PREPARATION OF FISH SCALES AS BIOSORBENT FOR THE REMOVAL OF HEAVY METALS IN WATER SOURCE FROM R.S.MANGALAM AREA (Ramanathapuram Dt)
Dissertation submitted inGovernment Arts college, Paramakudi Affiliated to Alagappa University, Karaikudi in partial fulfilment of the requirement
MASTER OF SCIENCE IN BIOCHEMISTRY
Submitted by: G.SARAVANAN Reg.No:1416316023
Under the guidance and supervision of Dr. K.R.T.ASHA M.Sc., M.Phil., Ph.D.,
DEPARTMENT OF BIO CHEMISTRY GOVERNMENT ARTS COLLEGE PARAMAKUDI - 623701.
APRIL-2018
Dr. K.R.T.ASHA M.Sc., M.Phil., Ph.D., Head of the Department, Department of Bio-Chemistry, Government Arts College, Paramakudi – 623701 Email: [email protected]
CERTIFICATE
This is to certify that this dissertation entitled “PREPARATION OF FISH SCALES AS BIOSORBENT FOR THE REMOVAL OF HEAVY METALS IN WATER SOURCE FROM R.S.MANGALAM AREA (Ramanathapuram Dt)’’ Submitted by G.SARAVANAN (Reg.no:1416316023)in partial fulfilment of the MASTER OF SCIENCE IN BIOCHEMISTRY carried out by his under my guidance and supervision in the Department of Biochemistry, Government Arts College, Paramakudi. During the period of his study in the academic year 2016-2018. It is further certified that this dissertation or any part there of has not been submitted elsewhere for the award of any degree.
Dr. K.R.T ASHA Dr. K.R.T.ASHA
Head of the department Project Guide
Principal
Dr. K.R.T.ASHA M.Sc., M.Phil., Ph.D., Head of the Department, Department of Bio-Chemistry, Government Arts College, Paramakudi – 623701 Email: [email protected]
CERTIFICATE
This is to certify that this dissertation entitled “PREPARATION OF FISH SCALES AS BIOSORBENT FOR THE REMOVAL OF HEAVY METALS IN WATER SOURCE FROM R.S.MANGALAM AREA (RamanathapuramDt)’’ Submitted by G.SARAVANAN (Reg.no:1416316023) in partial fulfilment of the MASTER OF SCIENCE IN BIOCHEMISTRY carried out by his under my guidance and supervision in the Department of Biochemistry, Government Arts College, Paramakudi. During the period of his study in the academic year 2016-2018. It is further certified that this dissertation or any part there of has not been submitted elsewhere for the award of any degree.
Signature of the Candidate Signature of the Guide
Signature of Head of Department Signature of the External
Examiner
Principal DECLARATION
I hereby state that to the best of my knowledge and belief the dissertation entitled “PREPARATION OF FISH SCALES AS BIOSORBENT FOR THE REMOVAL OF HEAVY METALS IN WATER SOURCE FROM R.S.MANGALAM AREA (Ramanathapuram Dt)” is the result of a study originally carried out by me under the guidance of theDr. K.R.T.ASHA M.Sc., M.Phil., Ph.D., Department of Biochemistry, Government Arts College, Paramakudi, Affiliated to Alagappa University , Karaikudi in partial fulfilment of the degree of Master of Science in Biochemistry.
I further declare that this project or any part therefore has not been submitted in this University or elsewhere for any other degree or diploma.
Place: Paramakudi (SARAVANAN.G)
Date: Signature of the student
.
ACKNOWLEDGEMENT
With great fear & awe being filled and flown in my heart, soul, body, mind and spirit. I thank god – the creator of every being of the world for having showered his blessing and abundant grace upon me to complete the project successfully.
“A Leader is the one who knows goes and shows of the way”
Director of all efforts with proper counselling makes one to be successful. My sincere thanks to my guide Dr. K.R.T.ASHA M.Sc., M.Phil., Ph.D., Head of the department, Department of Biochemistry, Government Arts College, Paramakudi, who is tireless in directing effort to set the objective in a novel away.
I express my sincere thanks to Dr. M. MANIMARAN M.A., M.A., M.Phil., Ph.D., Principal, students affairs, Government arts collage Paramakudi, for giving me this opportunity and encouragement.
“A good teacher is a good learner”
In sincerely thanks to Mrs. V. Velvizhi M.Sc., B.Ed., M.Phil., Mr. M. Muneeswaran M.Sc., M.Phil., Mrs. K.Kavitha M.Sc., B.Ed., M.Phil., M.PorkodiM.sc., M.Phil., Ms.K.Santha M.Sc., B.Ed. Mr. T. ShanmugaSundaramM.Sc, Mr. M. NatarajaPrabhu M.Sc. Ms. S. Nivetha M.Sc. Mrs. S. Umadevi, M.Sc. lectures, and staffs, Department of Biochemistry, Government arts college, Paramakudi, for their support and encouragement.
I have great pleasure in expressing my sincere and heart full thanks to Dr. K.R.T.ASHA M.Sc., M.Phil., Ph.D., Head of the Department, Department of biochemistry, for this kind help and supports during my experimental study.
“Parents are these blessing from god”
Who has sacrificed their lives in all aspects to their maximum-sincere thanks to them.. I would like to record my sincere thanks to My Parents and Brothers, for their moral timely help and encouragement.
