding and collecting the majority of heavy metals with no specific activity..g. 1.. 2003).. activated sludge from sewage treatment plants (Hammaini et al. aquatic macrophytes (Keskinkan et al. (2002) have carried out a preliminary study on the 'Use of olive mill residues as heavy metal sorbent material 30 . The adsorption capacity was determined to be 0. 2003). the waste mycelia available from fermentation processes. while others are specific for certain metals. This type of biosorbent consists of dead and metabolically inactive cells. Pagnanelli et al.564 mM/g of biosolids. Biosorbent material: Strong biosorbent behaviour of certain micro-organisms towards metallic ions is a function of the chemical make-up of the microbial cells.
entrapment in inter and intrafibrilliar capillaries and spaces of the structural polysaccharide network as a result of the concentration gradient and diffusion through cell walls and membranes.5 mg/g under different operating conditions. 2003) were 0. sulphhydryl and carboxyl groups in proteins. representing many different types of marine macro-algae. However most of the contributions studying the uptake of toxic metals by live marine and to a lesser extent freshwater algae focused on the toxicological aspects. hydroxyls in polysaccharide and mainly carboxyls and sulphates in polysaccharides of marine algae that belong to the divisions Phaeophyta. There are several chemical groups that would attract and sequester the metals in biomass: acetamido groups of chitin. Another inexpensive source of biomass where it is available in copious quantities is in oceans as seaweeds.29 mmol/g for Cu-Zn and 0. adsorption by physical forces. chelation. it does not necessarily mean that the presence of some 31 .32 mmol/g for metal system such as Cu-Cd. The simultaneous biosorption capacity of copper. amido.and the results revealed that copper was maximally adsorbed in the range of 5. Although abundant natural materials of cellulosic nature have been suggested as biosorbents. cadmium and zinc on dried activated sludge (Hammaini et al. structural polysaccharides of fungi. However. amino and phosphate groups in nucleic acids. very less work has been actually done in that respect. 0.32 mmol/g for Cd-Zn.0 to 13. Rhodophyta and Chlorophyta. mainly ion exchange. The mechanism of biosorption is complex. and pollution indicators by live. metabolically active biomass. The results showed that the biomass had a net preference for copper followed by cadmium and zinc. metal accumulation. Focus on the technological aspects of metal removal by algal biomass has been rare. amino..
Review of Past Works on Adsorption Heavy metals are some of the major factors of environmental contaminations. In terms of environmental threats.10. for this purpose is often inefficient and/or very expensive (Cheung et.. and evaporative recovery. 1. al. Apart from toxicological criteria. such as ion exchange. Strategic and precious metals though not environmentally threatening are important from their recovery point of view. on the basis of which they would be divided into four major categories: (i) toxic heavy metals (ii) strategic metals (iii) precious metals and (iv) radio nuclides. it is mainly categories (i) and (iv) that are of interest for removal from the environment and/or from point source effluent discharges. 1. The toxicity and interesting solution chemistry of elements such as chromium. the interest in specific metals may also be based on how representative their behaviour may be in terms of eventual generalization of results of studying their biosorbent uptake.9. reverse osmosis. chemical precipitation. perhaps due to steric. the use of conventional technologies. Some of the works carried-out by a number of 32 . either because of high operating cost or the difficulty in treating. these methods are commercially impractical. For example. conformational or other barriers.2. Physical and chemical methods have been proposed and applied to remove metal ions from effluents. arsenic and selenium make them interesting to study.functional group guarantees biosorption. Choice of metal for biosorption process The appropriate selection of metals for biosorption studies is dependent on the angle of interest and the impact of different metals. but in general. 1997).
are inexpensive but ineffective. Pb and Zn in four different types of soils. but is readily soluble under extreme pH conditions (Huang and Blankenship. 1989). Ions of toxic metals can bind to the mineral surface in a number of ways. A number of adsorbent materials have been studied for their capacity to remove heavy metals. metals were extracted predominantly from the carbonate fraction.. reverse osmosis and other methods become inefficient when contaminants are present in trace concentrations. adsorption.researchers will be reported as a form of review on past works on the adsorption of metals from aqueous solutions containing metal ions and how effective the various adsorbent used have been able to remove or adsorb the metal ions. Morera et al. crushed coals etc. Trivedi et al.. such as ion exchange resins are totally effective but expensive and others. 2000). Cu. 33 . activated alumina. with a slight variation. (2001) evaluated the mobility and distribution of Cd. The process of adsorption is one of the few alternatives available for such situations (Huang and Morehart. Chemical contaminants at low concentrations are difficult to remove from water. ion exchange resins. Ni. Chemical precipitation.. Activated carbon is very effective in removing heavy metals. including absorption. Some of these materials. 1991). Sequential extraction analyses showed that in the case of soils with a higher content of carbonates. (2001) investigated adsorption of metals onto goethite surface and found a connection between metal affinities for goethite and order Cu > Pb > Zn > Cd > Co > Ni > Mn > Ca > Mg. The authors also confirmed the high affinity of Cu with organic matter. which tends to follow the decrease in electronegativity and radii of the hydrated cations. precipitation and cation exchange (Steele et al. including activated carbon. Ni or Zn. such as coal and straw. They concluded that soils have a higher affinity with Pb and Cu than with Cd.
3 to 5. The adsorption kinetics of Mn2+.Ni2+ and Cu2+ on M . They compared M . In this study Slow Sand Filters (SSFs) were tried to remove heavy metals and found very effective (Muhammad et al. Equilibrium adsorption times without any change of concentrations (Cr) remaining without adsorption of heavy metals were obtained from kinetic curves related to Mn2+.. 1997). Experimental results on the influences of process variables in removing heavy metals by SSFs demonstrated that adsorption was one of the mechanisms of the removal of heavy metals (Muhammad et al.2514. 1997). Adsorption isotherms of heavy metals on M . The adsorption rate constants were determined from obtained kinetics curves suitable for first degree of rate kinetics. This research deals with the results of the batch adsorption tests to establish adsorption isotherms and adsorption capacity of the sand for the selected heavy metals. Fe2+. Ni2+ and Cu2+. The solution was diluted and analyzed with a UNICAM 929 Atomic Absorption Spectrometer (AAS). chitosan and agar according to their percent uptake yields of the heavy metals.2514 from aqueous solution were determined. Sufficient amounts of sample were taken from solutions containing adsorbent.Peat moss has been found as very effective in adsorbing heavy metals (Ho. The removal of some heavy metals ions (Mn2+. To confirm this prediction/hypothesis. Ni2+ and Cu2+) from aqueous solution by adsorption was investigated by Uzun and Guzel (2000). batch adsorption tests were carried out.2514.Fe2+. 1995).. chitosan and agar were used as adsorbents. The adsorption isotherms of heavy 34 . Fe2+.2514 commercial activated carbon were investigated.5 and the equilibrium adsorption contact times were determined for M . The commercial activated carbon (Merck 2514). All experiments were carried out in a pH range from 5. These adsorption isotherms were seen to be consistent with Freundlich's adsorption isotherm.