“More over as friends stand behind the success of the man”
I heart full thank my friend K.Ajeethkumar M.Sc. S. UmadeviM.sc.S.DhivyaBharathi, V.Manikandan, J. FathimaNancy Sahana, K. Lavanya and my classmates for having given me encouragement and rendered their service in completing the project Last but not the least I thank every one who encouraged and helped me to make this project a real success.
SPECIAL ACKNOWLEDGEMENT
We heart fully thank, Thiru.T.Anbalagan, I.A.S.,Member-Secretary, Tamilnadu State council For Higher Education, Chennai.For selecting our project entitled “PREPARATION OF FISH SCALES AS BIOSORBENT FOR THE REMOVAL OF HEAVY METALS IN WATER SOURCE FROM R.S.MANGALAM AREA (Ramanathapuram Dt)‟‟ under „„Student Mini Project‟‟ Scheme and for granting us the fund.
Dr. K.R.T. Asha SARAVANAN.G
Project Guide Candidate
PRINCIPAL
CONTENTS
S.NO PARTICULARS PAGE.NO
1 ABSTRACT 1
2 INTRODUCTION 2
3 REVIEW OF LITRATURE 15
4 AIM AND OBJECTIVES 19
5 METERIALS AND METHODS 20
6 RESULT AND DISCUSSION 30
54 7 CONCLUSION
REFERANCE 55 8
ACRONYMS AND ABBREVIATIONS
EPA - Environmental Protection Agency
CDA - Copper Development Association
DWE - Drinking Water Inspectorate
AAS - Atomic Absorption Spectroscopy
SEM - Scanning Electron Microscope
EDAX - Energy Dispernsive X-ray Analysis
FTIR - Fourier -Transform Infrared Spectroscopy
WHO - World Health Organization
Cu - Copper
Pb - lead
Zn - Zinc
Hg - Mercury
Ml - Millilitre
Mg - Milligram
Gm - Gram
PPM - Parts Per Million
PPB - Parts Per Billion
L - litre ABSTRACT
Biosorption is one of the biological treatments that hasemerged as a new technology for the removal and recovery of metal ions from aqueous solutionswhich is more environmental friendly. In this study biosorption using lenthrinus lentjan fish scales wereused with theintention to removeheavy metals such as copper, zinc, plumbum, and mercury ions from synthetic water.In the preliminary water analysis, the results indicated that several factors including Total Dissolved solids, (11,039mg/l) Electrical conductivity 15,770,
Hardness (as CaCo3) (5200), Concentration of chlorite (10000mg/l)calcium (1300), shows higher value. After the treatment with biosorbent (fish scale powder) the value was found to be very less, the concentration of Total dissolved solids (9184mg/dl) Electrical conductivity
(13120), Hardness (as CaCo3) (4000) Concentration of chlorite (9200) and calcium (1000) . The optimumadsorption capacities of fish scale was investigated under several condition namely, pH, biosorbentdosage, initial heavy metals concentration, and contact time while final concentration was obtainedby using the maximum percentage removals were observed at pH 5 and dosage 0.6g at biosorbent concentration,at 160 rpm agitation speed with maximum removal achieved at 3 hours.FTIR analysis shows the presenceN-H aliphatic primary amine, C-H Alkane, S-H Thiol, C=C Alkene, N-O Nitro compound, CH- alkane Methyl group, C-O Primary alcohol, C=C Alkene Vinylidenefunctional group in the fish scale surface (biosorbent). SEM,EDAX and AAS analysis shows thatpresence of the heavy metal absorption by fish scales, and in SEM analysis the micrograph clearly shows that the presence of new shiny bulky particles over thesurface of heavy metals loaded biosorbent which are absent in the native biosorbent. Theseresults confirm the binding of metal ions in fish scales through Biosorption process.
INTRODUCTION
INTRODUCTION
One of the main problems of the society in this century is the environmental pollution. The main pollutants include toxic metal, the quantity of which permanently increases in the environment as the result of increased industrial activity. Once toxic metal ions are present in the environment they undergo cycles between its abiotic and biotic elements, posing toxicity in the latter group. Since it is impossible to degrade those pollutants by any means, the only way to remove them from environment is to exclude metal ions from cycling through concentration with a possible recovery and reuse (Volesky, 1997). This would also reduce the consumption of non-renewable resources (Chojnacka, 2010). The problem is of particular significance to human as the final consumer, since on each level of the trophic chain biomagnifications occurs. If toxic metals become bioaccumulated by an organism of human, several disadvantageous symptoms form eg. Neurological, gastrointestinal and immunological systems are observed. Among toxic heavy metals, cadmium is one of the most dangerous for human health (Mandjiny et al., 1998). The industrial uses of cadmium are increasing in plastics, paint pigments, mining, electroplating, batteries and alloy industries (Al-Asheh and Duvnjak, 1997). Cadmium is a highly toxic element and considered as a carcinogen. It can enter the human body by drinking water, eating food, breathing or smoking. Most of the cadmium that enters thebody goes to kidney and liver and can remain there for many years and can cause serious damage to kidney and bones (N. Burham, M.E. Aly., 2014)
Metal biosorption is the removal of metal ions by inactive, nonliving biomass due to highly attractive forces present between the two (Volesky and Holan, 1995). Particularly, it is due to the presence of certain functional groups, such as amine, carboxyl, hydroxyl, phosphate, sulfhydryl etc., on the cell wall of the biomass. The process involves a solid phase (biomass) and a liquid phase containing metal ions (solution of metal ions/waste-water). The removal of heavy metals from our environment especially water is now shifting from the use of conventional adsorbents to the use of biosorbents. The presence of heavy metals in the environment is of major concern because of their toxicity, bio accumulating tendency, and threat to human life and environment. In recent years, many low cost sorbents such as algae, fungi, bacteria and agricultural by-products have been investigated for their biosorption capacity towards toxicology of heavy metals and the biosorption capacity of biosorbents compared to conventional adsorbents(Mary Rhovian B. Bacani,et al 2017.)
FISH SCALE
The skin of most fishes is covered with scales, which, in many cases, are animal reflectors or produce animal coloration. Scales vary enormously in size, shape, structure, and extent, ranging from strong and rigid armour plates in fishes such as shrimpfish’s and box fishes, to microscopic or absent in fishes such as eels and anglerfishes. The morphology of a scale can be used to identify the species of fish it came from.
Cartilaginous fishes (sharks and rays) are covered with placoid scales. Most bony fishes are covered with the cycloid scales of salmon and carp, or the ctenoid scales of perch, or the ganoid scales of sturgeons and gars. Some species are covered instead by scutes, and others have no outer covering on the skin.
scales are part of the fish's integumentary system, and are produced from the mesoderm layer of the dermis, which distinguishes them from reptile scales. The same genes involved in tooth and hair development in mammals are also involved in scale development. The placoid scales of cartilaginous fishes are also called dermal denticles and are structurally homologous with vertebrate teeth. It has been suggested that the scales of bony fishes are similar in structure to teeth, but they probably originate from different tissue. Most fish are also covered in a protective layer of mucus (slime).
Types of scales
In most biological nomenclature, a scale (Greekλεπίςlepis, Latinsquama) is a small rigid plate that grows out of an animal's skin to provide protection. In lepidopteran (butterfly and moth) species, scales are plates on the surface of the insect wing, and provide coloration. Scales are quite common and have evolved multiple times through convergent evolution, with varying structure and function.
Fish scales are dermally derived, specifically in the mesoderm. This fact distinguishes them from reptile scales paleontologically. Genetically, the same genes involved in tooth and hair development in mammals are also involved in scale development.Scales are generally classified as part of an organism's integumentary system. There are various types of scales according to shape and to class of animal.
Cosmoid scales
True cosmoid scales can only be found on the Sarcopterygians. The inner layer of the scale is made of lamellar bone. On top of this lies a layer of spongy or vascular bone and then a layer of dentine-like material called cosmine. The upper surface is keratin. The coelacanth has modified cosmoid scales that lack cosmine and are thinner than true cosmoid scales.
Ganoid scales
Ganoid scales can be found on gars (family Lepisosteidae), bichirs, and reedfishes (family Polypteridae). Ganoid scales are similar to cosmoid scales, but a layer of ganoin lies over the cosmine layer and under the enamel. Ganoin scales are diamond shaped, shiny, and hard. Within the ganoin are guanine compounds, iridescent derivatives of guanine found in a DNA molecule. The iridescent property of these chemicals provide the ganoin its shine.
Placoid scales
Placoid scales are found on cartilaginous fish including sharks. These scales, also called denticles, are similar in structure to teeth, and have one median spine and two lateral spines.
Leptoid scales
Leptoid scales are found on higher-order bony fish. As they grow they add concentric layers. They are arranged so as to overlap in a head-to-tail direction, like roof tiles, allowing a smoother flow of water over the body and therefore reducing drag. They come in two forms:
Cycloid scales have a smooth outer edge, and are most common on fish with soft fin rays, such as salmon and carp. Ctenoid scales have a toothed outer edge, and are usually found on fish with spiny fin rays, such as bass and crappie.
EMPEROR FISH (LETHRINUS LENTJAN)
The Lethrinidae are a family of fishes in the order Perciformes commonly known as emperors, emperor breams, and pigface breams. These fish are found in tropical waters of the Pacific and Indian Oceans, and Lethrinus atlanticus is also found in the eastern Atlantic. They are benthic feeders, consuming invertebrates and small fishes. Some species have molariform teeth which they use to eat shelled invertebrates, such as mollusks and crabs. (Froese, et al., 2013)
Lethrinus lentjan is a species of emperor fish. It has a distinctive blood-red colouration around the margin of the gill covers. It is widespread around the Indo-West Pacific, and is reef-associated. This species is fished commercially and for sport.
Lethrinus lentjan
Scientific Classification
Kingdom Animalia
Phylum Chordata
Class Actinoperygii
Order Perciformes
Family Lethrinidae
Genus Lethrinus
Species L.lentjan Binominalname Lethrninuslentjan
Description
This is a large species, growing to approximately 50 cm in length. However specimens in the intertidal zone may be around 15 cm. The body is olive-green, becoming paler toward the belly. Bright red spot and edge of the gill cover look like an ear. Pale spots on scales and red patch on base of pectoral fins, inside mouth is bright red.
The scales are large and in a diamond pattern. There is a blood-red colouration around the margin of gill covers, and often at the base of the pectoral fins as well. The dorsal fin is white has a reddish margin. Both the caudal and dorsal fins have orange mottling. The pectoral fin may be pale orange, whitish or yellowish. It has thick, fleshy lips, and a somewhat protractiile snout. Size and possession limits
minimum size 25 cm possession limit of 5 per species in addition, a total possession limit of 20 applies for all Coral Reef Fin Fish.