2004) by these soils.29 g kg−1 in RD and RE respectively) and low cation exchange capacity (1. The objective of this work was to evaluate heavy metal sorption capacity of two subsurface horizons from an Eutric Regosol (ER) and a Distric Regosol (DR). Kd100 was used to establish the adsorption and retention selectivity sequences of the heavy metals (Covelo et al. 2001). in a competitive system. and Zn nitrates (between 10 and 400mg L−1) were prepared to obtain adsorption isotherms. The clay proportion in soils mineral fraction is 21. are important to determine heavy-metal availability to plants and their mobility throughout the soil. Kaolinite is the most frequent mineral in RD clay fraction (>50%) whereas in RE is between 10 and 30% in their clay 35 . buffered at pH 4.. Heavy-metal adsorption reactions. metal in solution was determined by ICP-OES (Perkin Elmer Optima 4300 DV). Desorption experiments were performed using the pellets resulting from adsorption experiments (Madrid and Diez. Each sample was treated with 200mL of an acetic acid (0. Cu.38 cmol(+) kg−1 in RD and RE respectively).5 and shaken for 24 hours at 25ºC. 1992)..94% in Distric Regosol and 26.3 and 19. Pb. is often controlled by metal ion binding to natural organic matter (Kinniburgh et al.08 and 0.02M) and sodium acetate (0. Twelve grams of soil samples were treated with 200mL of solution and shaken for 24 hours at 25ºC (Gomes et al.. which is of relevance in metal bioavailability and toxicity studies. The amount adsorbed (Ca) was calculated from the difference between initial and equilibrium concentrations.metals were studied. It is now well established that the free metal ion concentration. Ni. 1990). Cr. Ten solutions of mixtures of Cd.02M) solution. Both studied Regosols have low organic matter contents (5. After centrifugation.29% in Eutric Regosol. The equilibrium concentrations of heavy metals were determined after taking sufficient amount of samples from clear parts of solutions containing adsorbent and doing proper dilutions.
Pb > Zn > Cd > Cr > Ni > Cu is the adsorption selectivity sequence obtained in RE. indicating that the overall adsorption process was endothermic and spontaneous.fraction. Thermodynamic parameters such as ∆G0. RD has low mineralogical variety and oxides content than RE.3mg/g. Effects of foreign anions were also examined. Kinetic studies showed that the adsorption obeyed a second order and Elovich model. Freundlich and dubinin Radushkevic(D-R) isotherms were used to model the adsorption equilibrium data and the system follow three isotherms. Selectivity sequences obtained in DR are Pb > Zn > Cr > Cd > Ni > Cu (after adsorption experiments) and Cr > Zn > Ni > Pb > Cd > Cu (after desorption ones). Cu is the metal adsorbed and retained in lesser amounts in both studied soils. and ∆S0 were evaluated. The adsorption of the biosorbent was found to be 76. Langmuir. Optimum pH for Cr(VI) adsorption was to be 2. Coconut coir pith. Pb is retained in higher amounts than Ni by RE whereas RD retains higher amounts of Ni than Pb. hexadecyltrimethylammonium bromide. This fact is attributable to their low organic matter content because this soil property presents high affinity to Cu sorption and retention. Only third and fourth positions change. amasivayam and Sureshkumar (2007) used 36 . an agricultural solid waste was used by amasivayam and Sureshkumar (2007) as biosorbent for the removal of chromium(VI) from water and waste water after modification with a Cationic surfactant. The adsorbent was also tested for the removal of Cr(VI) from electroplating effluent. ∆H0. RE mineralogical variety influences the high Pb retention of this soil. Their retention selectivity sequence is Cr > Zn > Pb > Ni > Cd > Cu. which is higher or comparable to the adsorption capacity of various adsorbents reported in literature.0. Reduction of Cr(VI) to Cr(III) occurred to a slight extent during the removal. Both retention selectivity sequences are very similar.
respectively. whereas that of chromium to 143 and 95mg/g for S.. there is selectivity towards chromium around 92% with S.heaxdecyltrimethylammonium to modify the surface of coir pit. (2006). Equilibrium adsorbtion data showed good fit to all the three isotherms.xylosus. Langmuir.xylosus only. They went further that chromium removal was substantially greater for modified coir pit than for a raw coir pit.. it was observed that pH optima were very close. In Cd(II) biosorption experiments.xylosus and Pseudomonas respectively. there is a profound selectivity for cadmium biosorption.0 for Pseudomonas sp. optimum ph for chromium removal was found to be 2. In binary mixtures with Cd (II) ions as the dominant species. In this work. maximum uptake capacity of cadmium was estimated to 250 and 278 mg/g.0 and the reduction of Cr(VI) to Cr(III) also took place during adsorbtion process. biomass concentration and contact time was determined. reaching 96% and 89% for pseudomonas sp. It was shown that when Cr(VI) ions are the dominant species. freundlich and dubinin raduskevich. at 10 mg/L Cd(II) and 5mg/L Cr(VI). and their selectivity in binary mixtures was investigated by Ziagova et al. 6. From Cadmium uptake values 278 and 250mg/g for Pseudomonas sp.xylosus and 7.xylosus. comparing to Cr(VI).0 and 4.xylolus and pseudomonas sp. The removal of chromium ion from aqueous solution by surfactant modified coir pit was found to be effective. Desorption studies showed that apart from ion exchange. and S. and it was spontaneous.0 for S. 37 .. chemisorptions might also govern the chromium uptake by the surfactant modified adsorbent Biosorption of Cd(II) and Cr(VI) ions in single solution using staphylococcus xylosus and pseudomonas sp.0 for S. respectively. Langmuir and freundlich models were applied to describe metal biosorption and the influence of pH. Adsorbtion process flowed second order kinetics and elovich model. and S.where the estimated values are 1.
it was concluded that both bacteria can be used successfully for cadmium removal. Their elemental analysis indicated that there is an increase in the sulphur content of the fractionalized biomass from initial 0. Cr(VI). suggesting the incorporation of thio group on HLS. they observed a profound selectivity for cadmium biosorption against chromium.36% to 3.. (2007) fractionalized husk of lathyrus sativus(HLS) by introducing thio groups with the help of carbon disulphide treatment in alkaline environment. Effects of contact time and pH on the adsorption process were investigated and the isothermal studies were carried out using 1g of leaves in 50ml synthetic waste water at different metal ions concentrations while the initial pH of the synthetic waste water was about 5. Also. Abdel-Ghani et al.xylosus only. and Temkin isotherms to examine their experimental results in other to obtain the appropriate model and they found out that Temkin isotherms represent the measured sorption data well.. Freundlich. They concluded that Casuarina Glauca tree leaves were able to simultaneously remove chromium and lead ions from the aqueous solutions. and other toxic metals. They observed after 120minutes of contact between the adsorbent and the adsorbate that an increase in the pH resulted in a higher metal removal which showed that tree leaves can be used for the sorption of Cr(III) and Pb(II) from mixed solutions.7% of the priastine biomass. using both bacteria. Also. when Cr(VI) ions are the dominant species in the solution.respectively. They used Langmuir. Panda et al. It was concluded that this is a first step towards creation of highly selective biosorbents for Cd(II). in the binary systems examined when Cd(II) ions are the dominant species in the solution. there is selectivity towards chromium with S. The 38 . (2008) carried out adsorption of Cr(III) and Pb(II) from a solution onto Casuarina Glauca tree leaves as the adsorbent.
They concluded that fractionalized biomass enhances the biosorption capacity of HLS in the treatment of industrial effluent. respectively. They also deduced that in the case of unmodified HLS.Passiflora edulis Sims.involvement of the hydroxyl groups mainly in the fractionalization process is demonstrated by Fourier transform infrared (FTIR) spectroscopic study.8 and 23. (2006) used a yellow passion-fruit shell (YPFS. They observed that the adsorption capacity of the fractionalized biomass with respect to Cadmium and Nickel increased by about 50% compared to that of pristine one.48×10-2 and 4. respectively. obtaining the biosorption constant rates.6mg of Cadmium and Nickel. Jacques et al. presenting a biosorption capacities for Cr(III) and Pb(II) which in-turn makes its use in 39 .0. F. They concluded that YPFS is an excellent alternative biosorbent for the removal of Cr(III) and Pb(II) from aqueous solutions because of its direct use without any chemical treatment..70×10-3g/mg/min using metallic ion solution. flavicarpa Dedener) as an alternative biosorbent for the removal of Cr(III) and Pb(II) ions from aqueous solutions.6mg/g for Cr(III) and Pb(II).1 and 151. It was observed that the maximum biosorption capacities of YPFS were 85. for Cr(III) and Pb(II). 1g of fractionalized HLS adsorbs 52. respectively. 1. thereby registering about 50% adsorption increment compared with that of control biomass. They found out that at pH 5. The effects of pH and contact time on the biosorption capacities were studied and they observed that the biosorption kinetics follows a pseudo second order kinetic model. adsorption process involving the fractionalized biomass obeys Langmuir isotherm model and attains equilibrium in 10minutes compared with 60minutes attainment of the unmodified biomass. They reported that the high biosorption capacities of YPFS places this biosorbent as one of the best biosorbents for the removal of Cr(III) and Pb(II) from aqueous effluents.