Lethrinus lentjan is widely distributed. It is a sequential protogynous hermaphrodite and likely lives to at least 19 years. It is a component of commercial and artisanal fisheries throughout its range and has experienced some localized overfishing. Significant population declines on a global level are not suspected at this time; therefore, it is listed as Least Concern. Monitoring and regulation are recommended in areas of heavy fishing pressure. Lethrinus lentjan is a very important commercial species throughout its range and is caught using handlines, traps and gillnets. Lethrinus lentjan is also collected as bycatch in shrimp trawl fisheries. Lethrinus lentjan is a component of mixed-species stocks off western Australia and throughout its range. Lethrinus lentjan is marketed fresh and is a major component of long-line fisheries in Malaysia. In the southern Persian Gulf, L. lentjan is collected using traditional wooden dhows using baited dome-shaped wire traps and is very common in markets in the region.
Lethrinus lentjan inhabits coastal, sandy areas, coral reefs, and deep lagoons to depths of 50 m. Lethrinus lentjan diet consists of crustaceans, molluscs, echinoderms, polychaetes and fishes. Juveniles prefer amphipod and crustacean larvae, while adults target crustaceans, molluscs, and echinoderms recorded Lethrinus lentjan maximum age to be 11 years in the southern Persian Gulf. However, recorded a maximum age of 19 years for Lethrinus lentjan
Copper is naturally deposited in rocks as mineral form, which is mostly associated with sulfur. Examples of common minerals that contain copper are azurite, malachite, tennantite, halcopyrite and bornite. Anthropogenic sources of copper include the production of plastic material, copper and other nonferrous smelting, and steel blast furnaces (EPA, 2006). Although copper is an essential nutrient to humans, excess intake of copper would causeacute and chronic adverse health effects such as stomach and intestinal distress, liver and kidneydamage, and anemia (EPA, 2006). Not only does toxicity of copper cause physical damages tothe human body, it can also worsen the symptoms of mental diseases. High levels of copperhave been associated with people with mental illness, such as paranoia, obsessive- compulsiveschizophrenia(CDA, 2006), and Alzheimer’s disease. Examples of conventional copper removal methods are ion exchange, chemical precipitation, ultra filtration, and electrochemical deposition. These removal methods are expensive due to implementation of new infrastructures and are not environmentally friendly because they increase the volume of chemical and biological sludge due to the additional chemicals in the treatment. Compared with conventionalmethods for copper reduction, biosorption is a better alternative.
Heavy metals LEAD
Lead is a chemical element with symbol Pb (from the Latinplumbum) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and has a relatively low melting point. When freshly cut, lead is bluish-white; it tarnishes to a dull graycolor when exposed to air. Lead has the highest atomic number of any stable element and concludes three major decay chains of heavier elements
Lead used to be common in the environment due to its widespread historic use in petrol, paint and water pipes, as well as its natural occurrence in soils as a consequence of local geological conditions. From the 1970s onwards these uses of lead have been prohibited across Europe and the human health risks have studied extensively and are generally well understood. The health risks relate to the way lead can build up in the body. Those at particular risk are infants and children because lead can have an adverse impact on mental development. Lead may also be factor in behavioural problems. Worldwide it is recommended that human exposure to lead is kept to a minimum and lead is therefore controlled in air, soil, food and water. A full report on the internationally agreed health based knowledge about lead can be found on the World Health Organisation website. IA less common cause of lead in drinking water is the illegal use of lead based solder to join together sections of copper pipe. Lead solder is still sold for use on closed central heating systems and mistakes occasionally happen whereby unqualified plumbers or householders use lead solder on drinking water pipes contrary to the law. For all these reasons, the amount of lead in drinking water at a particular property may sometimes be above the health based standard. (DWI, 1970) As a result of human activities, such as fossil fuel burning, mining, and manufacturing, lead and lead compounds can be found in all parts of our environment. This includes air, soil, and water. Lead is used in many different ways. It is used to produce batteries, ammunition, metal products like solder and pipes, and X-ray shielding devices. Lead is a highly toxic metal and, as a result of related health concerns (see below), its use in several products like gasoline, paints, and pipe solder, has been drastically reduced in recent years. Today, the most commonsources of lead exposure in the United States are lead-based paint and possibly water pipes in older homes, contaminated soil, household dust, drinking water, lead crystal, lead in certain cosmetics andtoys, and lead-glazed pottery.
Lead can cause severe damage to the brain and kidneys and, ultimately, death. By mimicking calcium, lead can cross the blood-brain barrier. It degrades the myelin sheaths of neurons, reduces their numbers, interferes with neurotransmission routes, and decreases neuronal growth. Symptoms of lead poisoning include nephropathy, colic-like abdominal pains, and possibly weakness in the fingers, wrists, or ankles. Small blood pressure increases, particularly in middle-aged and older people, may be apparent and can cause anemia. Several studies, mostly cross-sectional, found an association between increased lead exposure and decreased heart rate variability. In pregnant women, high levels of exposure to lead may cause miscarriage. Chronic, high-level exposure has been shown to reduce fertility in males. (Sokol, R. C. 2005).