2008) that the hydrothermally solidiﬁed materials developed strength despite the formation of hydrogarnet. They concluded that the mesopore volume increased. sorbate concentration and adsorbent dose. the adsorption of Ni(II) ions on CA was comparatively higher than CCCA and CCS.4nm. They remarked that the hydrothermally solidiﬁed materials showed an excellent humidity-controlling ability due to adsorption and desorption of water vapor by utilizing their mesopores.0. Chitosan coated calcium alginate(CCCA) and chitosan coated silica(CCS). quartz and slaked-lime with different forming pressures. contact time. They observed (Hirotaka et al. Mesoporous materials were prepared by Maeda and Ishida (2007) using hydrothermal treatment of powder-compacts consisting of metakaolinite. SEM. This result 40 . and Langmuir isotherms. They concluded that biomaterials are more effective for the removal of Ni(II) from aqueous medium. The biosorbent were characterized by FTIR.. was studied by Vijaya et al. They observed that the adsorption of Ni(II)ions onto the biopolymers follows a pseudo second order kinetics and that the equilibrium adsorption data for Ni(II) on CA. (2007).commercial view point interesting because of its low preparation cost and large availability in the tropical countries. using equilibrium batch and column flow techniques. They noted that the optimum pH was found to be 5. thus enhancing the water vapor adsorption–desorption ability of the materials.. and the volume and speciﬁc surface area increased with decreasing the forming pressure.CCCA and CCS were fitted to Freundlich. such as calcium alginate(CA). exhibited a broad pore size distribution of more than 3. TGA and surface area analysis. Removal of Nickel(II) from aqueous solutions through adsorption onto biopolymer sorbents. The extent of adsorption was found to be a function of the pH of the solution.
The results suggested that the pseudosecond-order model (R2 > 0.43 kJ mol−1 (at 296± 2 K). Meral and Ayhan (2008) studied the effect of temperature. In this work. 31. the speciﬁc BET surface area and zeta-potential of the QTR were analysed. Besides. The best interpretation for the experimental data was given by the Langmuir isotherm and the maximum adsorption capacity (86. indicating the spontaneous. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to investigate QTR structure and morphology. Langmuir. pseudo-second-order. respectively. The kinetic data was tested using pseudo-ﬁrst-order. enthalpy (∆H◦) and entropy (∆S◦) of Pb adsorption on modiﬁed tannin resin were calculated as −5. naturality and abundance. Elovich and intra-particle diffusion model. Thermodynamic functions. They concluded that.207 mg g−1) of Pb(II) was obtained at pH 5 and 296 K. Also.127 J mmol−1 K−1.999) was the best choice among all the kinetic models to describe the adsorption behavior of Pb(II) onto QTR. Freundlich and Tempkin adsorption models were used to represent the equilibrium data.84 kJ mol−1 and 0.agreed well with the prediction made using the Kelvin equation and Arai’s correction equation. it is apparent that QTR can serve as an appropriate adsorbent in removal process of Pb(II) ions from aqueous solution in terms of its high sorption capacity. The hydrothermally solidiﬁed materials prepared at 15MPa showed excellent humidity-controlling properties in the airtight chamber. 41 . pH and initial metal concentration on Pb(II) biosorption on modiﬁed quebracho tannin resin (QTR). the change of free energy (∆G◦). chemically modiﬁed tannin resin as a sorbent is an efficient and economical alternative in Pb2+ ion removal from water. endothermic and the increased randomness nature of Pb2+ adsorption.
in a multi-layered adsorption system composed of the water trap and the hydrocarbon trap. the hydrocarbon removal efficiency was greatly improved owing to the elimination of water with the hydrophilic zeolite A in the upper layer. The competitive adsorption of water vapor and hydrocarbons in the exhaust gas from a gasoline vehicle on the hydrocarbon adsorption sites at low temperatures caused the decrease in the H/C removal efficiency during a cold-start. the hydrocarbon desorption can be delayed because of the latent heat of desorption of adsorbed water in the upper layer during evaporation. respectively.Tae et al. competitive adsorption of water vapor and hydrocarbons in the exhaust gas from a gasoline vehicle on the hydrocarbon adsorption sites at low temperatures causes decrease in the H/C removal efficiency during a cold-start and in the multi-layered adsorption system composed of the water trap and the hydrocarbon trap.. Therefore. the hydrocarbon removal efficiency was greatly improved owing to the elimination of water with the hydrophilic zeolite A in the upper layer. this double-layered zeolite-based hydrocarbon trap showed the better performance compared with the conventional hydrocarbon trap during a cold-start. in which zeolite A and zeolite beta was selected for the water trap and the hydrocarbon trap. Furthermore. Therefore. They concluded that. with the goal of reducing hydrocarbon emissions during a cold-start. also the hydrocarbon desorption can be delayed because of the latent heat of desorption of adsorbed water in the upper layer. It was reported that. The adsorption and desorption of hydrocarbons was examined in the monolithic adsorber during a vehicle test as well as in a lab-scale micro-reactor as a powder form. this double-layered zeolite-based hydrocarbon trap showed the better performance compared with the conventional hydrocarbon trap during a cold-start. (2008) used hydrocarbon (H/C) trap developed using a multilayered zeolite. 42 .
in particular aromatic molecules. they remarked that. They observed from their survey of about 100papers that low. the extent of chemical modiﬁcations. low-cost materials are sorely needed that are comparable to activated carbon or synthetic resins in-terms of adsorption capacity and should be locally available. They noted that. instead of using commercial activated carbon and synthetic resins. which make them suitable for industrial effluents containing phenol and its derivatives. biomass. Therefore. zeolites. some solid waste such as sludge has become one of the society’s most vexing 43 . dried activated sludge. Chemical contamination of water from a wide range of toxic compounds. which have high adsorption capacity and are locally available. is a serious environmental problem owing to their potential human toxicity (Su-Hsia and Ruey-Shin. and various low cost natural adsorbents for the removal of phenol and its derivatives from contaminated water. synthetic resins. They noted that the adsorption capacities of the adsorbents presented here vary signiﬁcantly depending on the characteristics of the individual adsorbent. red mud. and the concentrations of solutes. 2008). Su-Hsia and Ruey-Shin (2008) reviewed the technical feasibility of the use of activated carbon.cost adsorbents have demonstrated outstanding removal capabilities for phenol and its derivatives compared to activated carbons (Su-Hsia and Ruey-Shin.In this work. 2008). and other adsorbents. On the other hand. The present review shows that some such materials have equivalent or even more adsorption capacity to activated carbon and synthetic resins. HiSiv 1000 and IRA-420 display high adsorption capacity of phenol and XAD-4 has good adsorption capability for 2-nitrophenol. and cetyltrimethylammonium bromide-modiﬁed montmorillonite. sludge. Adsorbents that stand out for high adsorption capacities are coal-reject. Of these synthetic resins. researchers have worked on inexpensive materials such as coal ﬂy ash. residual coal treated with H3PO4.
Redlich-Peterson and Langmuir-Freundlich adsorption models were used for the mathematical description of adsorption equilibrium and isotherm constants were evaluated at 25 °C.9 mg g−1. Last but not the least. if the alternative adsorbents mentioned previously are found to be highly efficient for the removal of phenol and its derivatives. the use of low-cost adsorbents may contribute to the sustainability of the surrounding environment and undoubtedly.0. fertilizer wastes. Ozlem et al. they were still non-economic.problems (Su-Hsia and Ruey-Shin. respectively. a vinyl sulfone type reactive dye. Su-Hsia Lin and Ruey-Shin Juang concluded that. at an initial pH value of 1.7 and 50. If the solid waste can be converted into low-cost adsorbents for the treatment of discharged wastewater. (2008) studied the potential use of cotton plant wastes-stalk (CS) and hull (CH) as sorbents for the removal of Remazol Black B (RB5). According to the Langmuir model. Simple mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. 2008). All models except the Freundlich model were applicable for the description of dye adsorption by both sorbents in the concentration range studied. The Freundlich. different types of coal. the cost of removal might decrease.. Although the organoclays revealed good adsorption capability. (CS) and (CH) sorbents exhibited the highest RB5 dye uptake capacities of 35. It was 44 . not only the industries but the living organisms and the surrounding environment will also beneﬁt from the potential toxicity due to phenol and its derivatives. The results indicated that adsorption was strongly pH-dependent but slightly temperature-dependent for each sorbent-dye system. Langmuir. and soon. Preliminary studies have also revealed the applicability of the substances such as dried activated sludge. red mud. low-cost adsorbents will offer alot of promising beneﬁts for commercial purpose in the future. as scavengers of phenol and its derivatives.
1%. and adsorption kinetics followed the pseudo second-order type kinetic model for each sorbent.found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye. the maximum BB54 uptake of 2. As a widely used and hazardous dye. the wastes of cotton plant. they can be put in use as economical sorbents for the wastewater treatment. FTIR spectrum result revealed the presence of adsorbing groups such as carboxyl. the batch sorption equilibrium was obtained within 5 minutes and kinetic studies suggested that the sorption followed the internal transport mechanism. contact time and temperature on the sorption of BB54 to the EPS were examined.005 g/g was obtained and chemical analysis of the EPS indicated the presence of protein (30. They concluded that. basic blue 54 (BB54) was chosen as the model dye to examine the adsorption performance of the EPS (Zhang et al. w/w). Using the Langmuir model parameters. Since cotton stalk and hull. (2008) used extracellular polymeric substance (EPS) of Proteus mirabilis TJ-1 as a novel biosorbent to remove dye from aqueous solution in batch systems. High-molecular weight of the EPS with more binding-sites and stronger van der Waals forces together with its specific construct led to the excellent performance of dye adsorption (Zhang 45 . hydroxyl and amino groups in the EPS. w/w) and acid polysaccharide (63. At various initial dye concentrations (50–400 mg/L). Zhang et al. According to the Langmuir model. abundantly and locally available. Results obtained from this study showed that cotton stalk or cotton hull can be used as an adsorbent for the removal of RB5 dye from the aqueous solution in a static batch system.9%. thermodynamic constant ∆G° was also evaluated for each sorption system.. 2008). are freely. initial dye concentration.. Scanning electron microscopy (SEM) images showed that the EPS with a crystal-linear structure was whole enwrapped by adsorbed dye molecules. The effects of pH.
Optimum pH for ion exchange was 5.0 for Lewatit MP 64 and 6. owing to the presence of carboxyl. mirabilis TJ-1 is an effective biosorbent to remove BB54 from aqueous solution which also shows potential board application as a biosorbent for both environmental protection and dye recovery.0 for Lewatit MP 500. The ion exchange process. which have been approved to be the preferred groups for most sorption processes. 2008). The optimum pH for Cr(VI) adsorption was found as 5. which is dependent on pH. but Lewatit MP 500 shows stronger binding. contact time and temperature. The maximum chromium sorption occurred at approximately 60 min for Lewatit MP 64 and 75 min for Lewatit MP 500..41 mmol/g resin for Lewatit MP 64 and Lewatit MP 500 anion exchangers. They concluded that. The suitability of the Freundlich and Langmuir adsorption models was also investigated for each chromium–sorbent system. The concentration of Cr(VI) in aqueous solution was determined by UV–visible spectrophotometer. pH. adsorbent dose. The uptake of Cr(VI) by the anion exchange resins was reversible and so it has good potential for the removal of Cr(VI) from aqueous solutions (Pehlivan and Cetin.et al. hydroxyl and amino groups in the EPS. Batch shaking sorption experiments were carried out to evaluate the performance of Lewatit MP 64 and Lewatit MP 500 anion exchange resins in the removal of Cr(VI) from aqueous solutions. The maximum Cr(VI) adsorption at pH 5. both resins have a large collective sorption with Cr (VI) ion. The sorption of Cr(VI) from aqueous solutions with macroporous resins which contain quarternary amine groups (Lewatit MP 64 and Lewatit MP 500) was studied by Pehlivan and Cetin (2008) using varying Cr(VI) concentration. The isotherm plots showed a high sorption for pH 3–5 for both of the resins.40 and 0. respectively. They concluded that. 2008). EPS of P.0 for 46 . showed maximum removal of Cr(VI) in the pH range 3–7 for an initial Cr(VI) concentration of 1 × 10−3 M.0 is 0.
TOS material was prepared by treatment of olive stones with concentrated sulphuric acid at room temperature followed up by a subsequent neutralization with 0. the sorption efficiency of TOS is compared to those of other low-cost sorbents materials yet described in the literature.2 and 526.0 for Lewatit MP 500. The results found in the course of this study suggest that ion exchange mechanism is the most appropriate mechanism involved in cadmium and safranine removal. sorption efficiency of treated olive stones (TOS) towards cadmium and safranine removal from their respective aqueous solutions was investigated. raw olive stones were treated with concentrated sulphuric acid without heating or using any special atmosphere 47 . pH effect and thermodynamic parameters. 2008). They concluded that. 75 min for Lewatit MP 500.Lewatit MP 64 and 6. The resulting material has been thoroughly characterized by SEM. Finally. The preliminary results indicate that TOS exhibit a better efficiency in terms of sorption capacities toward the two pollutants (128.3 mg/g for cadmium and safranine.1 M NaOH aqueous solution. MAS 13 C NMR. sorption isotherms. the sorption process is ascertained to occur fast enough so that the equilibrium is reached in less than 15 min of contact time. energy-dispersive X-ray (EDX). In this work. FTIR and physicochemical parameters were calculated. Moreover. The sorption study of TOS at the solid–liquid interface was investigated using kinetics. respectively) than those reported so far in the literature. The adsorption of Cr(VI) increased with agitation period and attained an optimum at about 60 min for Lewatit MP 64. These ion exchangers can be used as an efficient sorbent for the removal of Cr(VI) from aqueous solution and are thus attractive sorbents for the treatment of wastewater containing Cr(VI) ion at trace levels and can also be used for reversible uptake of Cr(VI) and successfully applied to water and industrial wastewater samples(Pehlivan and Cetin.
leading to a low-cost sorbent with a good affinity for positively charged species.. They concluded that. Cr(VI). and silica gel showed high values for all metals. Cu(II) and Pb(II) from waste water was investigated by Katsumata et al. tobermorite. simple and cheap for the removal of heavy metals. The obtained material was characterized and used for basic dye and heavy metal removal from aqueous solutions. The kinetic and sorption data fitted well the second-order kinetic model and the Langmuir model. Cr (VI) and Cu (II) in rinsing wastewater from plating factory and since the economical adsorbents used can be obtained commercially because they are easily synthesized. kaolin. magnetite. (2003) using column method. The obtained sorption capacities toward safranine and cadmium were better than many low-cost materials yet reported in the literature. The proposed ion exchange sorption mechanism is discussed on the basis of SEM. the wastewater treatment system developed is rapid. This removal method of heavy metals proved highly effective as removal efficiency tended to increase with increasing pH and decrease with increasing metal concentration (Katsumata et al. 48 . FTIR and mass balance results. with good values of the determination coefficient.environment. They remarked that. MAS 13 C NMR. tobermorite. the column method was effective in the removal of Cd (II). 2003).. silica gel and alumina as adsorbents for the removal of Cd(II). respectively. magnetite. They observed that the removal percentages by adsorption onto montmorillonite. the adsorption process shows a chemisorption reaction process. The removal of heavy metals from plating factory wastewater with economical materials such are montmorillonite. The sorption process was found to be pH independent. based on heat of adsorption. EDX.