The rise and fall in exposure to airborne lead from the combustion of tetraethyl lead in gasoline during the 20th century has been linked with historical increases and decreases in crime levels, a hypothesis which is not universally accepted. (Casciani, D.,. 2014)
REGULATORY LIMITS
● EPA – 15 parts per billion (ppb) in drinking water, 0.15 micrograms per cubic meter in air. (CHSR,2009)
Environmental effects
The extraction, production, use, and disposal of lead and its products have caused significant contamination of the Earth's soils and waters. Atmospheric emissions of lead were at their peak during the Industrial Revolution, and the leaded gasoline period in the second half of the twentieth century. Elevated concentrations of lead persist in soils and sediments in post-industrial and urban areas; industrial emissions, including those arising from coalburning,continue in many parts of the world, particularly in the developing countries.(UNEP,2010)
Lead can accumulate in soils, especially those with a high organic content, where it remains for hundreds to thousands of years. It can take the place of other metals in plants and can accumulate on their surfaces, thereby retarding photosynthesis, and preventing their growth or killing them. Contamination of soils and plants then affects microorganisms and animals. Affected animals have a reduced ability to synthesize red blood cells, which causes anemia. (IEA, Clean Coal Centre, 2012)
ZINC
Zinc is a chemical element with symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. In some respects zinc is chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and the Zn2+ and Mg2+ions are of similar size. Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined by froth flotation of the ore, roasting, and final extraction using electricity (electrowinning).
Zinc is an essential mineral, including to prenatal and postnatal development. Zinc deficiency affects about two billion people in the developing world and is associated with many diseases. In children, deficiency causes growth retardation, delayed sexual maturation, infection susceptibility, and diarrhea. Enzymes with a zinc atom in the reactive center are widespread in biochemistry, such as alcohol dehydrogenase in humans. Consumption of excess zinc can cause ataxia, lethargy and copper deficiency. (Maret, Wolgang., 2013)
Risks of zinc excess Toxic effects in humans are most obvious from accidental or occupational inhalation exposure to high concentrations of zinc compounds, such as from smoke bombs, or metal- fume fever. Modern occupational health and safety measures can significantly reduce potential exposure. Intentional or accidental ingestion of large amounts of zinc leads to gastrointestinal effects, such as abdominal pain, vomiting and diarrhoea. In the case of long- term intakes oflarge amounts of zinc at pharmacological doses (150–2000 mg/day), the effects (sideroblastic anaemia, leukopenia and hypochromic microcytic anaemia) are reversible upon discontinuation of zinc therapy and/or repletion of copper status, and are largely attributed to zinc-induced copper deficiency. High levels of zinc may disrupt the homeostasis of other essential elements. For example, in adults, subtle effects of zinc on copper utilization may occur at doses of zinc near the recommended level of intake of 15 mg/day and up to about 50 mg/day.
Environmental effects General consensus exists that the larger the margin of safety the lower is the environmental risk. Margins of safety of < 1.0 are usually indicative of a higher potential for risk and may require further evaluation. The bioavailability and toxicity to freshwater organisms are typically highest at high pH (unicellular algae), low alkalinity, low dissolved oxygen and elevated temperatures. Soluble zinc species are the most bioavailable and toxic and the aquo ion is one of the most toxic of the dissolved species of zinc however it decreases in the availability concentration at high alkalinity and pH greater than 7.5. Water hardness is a major modifier of acute zinc toxicity; increased alkalinity or water hardness decreases acute toxicity to freshwater organisms. As pointed out earlier most zinc introduced into aquatic systems sorbs to iron and manganese oxides, clay minerals, and organic materials and eventually partitions into sediments. Soft water increases zinc toxicity to aquatic organisms and USEPA ambient water quality criteria are based on water hardness. The ranking of different metals puts zinc in the top tier of water impairments due to metals (G.M. Rand, et al, 2012).
EFFECTS ON HUMANS Nutritional zinc deficiency in humans has been reported in a number of countries. Acute toxicity arises from the ingestion of excessive amounts of zinc salts, either accidentally or deliberately as an emetic or dietary supplement. Vomiting usually occurs after the consumption of more than 500 mg of zinc sulfate. Mass poisoning has been reported following the drinking of acidic beverages kept in galvanized containers; fever, nausea, vomiting, stomach cramps, and diarrhoea occurred 3–12 h after ingestion. Food poisoning attributable to the use of galvanized zinc containers in food preparation has also been reported; symptoms occurred within 24 h and included nausea, vomiting, and diarrhoea, sometimes accompanied by bleeding and abdominal cramps Manifest copper deficiency, which is the major consequence of the chronic ingestion of zinc, has been caused by zinc therapy (150–405 mg/day) for coeliac disease, sickle cell anaemia, and acrodermatitisenteropathica. Impairment of the copper status of volunteers by dietary intake of 18.5 mg of zinc per day has been reported . Zinc supplementation of healthy adults with 20 times the recommended dietary allowance for 6 weeks resulted in the impairment of various immune responses. Gastric erosion is another reported complication of a daily dosage of 440 mg of zinc sulfate. Daily supplements of 80–150 mg of zinc caused a decline in high-density lipoprotein cholesterol levels in serum after several weeks, but this effect was not found in some other studies. In an Australian study, no detrimental effect of 150 mg of zinc per day on plasma copper levels was seen in healthy volunteers over a period of 6 weeks.
MERCURY
Mercury is a chemical element with symbol Hg and atomic number 80. It is commonly known as quicksilver and was formerly named hydrargyrum. A heavy, silvery d- block element, mercury is the only metallic element that is liquid at standard conditions for temperature and pressure; the only other element that is liquid under these conditions is bromine, though metals such as caesium, gallium, and rubidium melt just above room temperature.
Health effects ● The EPA has determined that mercuric chloride and methylmercury are possible human carcinogens. The nervous system is very sensitive to all forms of mercury. ● Exposure to high levels can permanently damage the brain, kidneys, and developing fetuses. Effects on brain functioning may result in irritability, shyness, tremors, changes in vision or hearing, and memory problems. ● Short-term exposure to high levels of metallic mercury vapors may cause lung damage, nausea, vomiting, diarrhea, increases in blood pressure or heart rate, skin, rashes, and eye irritation. High doses of mercury can be fatal to humans, but even relatively low doses of mercury containing compounds can have serious adverse impacts on the developing nervous system,and have recently been linked with possible harmful effects on the cardiovascular, immune and reproductive systems5. Mercury and its compounds affect the central nervous system,kidneys, and liver and can disturb immune processes; cause tremors, impaired vision and hearing, paralysis, insomnia and emotional instability. During pregnancy, mercury compoundscross the placental barrier and can interfere with the development of the foetus, and cause attention deficit and developmental delays during childhood. (PTWI,2003) Mercury will cause severe disruption of any tissue with which it comes into contact in sufficient concentration, but the two main effects of mercury poisoning are neurological and renal disturbances. The former is characteristic of poisoning by methyl- and ethylmercury(II) salts, in which liver and renal damage are of relatively little significance, the latter of poisoning by inorganic mercury. In general, however, the ingestion of acute toxic doses of any form of mercury will result in the same terminal signs and symptoms, namely shock, cardiovascularcollapse, acute renal failure and severe gastrointestinal damage. Acute oral poisoning results primarily in haemorrhagic gastritis and colitis; the ultimate damage is to the kidney. Clinical symptoms of acute intoxication include pharyngitis, dysphagia, abdominal pain, nausea and vomiting, bloody diarrhoea and shock. Later, swelling of the salivary glands, stomatitis, loosening of the teeth, nephritis, anuria and hepatitis occur (Stockinger, 1981). Ingestion of 500 mg of mercury (II) chloride causes severe poisoning and sometimes death in humans (Bidstrup, 1964). Acute effects result from the inhalation of aircontaining mercury vapour at concentrations in the range of 0.05–0.35 mg/m3. Exposure for a few hours to 1–3 mg/m3 may give rise to pulmonary irritation and destruction of lungtissue and occasionally to central nervous system disorders (Skerfving&Vostal, 1972).
Regulatory limits ● EPA – 2 parts per billion parts (ppb) in drinking water ● FDA – 1 part of methylmercury in a million parts of seafood. ● OSHA – 0.1 milligram of organic mercury per cubic meter of workplace air and 0.05 milligrams per cubic meter of metallic mercury vapor for 8-hour shifts and 40-hour work week. (CHSR,2009) The EPA has determined that mercuric chloride and methylmercury are possible human carcinogens.
Mercury can be absorbed through the skin and mucous membranes and mercury vapors can be inhaled, so containers of mercury are securely sealed to avoid spills and evaporation. Heating of mercury, or of compounds of mercury that may decompose when heated, should be carried out with adequate ventilation in order to minimize exposure to mercury vapour. The most toxic forms of mercury are its organic compounds, such as dimethylmercury and methyl mercury. Mercury can cause both chronic and acute poisoning. (Environment Protection Agency, 2008).
The aim of the present study is find the effect of biosorbent (fish scale powder) for the removal of heavy metals in water sources (R.S.Mangalam area)
REVIEW OF LITERATURE
Water contains large amount of contaminants, especially heavy metals, organic toxicants, and human pathogens. All heavy metals are non-biodegradable and persistent in the environment. Therefore, the removal of heavy metal from water has become one of the most imperative environmental issues. Conventional water treatment such as ion exchange, membrane technologies and adsorption on activated carbon are particularly costly and not economical. In recent years, attention has been focused towards biosorption method where it has natural potential of the biomass to immobilize dissolved components for instance, heavy metal ions, on its surface. (A. Sonune, R. Ghate., 2004) Contamination of aquatic bodies by various pollutants (synthetic and organic) such aspesticides, poly-aromatic hydrocarbons, heavy metals, etc., have caused imbalance in thenatural functioning of ecosystem. Among these, heavy metals cause severe damage to livingsystems at various levels. Heavy metals enter the water supply by industrial and consumerwastes or even from acid rain breaking down soil and rocks and releasing heavy metals intostreams, lakes and ground water(Kar R N, et al.,1992,) Some metals, such as Zn and Fe ions are considered bio essential. However, even bioessential metals may cause physiological and ecological problems if present at significant concentrations . Small amount of heavy metal can result in physiological damage and easily absorbed into the human body (Wong et al., 2003; Othman et al., 2011). Due to its toxicity towards aquatic, human and other forms of life, its removal from polluted water has become one of the most imperative environmental issues (Villaescusaet al., 2004; Akar and Tunali, 2006; Witek-Krowiaket al., 2011). Currently, the uses of conventional method namely physical, chemical, and physicochemical have been applied to remove heavy metal from water. However, the application of these methods such as chemical precipitation, electrochemical treatment, membrane technologies, adsorption on activated carbon often limited due to their high operating costs, low selectivity, incomplete removal, and production of large quantities of wastes (Das et al., 2008; Witek-Krowiaket