91 mol/kg at pH 4. Cd(II) and Pb(II) from aqueous solution at different pH values 1–5 was also investigated. cross-linked a grape waste using a concentrated sulphuric acid form an adsorption gel which was then characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. which was not 49 . since most of the industrial wastewaters contaminated with Cr (VI) are highly acidic. pH of metal solution. which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1. contact time and adsorption isotherm of Cr(VI).. It was observed that the cross-linked grape waste gel was found to selectively adsorb Cr (VI) over other metal ions tested. Cross-linked grape waste gel has been found to be selective to Cr (VI) ion and highly effective for its removal from synthetic aqueous solution and that. cross-linked grape waste gel can be good candidate for waste water treatment and due to large generation of grape waste each year. Zn(II). They concluded that. (2000).Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions (Rumi et al. Rumi et al.. leaves for the adsorption of Pb (II). Cu (II) and Ni (II) ions were studied by Salehi et al. The effects of different parameters such as contact time of biosorbent and sorbents. seems to be a promising adsorbent. The adsorption of different metal ions like Cr(VI). simple production process of cross-linked grape waste gel. Fe(III). The maximum sorption of all metals was carried out in pH 4. They remarked that the cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr (VI) removal.. (2008). In this study the ability of Cercis siliquastrum L. Adsorption tests were conducted in batch mode to study the effects of pH. Cr(III). Increasing the initial metal concentration in lower values caused a steep growth in biosorption. 2008). and initial metal ion concentration on the biosorption were investigated.
The maximum uptake for all metal ions was obtained in pH 4. Preliminary studies on the antifertility effect of pawpaw seeds (Carica papaya) on the gonads of male albino (Wistar) rats was investigated by Udoh and Kehinde (1999). Cu (II) and Ni (II) can be best described by the second-order kinetic.9998 for all the sorbate-sorbent systems. among the tested metal ions. Experimental data were exploited for kinetic evaluations related to the sorption process. According to the obtained correlation coefficient values. The biosorption of the metal ions were studied by Langmuir and Freundlich adsorption isotherm models. According to our results. The overall adsorption rate of the Pb (II). leaves has been investigated for removing heavy metals. An oral dose of crude ripe pawpaw seeds at 100 mg/kg body weight and 50 mg/kg body weight were administered orally for 8 weeks and histological observations at a high dose of 100 mg/kg body weight showed degeneration of the germinal epithelium and germ cells. the affinity of the leaves to metal ions was in the order of Pb (II)> Cu (II)> Ni (II). such as Pb (II). The results obtained in this study indicated the highest adsorption ability of C. siliquastrum leaves proved that the process conform Langmuir better than Freundlich isotherm model. They concluded that. It was observed that the data were fitted very well to Langmuir adsorption isotherm model. a reduction in the number of Leydig cells and the presence of vacuoles in the tubules and at a low dose of 50 mg/kg body weight little 50 . The study of metals biosorption by C.observed in higher values. Freundlich model could predict Pb (II) and Cu (II) adsorption adequately but it was not suitable for Ni (II) sorption. In the optimum sorption condition. the potential of Cercis siliquastrum L. siliquastrum for Pb (II). second-order kinetic provided a good description of biosorption for the tested metals with regression correlation coefficients more than 0. Cu (II) and Ni (II) from aqueous solution.
These immunomodulatory activities of crude Carica® Seed Extract and its bioactive fractions were examined in vitro using lymphocyte proliferation assays and complement-mediated hemolytic assay. Mariluz et al. and ripped then dried pawpaw seeds (PPSE) as an antioxidative agent. 51 . Robert and Dane (2008) tested the effectiveness of the Methanolic extracts from under-ripped. Under-ripped seeds contained more total phenolic compounds than ripe seeds.effect was observed. Three major observations were made in this study: (1) the crude Carica® Seed Extract and two other bioactive fractions significantly enhanced the phytohemagglutinin responsiveness of lymphocytes. The development of value added products from pawpaw seeds may lead to successful commercialization of this underutilized fruit (Robert and Dane. however.. 2003). These findings provide evidence for Immunostimulatory and antiinflammatory actions of Carica® Seed Extract (Mariluz et al. The product claims to improve immunity against common infection and body functioning. 2008). Carica papaya seed extract is currently being marketed as a nutritional supplement with purported ability “to rejuvenate the body condition and to increase energy”. ripped. but ripe seeds showed the highest reducing potential. there was disorganization in some of the seminiferous tubules while others appeared normal. (2003) analyzes the chemical constituents of the Carica® Seed Extract and determine the potential immunomodulatory properties of the different bioactive fractions. and (3) some of the bioactive fractions of Caricas seed extract were able to significantly inhibit the classical complement-mediated hemolytic pathway. (2) none of the Carica® Seed Extract (at the concentrations used in this study) was able to protect the lymphocytes from the toxic effects of chromium..
With an increase in the concentrations of these metals. Data gathered from Electrical Stirred Flow Unit (ESFU) used for kinetic study indicated that almost steady state adsorption conditions were reached after 2-4 h of unit working for the adsorption of Pb (II). The constants rate represented capacity and intensity factors of the best fitted equations showed that the increasing trend of adsorption capacity have the order: calcite> montmorillonite> kaolonite in their tendency to retain HM. leaf and root as an adsorbent of chromium (Cr). the same trend of HM retention was detected.e. compared to the alluvial clay soils. calcite < montmorillonite< kaolinite. The effect of contact time. Cd (II) and Zn (II). The metal uptake capacity of the root for different metals was found to be in the order: 52 . These explain the low effect of pollution of heavy metals on the calcareous soils.2%. At 2000 ppm metal concentration and 2h reaction time. nickel (Ni). kaolonite and calcite) for their ability to remove heavy metals (HM). These minerals were applied in chloride form dissolved in aqueous solutions of these metals at two concentrations (2000 and 6000 ppm). initial metal concentration and type of natural soil minerals on the adsorption process at 20±2C° was studied using kinetic approach. cadmium (Cd) and lead (Pb) at ambient temperature. they observed that the maximum Pb metal removed from the solution was found in calcite by about 74. copper (Cu). followed by montmorillonite and kaolonite by about 66% and 58% respectively. They concluded that. Prasad and Freitas (2000) investigated the potential of Quercus ilex phytomass from stem.Wahba and Zaghloul (2007) compared three different soil minerals (montmorillonite. Calcite tend to absorb Pb more than other heavy metals at both concentrations 2000ppm and 600ppm and the type of mineral has a great role on the adsorption of heavy metals: i.
53 . ilex phytomass as a biofilter of toxic trace metals and the need for enhancing the efficiency of the Q. This proves that the root biomass of Q. where concentrations can be as high as 428.e. The trend of adsorption of the phytomass was similar for Ni and Cd. Cr exhibited the least adsorption values for all the three types of phytomass compared to other metals. when 1-year-old seedlings were treated with Ni (2000 mg/l) in pot culture experiments. stem Ni>Pb>Cu>Cd>Cr. i. Desorption with 10 mM Na4 EDTA was effective (55–90%) and.Ni>Cd>Pb>Cu>Cr. It was shown that Ni is sequestered mostly in the roots.. The biosorption results of recycled phytomass suggested that the selected adsorbents are re-usable..63 ng/g dry wt. and leaf Ni>Cd>Cu>Pb>Cr. compared to 7.4 ng/g dry wt. ilex phytomass as an adsorbent of metals were evident. root>leaf>stem. there exists the possibility of recycling the phytomass. ilex has the capacity for complexing Ni. The advantages and potential of the Q. control (garden and greenhouse soil) topsoil where Ni was present in trace amounts. The highest amount adsorbed was Ni (root>leaf>stem). hence.