al., 2011). A new approach to remove heavy metals in water has lead to exploration of the biosorption method as an alternative for conventional methods. It can be defined as a technique using physico-chemical binding for the removal of a metal or metalloid species or radionuclides or particulates from solution using biological material (Goket al., 2011). Seashell, mandarin peels, rice bran, crab carapace, pecan nutshell, algae-yeast, peanut shell, palm shell, and others have been discovered as a natural biosorbent to remove heavy metal (Tudor et al., 2006; Pavanet al., 2006; Kadir et al., 2013; Lu et al., 2007; Vaghettiet al., 2009; Goket al., 2011; Witek- Krowiaket al., 2011; Kadir and Puade, 2013).Febriantoet al., (2009) reported that biosorption process is nonpolluting, easy to operate, offers high efficiency of treatment of waters containing low metal concentrations and possibility of metal recovery. Recently, studies had reported the used of fish scale in biosorption (Nadeem et al., 2008; Rahamanet al., 2008; Srividya and Mohanty, 2009; Othman and Irwan, 2011). Developed by the modern necessity and demand, heavy metals are on the top of the mining list and simply defined as a metal that is heavy in its atomic weight. Heavy metal is a member of loosely-defined subjects of elements that exhibit metallic properties which mainly includes the transition metals, some metalloids, lanthanides, and actinides. Many definitions have been proposed – some based on density, some on atomic number or atomic weight, and some on chemical properties or toxicity. (Mary Rhovian) The cell wall surface of fish scale contained several of functional group such as carbonyl, nitro, and amine groups for metal ions attached onto fish scale and the porous layer may provide a good possibility of metal ions to be adsorbed on its surface (Kumar et al., 2008; Nadeem et al., 2008; Vieira et al., 2011). However, limited research has been reported on the use of fish scales from Asian countries such as Malaysia. Therefore, this research will explore the unexploited property of local fish scales, M. tilapia available in abundance as waste material from the wet market, as a new biosorptive approach to remove target heavy metals such as Zn and Fe ions from water(Nadeem et al., 2008).
A number of methods have been developed for the removal of heavy metals from liquid wastes such as precipitation evaporation electroplating ion exchange membrane process etc., however, this methods have several disadvantages such as unpredictable metal ion removal high reagent requirement generation of toxic sludge etc., biosorption is a process, which represents biotechnological innovation as well as a cost effective excellent tool for removing heavy metals from Aqoues solution. This artical provides a selective overview of passed achievements and present scenario of biosorbent studies carry out on some promising natural biosorbents (algae, fungi, bacteria, yeast) and waste materials could serve as on economical means of treating effluents charged with toxic metolic ions (NilanjanaDas,Et al.,2007) Biosorption of heavy metals by Mozambique tilapia (M. tilapia) fish scales is one of the treatments that haveemerged as an environmental friendly method for the removal of metal from synthetic and domestic wastewater. Theobjectives of this study are to characterize the fish scale, determine the adsorption isotherm and biosorption kinetics insynthetic wastewater, and efficiency of fish scale in removing zinc (Zn) ion and ferum (Fe) ions in domestic wastewaterIn addition, Langmuir and pseudo-second-ordermodels exhibited the best fit data for isotherm and kinetic study, respectively. This study highlighted that M. tilapia fishscale is a promising adsorbent in removing Zn and Fe ion from synthetic and domestic wastewater solution.(N. Othman et al.,2016)
BIOSORPTION
Biosorption is defined as the ability of biological materials to accumulate heavy metals from water through metabolically mediated or physical-chemical pathways of uptake (Ahalya et al., 2003). The biological materials used in the process are usually inexpensive dead biomass that are naturally abundant or waste biomass of algae, moss, fungi or bacteria (Kratochvil and Volesky, 1998). Advantages of biosorption are the significant amount of energy savings from a more efficient water treatment system operating for fewer hours; it is economically attractive because waste biomass is inexpensive and widely available (Mustafiz et al., 2002). . One of the potential biosorbent for heavy metal removal is fish scale. A number of fish scale namely LabeoRohita, Catlacatlaand Atlantic Cod had been reported and give promising result world widely. Therefore, this research will explore the unexploited property of local fish scales (Tilapia), as a new biosorptiveapproach to remove target heavy metals such as ferum, zinc, and plumbum from water. Moreover, it is important to investigate optimum condition for heavy metal removal such as pH, biosorbent dosage, initial heavy metals concentration, contact time. (A. Witek-rowiak. Et al.,2011)
Biosorption also offers low operating cost, minimization of chemical and biological sludge, and no additional nutrient requirements (Kratochvil and Volesky, 1998). A recent study done by Mustafiz et al. (2003) suggested that fish scales of Atlantic cod, GadusmorhuaLinnaeus, be a better alternative to reduce the level of lead, arsenic and chromium in water. Following Mustafiz et al. (2003), this study will investigate the sorption capabilities of fish scales of Tilapia niloticaLinnaues for the uptake of copper in water. Scales of tilapia were used instead of Atlantic cods’ because tilapias are less expensive and have higher availability than Atlantic cod in the Bay Area. The uptake abilities of scales from different fish species should be similar because most fish scales contain significant portions of organic protein (collagen), and the structure of collagen shows that it contains the possible functional groups, such as phosphate, carboxyl, amine and amide, that are involved in the biosorption of heavy metals (Mustafiz et al., 2003). Fish scales such as any other biomaterial are composed of organic and inorganic matter. Specific studies with fish scales from cod, porgy, and flounder have established that the proteins, the organic fraction present in fish scales, seem to be the major factor governing the adsorption ability, because of the nitrogen-containing ligands present.