05 M HCl depending on the starting solution used. (carboxylic group). Na2CO3 (carboxylic and lactonic groups) and NaOH (carboxylic.05 M NaOH and 0.05 M HCl contained in 250 mL capacity glass bottles with tight glass corks.025 M Na2CO3. 0.05 M NaHCO3. The sample collected thereafter is therefore referred to as Defatted Carica Papaya Seeds (DPS). After 24 hr. 0.05 M NaOH or 0.2 Surface Chemistry of DPS adsorbents Surface chemistry of the DPS adsorbent was characterized by adopting the Boehm titration and pH drift (or pHpzc – pH of point of zero charge) methods.5 g of a well grinded DPS were dispersed in duplicate in 50 mL each of 0.The number of surface basic sites was calculated from the amount of HCl that reacted with the filtrate. The defatted sample of Carica papaya was collected and dried in a fume hood to allow residual hexane to go off the sample. Nigeria and left under the sun to dry.1.CHAPTER 2 2. the samples were filtered using whatman No. The bottles were shaken using an end-to–end shaker (Grant instrument ltd. Preparation of DPS adsorbent The seeds of Carica papaya were collected from the open markets in Benin City. The crushed seeds were then defatted using the soxhlet extraction method with hexane as the solvent. lactonic and phenolic groups). After seven days. 2.1 filter paper and titrated with 0.0. The amount of acidic groups on the surface of the DPS adsorbent were approximately probed as follows: NaHCO3. 54 . Boehm titration method is described as follows: 0. England) at 180 rpm for 24 hr. the seeds were collected and crushed. Materials and Methods 2.
3 Infrared Spectroscopy The technique of Devarly et al. The specific surface area of DPS adsorbent was calculated from the following equation (Gregg and Singh.01 M KCl were prepared and added into a series of glass bottles with corks.. 2.01 M HCl or 0. 2006). This method has been proven to be as efficient as the BET and Ethylene Glycol Monoethyl Ether (EGME) methods of determining SSA (Yukselen and Kaya.01 M NaOH. and M is the molecular weight of metal ion in g mol-1. After constant value of pHinitial had been reached. The pH of initial solutions were measured with a pH meter and noted as pHinitial. This set up was shaken for 48 hr. aMB is the is Avogadro’s number. 6. 0. Their pH values were adjusted in range between 2 and 12 at interval of 0. After 48 hr. 2008). S MB = g × a MB × M × 10 −20 (1) where SMB is the specific surface area in 10-3 km2 kg-1.5 using either 0. 1982). A plot of pHinitial on the x-axis against the difference between pHinitial and pHfinal on the y-axis was made as shown in Fig.The method used for pHpzc of DPS adsorbent was a modification of (Devarly et al. The vibrational frequency of Carica papaya seeds was obtained from FTIR transmission 55 . (2008) was used with slight modification.1 pHPZC was a point where the curve cut the x -axis implying the point when pHinitial = pHfinal. The method is described as follows: 50 mL of 0. the second pH of the extracts noted as pHfinal was measured with a pH meter. g is the number of molecules g of metal ion adsorbed at the monolayer of fibers in kg kg-1 (or occupied surface area of one molecule of metal ion in Å². = m*M).15 g of the ground DPS sample was added to each bottle and then corked.02 x 1023 mol-1.
∆S and ∆G for the adsorption process were obtained from the relation lnb = ∆S/R − ∆H/RT with all the letters having their usual meanings. 2. 2. A 10% dilution of Carica papaya seed with KBr was grinded with agate mortar to have a homogenized mixture.5 g of DPS adsorbent were agitated for 2 hours at 180 rpm at 298 K. SHIMADZU 8400S FTIR instrument in the vibrational absorption range of 4000 – 500 cm-1 was employed. A pellet suitable for IR measurement was produced using the SHIMADZU MHP-1 mini hand press. other lower concentrations were prepared from the stock solutions.4.1.4H2O respectively. The thermodynamic parameters.4 Adsorption Studies Stock solutions of 1000 mg/L of Pb2+ and Cd2+ were prepared from analar grades of Pb (NO3)2 and Cd (NO3)2. ∆H. 56 . The grinded KBr powder was pressed with SHIMADZU MHP-1 mini hand press to form homogenized pellet for background measurement. Thereafter. The effect of temperature on the adsorption of Pb2+ and Cd2+ onto DPS adsorbent was studied by repeating the procedure for initial concentration at 313 K and 323 K.spectra of defatted and undefatted seeds by KBr method. Initial Concentration In studying the effect of initial metal ion concentration. The sample measurement was taken in the percent transmittance mode. 50 mL of both metal ion in the range of 10 – 500 mg/L and 0.
5 g each of DPS biosorbent in 50 mL of 250 mg/L of both metal ions contained in a series of glass bottles and adjusting the pH of the adsorbate solution with either 0.5 g of each particle size in 50 mL of 250 mg/ L of both Pb2+ and Cd2+. 300. All filtrates were analyzed using Atomic Absorption Spectrophotometry (AAS).4.3.1 g to 3. The effect of pH on adsorption capacity of DPS biosorbent was studied by dispersing 0.2. Fifty milliliters of 250 mg/L each of Pb2+ and Cd2+ containing 0. These mixtures were agitated for 2 hours at 180 rpm at room temperature (298 K). These were agitated for 2 hr at 180 rpm at 298 K. Particle size The effect of particle size on adsorption was studied with four different particle sizes (75. Samples were collected in duplicate and the averages of the results were used for analysis.0 g into glass bottles containing 50 mL of 250 mg/L each of Pb2+ and Cd2+.4.5 g of DPS adsorbent were agitated at 180 rpm at 298 K and samples were taken out of the shaker at different time intervals between 30 seconds and 120 minutes to study the effect of contact time.2. Kinetic data were further used to investigate the slow step occurring in the present adsorption system using Bangham’s equation (Faust and Aly.01 M NaOH or 0. Adsorbent Dose The effect of adsorbent dose was carried out by taking known weights of the DPS biosorbent ranging from 0. 57 .These were agitated for 2 hours at 180 rpm at room temperature (298K).01 M HNO3 in the range of 3 to 8. 2. 1987). The Langmuir and Freundlich isotherm models were used to study the adsorption isotherms of DPS adsorbent. 500 and 750 µm) of DPS biosorbent by dispersing 0.
The Langmuir and Freundlich isotherm models were used to study the adsorption isotherms of DPS adsorbent. This is done by weighing 0. 2. Kinetic data were further used to investigate the slow step occurring in the present adsorption system using Bangham’s equation. the solutions were then filtered and the filtrates were taken for analysis.2. 2. Effect of Temperature The influence of temperature on the removal process was studied at three different temperature values (40 and 50 °C). 7.5g of the sorbent into series of shaking bottles containing different concentrations of Pb2+ (10.5. the solutions were then filtered and the filtrates were then analysed.4. 200. 50. After 1hr.5g of the DPS in 50mL of Lead and cadmium solutions (250ppm each).4. This process was also carried out on Cd2+ at the same reaction conditions. After an hour. The pH was adjusted to 3. using AAS. Effect of pH The pH effect was studied on suspensions of 0. 5. and 250ppm) which are then placed inside the Grant Shaker Instrument and shaken for 1hr. 100. 4.5 Kinetic study Fifty millimeters (50 mL) of 250 mg/L each of Pb and Cd containing 0. respectively. 6.5 g of DPS adsorbent were agitated at 180 rpm at 298 K and samples were taken out of the shaker at different time intervals between 30 seconds and 120 minutes to study the effect of contact time. The filtrates were analyzed using AAS.4. The resulting mixtures were stirred for 1hr in the Grant Shaker instrument. and 8 Lead and cadmium solutions. 58 .
− ln(qe − qt ) + ln qe = kt The Pseudo Second Order Kinetic Model (PSOM) which is obtained as follows: (6) dqt 2 = k 2 (qe − qt ) dt (7) On rearrangement and integration 1 1 − = k 2t qe − qt qe 59 (8) . m is the weight (g) of DPS adsorbent used for the adsorption reaction. and t is time (min). Other kinetic models used for the analysis of kinetic data include: The Pseudo First Order Model (PFOM) which is obtained as follows dqt = k2 (qe − qt ) dt On rearrangement (4) dqt = kdt qe − qt (5) which on integration under the boundary conditions of t = 0 to t. and qt = 0 to qt.303V + α log(t ) t o (3) where V is the volume of solution (L) and α (<1) and k0 (g) are constants.Kinetic data were further used to investigate the slow step occurring in the present adsorption system using Bangham’s equation. Co ko m log log C − q m = log 2. gives a linear logarithmic expression.
Adsorption Isotherms The Langmuir isotherm is a valid monolayer sorption on a surface containing a finite number of binding sites. Qo is the 60 .6. can be obtained by the following equation: h = k 2 q e2 Where h is the initial sorption rate (mg/g min). The initial sorption rate h.When this is linearized. it gives t 1 t = + 2 qt k 2qe qe (9) where qe is the amount of Pb2+ and Cd2+ adsorbed at equilibrium (mg/g). qt is the amount of Pb2+ and Cd2+ adsorbed at time t (min) in mg/g and k2 is the rate constant of the PSOM for sorption of both metal ions. It assumes uniform energies of sorption on the surface and no transmigration of adsorbate in the plane of the surface. The Langmuir equation may be written as Q o bCe qe = 1 + bCe (Non-linear form) 1 1 1 = o + o q e Q bCe Q (Linear form) (10) (11) Where qe is the amount of solute adsorbed per unit weight of adsorbent (mg/g). (10) qt = k 2 q e2 t 1 + k 2qe t (11) 2. Ce is the equilibrium concentration of solute in the bulk solution (mg/L).
.m ) 2 qe. χ2 will be small in number.m (14) Where qe. χ2 will be a bigger number. The equivalent mathematical statement for the nonlinear chi square as given by (Kang et al. 2008) is: χ =Σ 2 (qe − qe. The other equilibrium isotherm models were used for adsorption data fittings Freundlich isotherm model qe = KF Ce1/ n logqe = logK f +1/ n logCe (12) (13) The non-linear chi-square error method of analysis was used to fit experimental qt data against theoritcal qt data. 61 . If data from model are similar to the experimental data.m is equilibrium capacity obtained by calculating from the model (mg/g) and qe is experimental data of the equilibrium capacity (mg/g). It is the value reciprocal of the concentration at which half the saturation of the adsorbent is attained. while if they differ.monolayer adsorption capacity (mg/g) and b is the constant related to the energy of adsorption (L g-1).
.098 ± 0.25 Table 1 highlights the quantitative surface chemistry analyses of DPS biosorbent consisting of the amount of acidic and basic functional groups..864 ± 0.117 ± 0.587 6. (2004) and Kang et al.CHAPTER 3 3. The presence of surface functional groups like carboxylic. lactonic and phenolic groups are known to constitute the acidity of the material while oxygen containing groups and oxygen free Lewis basic sites constitute the basicity. (2008) who observed the same trend on activated carbon fiber samples and activated carbon from jackfruit peel waste respectively.These atoms to a very great extent determine the surface chemistry of the seeds. The acidic pHPZC of 6. sulphur.. The pH at which the H+ and OH.25 shown by the DPS adsorbent is consistent with the Boehm titration result that presented dominance of acidic group of the surface of the seeds. Surface chemistry study is basically done to probe the acidity and basicity of the material under study.1 Surface Chemistry The surface of DPS adsorbent contains heteroatom like hydrogen.013 0. 62 .009 1. was also determined (Fig.0 Result and Discussions 3. known as the pH at point of zero charge (pHPZC). 2008). oxygen.were equal. Values of surface acidity and pHPZC of DPS biosorbent using Boehm’s titration Sample Carboxylic Lactonic Phenolic Acidic value Basic value pHPZC Meq/g of DPS adsorbent DPS adsorbent 0.022 2. This is in accordance with Mahir et al. 1). Table 1.078 0. halogen and phosphorus (Devarly et al. nitrogen.
1: pHpzc plot for biosorption of Pb 2+ and Cd 2+ onto DPS adsorbent The specific surface area of DPS adsorbent was found to be 143. Also a shoulder band from 1103 to 1091 cm-1 63 .1 m2 g-1) (Srinivasa et al. powder orange peel (128..91 m2 g-1) (Horsfall Jnr et al. 2007). This specific surface area is large when compared with lignocellulosic substrate (185 m2 g-1) (Boudesocque et al. 2008). 2007). 3.. 2009) and other biosorbents used for adsorption recently. pure wild cocoyam biomass (32.52 m2 g-1) (Sreelatha et al. S=O band from 1057 to 1049 cm-1 with a hypsochromic shift.7 m2 g-1) (Lu et al.5 4 3 2 C a g inp hn e H 1 0 0 -1 -2 -3 -4 2 4 6 8 10 12 Initial pH Fig.27 m2 g-1. Observed hypsochromic shifts include a shift in -OH band from 3371 to 3294 cm-1. prawn pond algae treated with acid (2. 2 it was observed that there were several small hypsochromic shifts in peaks when Pb metal ion was adsorbed onto DPS biosorbent..1 Infrared Spectroscopy In Fig.. palm shell powder (2. 2008)..
and 1.25. 2.was observed. The basic groups had 0. β-keto (enolic) esters. Ansari et al.117.β-unsaturated ketone. There was also an observed small shift in this region to 1647 cm-1.864 meq/g.587 meq/g and the pHPZC of DPS biosorbent was found to be 6. a sharp and distinct absorption was observed at 1651 cm-1 (C=O stretching). quinones and carboxylic acids. This is a clear indication of the presence of α..098. 64 . 0. (2009) have also observed similar hypsochromic shifts when they adsorbed Cd2+ on Polypogon monspeliensis waste biomass. lactonic and phenolic groups in DPS biosorbent are 0. From Boehm titration the amount of Carboxylic. FTIR plots of DPS biosorbent and metal loaded DPS biosorbent. Lactones. Fig. In the defatted spectrum.
This could mean that ion-exchange mechanism is not strictly the mechanism by which the metal ions are being adsorbed onto the surface of DPS biosorbent.2 Effect of pH In Fig. 3: Adsorption plot of Pb2+ and Cd2+ onto DPS biosorbent due to pH effect. 65 . 3 it was observed that there was no significant change in percentage of metal ion adsorbed especially for Pb2+ with change in pH (Pb2+ from 96 . However.98%).99% and Cd2+ from 85 .3. 105 100 % e a io a s r e m t l n d ob d 95 90 % Pb % Cd 85 80 75 3 4 5 pH 6 7 8 Fig. This might suggests that adsorption of the metal ions onto DPS biosorbent is not largely influenced by pH. percentage of Pb2+ adsorbed onto DPS biosorbent was more than for Cd2+. It is possible that the lone pair of electrons (Lewis base) on some of the functional groups in DPS biosorbent may have played a major role in the removal of the metal ions by (Lewis acid) DPS biosorbent.
qe. Increasing biosorbent dosage decreased the amount of both metal ion adsorbed with Pb2+ being more adsorbed than Cd2+ (Fig 4). 66 . (1995) and Ho and Ofomaja (2005). It is possible that the change in the solid/liquid ratio from 0. However. the percentage of metal ion adsorbed was observed to follow the reverse trend. 4: Effect of DPS biosorbent dose on adsorption of Pb2+ and Cd2+. has an inverse proportionality function to weight of biosorbent but a direct proportionality function to percentage adsorbed.5 1 1. Similar trend have been observed by Ho et al.3 Effect of biosorbent dose Fig. 0.5 2 3 adsorbent weight 84 82 80 Fig.1 0.003 to 0.3. 4 shows the amount of Pb2+ and Cd2+ adsorbed with varying DPS biosorbent weights in 250 mg/L of the single metal ion in aqueous solution.5 g of DPS biosorbent was chosen for use in this work not because it gave the highest adsorption capacity but because it showed sufficiently high percentage of metal ions adsorbed which were not significantly different from those obtained at higher dosage of DPS biosorbent. 20 18 16 am n adsorbed (m ou t g/g) 14 qe Pb qe C d % ad Pb % ad C d 98 96 94 92 %m etal ion adsorbed 12 90 10 88 8 86 6 4 2 0 0.1 may have directly resulted in this trend since amount adsorbed..
the higher the adsorption rate (Uzun and Guzel.6434 and Cd2+ r2=0.096 g mg-1 min-1) for same reason adduced before even though the adsorption capacity of DPS is more for Pb2+ than for Cd2+ (22.8997) (Faust.55 mg/g for Cd2+).4 Effect of Contact time Fig. The higher initial sorption rate of Cd2+ is likely because of the smaller ionic radii of Cd2+ which enables it to compete favourably with Pb2+ for same adsorption site on DPS biosorbent.028 g mg-1 min-1) than for Pb2+ (0.97Å) and Pb2+ (1. 2000). The overall Pseudo second order kinetic rate was low but was faster for Cd2+ (0. 5 suggests that increasing contact time increased the amount of metal ions adsorbed on DPS biosorbent.20 Å). From Bangham’s equation we observed that the adsorption is not strictly by pore diffusion but also film diffusion because of the reduced linearity of the plots (Pb2+r2=0.4 mg g-1 min-1 for Cd2+).17 mg/g for Pb2+ and 21. Both metal ions showed very high initial sorption rates (13. The ionic radii (Pauling) of the metal ions are Cd2+ (0. 67 .8 mg g-1 min-1 for Pb2+ and 44. The adsorption failed the pseudo-first order kinetic model implying that adsorption of Pb2+ and Cd2+ onto DPS biosorbent is not only time dependent but also concentration dependent.3. It has been noted that the smaller the ionic diameters. 1987).
into the Pseudo-second order kinetic model (PSO). (2009). The half-life (t0..998 to 48.61 min and 0.25 20 q ( gg t m/ ) 15 exp Pb2+ PSO M Pb2+ exp C d2+ PSO M C d2+ 10 5 0 0 20 40 60 80 100 120 140 time (mins) Fig.46 mg g-1 for Pb2+ and from 0. Wu et al. 2009). Calculations using the modified PSO kinetic model for data obtained in this study suggest that Rw for the adsorption of Pb2+ and Cd2+ is 0.48 min for Pb2+ and Cd2+ respectively (Wu et al. 3. This implies that the adsorption of Cd2+ approaches equilibrium faster than Pb2+.992 to 46. Pseudo-second order kinetic model plots for the adsorption of Pb2+ and Cd2+ onto DPS biosorbent. 5. Recently. Rw. introduced the “approaching equilibrium factor”. This further supports the rate constants and initial sorption rates obtained for the adsorption of both metal ions onto DPS biosorbent in this study. This observed trend is because there is 68 .5 Effect of initial metal ion concentration Increasing initial metal ion from 50 – 500 mg L-1 increased amount of both metal ion adsorbed onto DPS biosorbent from 0.004 respectively.5) for the adsorption process was found to be 1..44 mg g-1 for Cd2+.013 and 0.
6 and 7). This shows the strong future potential of this biosorbent in removing metal ions from waste water. Pavan et al. With increasing particle size (75 < 300 < 500 < 750 µm) of DPS biosorbent. adsorption capacity for both metal ions was observed to be slightly higher (≈14. The adsorption capacity of DPS biosorbent for Pb2+ was observed to be 1666.increasing concentration gradient between the biosorbent and the adsorbate. because of the shorter mass transfer zone.3 mg/g for Cd2+. the greater the rate of diffusion and adsorption. 2009).00 mg/g for Cd2+. This is consistent with literature that the smaller the particles size of an adsorbents. Fitting experimental data to Langmuir and Freudlich equilibrium models nonlinear regression. With the portion of DPS biosorbent not sieved.67 mg/g and for Cd2+ it was 1000.1 mg/g for Pb2+.. 2003). Tarley and Arruda. macrofungus biomass (38. Ponkan peel (112. and Zeolite (175 mg/g for Pb2+ and 137 mg/g for Cd2+. 2008. 69 . Babel and Kurniawan.. Adsorption capacities obtained in this study are higher than those obtained from biosorbents in recent times. causing a faster rate of adsorption (Singh et al.00 mg/g (Table 1). 2008 ). adsorption capacity decreased. Almond Shell (9. it was observed that the Freudlich gave better fit than Langmuir (Figs. Mohammad et al. 2004). This implies that the adsorption of Pb2+ and Cd2+ onto DPS biosorbent is on heterogeneous adsorption sites on the surface of DPS biosorbent which further strengthens the fact that DPS biosorbents has multi-adsorption sites as shown from the FTIR analysis.. Ahmet and Mustafa. intra-particle diffusion is reduced as the particle size reduces. 2009).4 mg/g for Pb2+ and 27.00 for Pb2+ and 7.3%). However.
600 500 exp P b2+ F M Pb2+ LM Pb2+ 400 q ( gg e m/ ) 300 200 100 0 0 5 10 Ce (mg/L) 15 20 Fig. 6: Langmuir (LM) and Freudlich (FM) isotherm model plots for the adsorption of Pb2+ onto DPS biosorbent 350 300 exp C d2+ F M C d2+ LM C d2+ 250 q ( gg e m/ ) 200 150 100 50 0 0 5 10 15 20 Ce (mg/L) 25 30 35 40 Fig. 7: Langmuir (LM) and Freudlich (FM) isotherm model plots for the adsorption of Cd2+ onto DPS biosorbent 70 .
spontaneous and exothermic in nature.55 313 K 35.63 0.09 4. ∆ G was found to increase slightly with increasing temperature.61 4.9286 0.56 61. The table suggests that the adsorption of Pb2+ and Cd2+ onto DPS biosorbent is highly feasible.3.35 4. Table 2: Thermodynamic parameters for the adsorption of Pb2+ and Cd2+ onto DPS biosorbent -∆ H (kJ mol-1) -∆ S (J mol-1) r2 -∆ G (kJ K-1 mol-1) 298 K Pb2+ Cd2+ 12.57 323 K 36.32 19.6 Thermodynamics of Adsorption Table 2 shows data for the various thermodynamic parameters in the adsorption of Pb2+ and Cd2+ onto DPS biosorbent.30 73.58 71 .9956 34.
in the adsorption of Pb2+ and Cd2+ gave an adsorption capacity of 1666.00 mg/g respectively. Its very high adsorption capacity suggests the strong potential of this adsorbent in the removal of metal ions from aqueous solution. spontaneous and exothermic in nature. The adsorption of both metal ions was found to be highly feasible.CHAPTER 4 Conclusion The use of a new adsorbent.67 mg/g and 1000. of contact time. 72 . defatted Carica papaya seeds. The adsorption of both metal ions was found to approach equilibrium in ≈20 min.
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respectively.4H2O 1g Cd → Xg Cd(NO3)2.41g Therefore. 2. 207g Pb → 331g Pb(NO3)2 1g Pb → Xg Pb(NO3)2 Then. Xg Cd(NO3)2.48g Atomic M. of Cd = 112. of Pb = 207g Therefore.41 Therefore.5990g Pb(NO3)2 in 1L standard flask is equivalent to 1000ppm Pb2+ For 1000ppm (1000mg/L) Stock Solution of Cd2+ MM of Cd(NO3)2.7442g Cd(NO3)2. The stock solutions of each metal ions were prepared as shown below: For 1000ppm(1000mg/L) Stock Solution of Pb2+ MM of Pb(NO3)2 = 331g Atomic M.4H2O in 1L standard flask is equivalent to 1000ppm Cd2+ 78 .Appendix Preparation of Stock solution of metal ions The chemicals used for the preparation of Pb2+ and Cd2+ were Pb(NO3)2 and Cd(NO3)2.48g Cd(NO3)2.4H2O Then. 1.4H2O.41g Cd → 308.4H2O 112.7442g Cd(NO3)2. 112.4H2O = 308.48 × 1 = 2. Xg Pb(NO3)2 = 331 × 1 = 1.4H2O = 308.5990g Pb(NO3)2 207 Therefore.
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