The amount of fish scale generated as waste from this consumption allows an abundant source of biomaterial. Some of the important uses of this biomaterial are as a base for animal feedstock, but a percentage could well be distracted as a cheap source of adsorbent materialfor the removal of contaminants from water. These thermally pre-treated fish scales present an average composition of 49.7% inorganic fraction and 50.3% of organic fraction, with an adsorptive capacity for Cu2+ that competes very favourably with that observed with Other fish species scales.
Fish scales was also been utilized by Rodriguezin the study entitled “Fish scales of Chanoschanosand Tilapia nilotica as natural sorption material in the recovery of Astaxanthin”. In this study, the researcher constructed a Fish Scale Adsorption Apparatus (FSAA) containing unshredded and shredded scales where synthetic astaxanthin dissolved in water was made to flow through. Results showed that the compressed shredded Tilapia nilotica scales were most effective in adsorbing astaxanthin. The comparison of fish scales configurations considered the discoloration of filtrate, the total volume of filtrate collected, the time it took the first flow of filtrate to be released from the FSAA and the length of time the flow lasted.The occurrence of slits on the sclerits of the unshredded tilapia scales and the presence of debris like collagen materials on unshredded tilapia scales as revealed by the scanning electron micrographs were observed to retain astaxanthin better than milkfish scales by producing greater amount of clear, colorless filtrate and greater retention time before filtrate is released (Rodriguez, 2013).
AIM AND OBJECTIVES
AIM: The aim of the present study is to preparation of fish scales as biosorbent for the removal of heavymetals in water source from R.S.Mangalam area.
OBJECTIVES: Collection and preparation of fish scales. Collection of water samples from different area in and around R.S.Mangalam Qualitative analysis(Preliminary) of water samples. Characterization of biosorbent such as Effect of pH, Biosorbent Dosage, Contact time. To determine the presence of chemical functional groups in biosorbent and water sample using FTIR ,EDAX and SEM To investigate the presence of heavymetals sorptionusing AtomicAbsorptionspectroscopy (AAS) inwater samples.
MATERIALSAND METHODS
1. COLLECTION OF SAMPLES
1.1 COLLECTION OF FISH SCALES
Fish scales were collected from the fish market located near the bus stand R.S.Mangalam, Ramanathapuram district.
Fig: 1 Fig: 2
1.2 COLLECTION OF WATER SAMPLES
Different water samplesare collected from in and around R.S.Mangalam area. such as Pallivasal street(1), valluvar street(2), Market Street(3), Akbar Street(4), location Image source from Google maps
Fig: 4 Locationof water samples collection
2. GLASSWARES AND CHEMICALS All the glass wares utilized were of borosil made and all the chemicals used for the equipments were of analytical grade.
3. PREPARATION OF FISH SCALES The mature fish scales were washed repeatedly with water to remove dust and soluble impurities from their surface. The fish scales were allowed to dry in sunshine in 2 days. The scales were kept in an oven at 750 C till the fish scales become a crispy. The dried scales were then converted in 90 microns mesh by grinding.The preserve samples are stored in proper polythene container.
Fig: 3 Fig: 4
4.QUALITATIVE (PREMILINARY) WATER ANALYSIS
The water samples of different areas(5) in R.S.Mangalam was collected ,and following parameters of such as pH, TDS, conductivity, Hardness, chloride, sulphate, calcium carbonate, alkaline, calcium, magnesium, iron, free ammonia, nitrate, chloride, fluoride, phosphate were analysed in water testing laboratory, at Madurai . The results were observed and recorded.
Preparation of stock solution(synthetic) A stock solution (1000mgL−1) was prepared by dissolving 800 microgram of, each metal ion such as Zinc sulphate, lead nitrate,coppersulphate and mercury sulphate were added and shaking it for 15 min at150rpm to obtain complete dissolution. The stock solution wasdiluted as required to obtain standard solutions of concentrationsof 20 microgram of each in 25 ml of water sample 1from R.S.Mangalam area.
5.Characterization of biosorbent-effect of pH, biosorbent dosage, contact timeand shaking time.
5.1 EFFECT OF pH Effect of pH on sample water Treatment: The reduction of all the heavy metals in the water sampleby the fish scale biosorbent was found to be pH dependent. The optimum pH of the metal ion uptake was determined by using, 25ml of metal ion solution containing 20μg of each heavy metal Cu, Zinc,lead andHg, were shaken with 0.2 g of the fish scale powder with varying pH range of 2 to 8 for0-5hrs. The optimumpH of the sample was determined using pH meter. The results were observed and recorded.
Fig: 6
5.3Effect of biosorbent concentration : In order to determine the optimum absorbent dosage on the extraction ofheavy metals in the water sample, was determined using 25ml solution containing varying range of biosorbent from 0.2 - 1g were added the mixture was shaken for 0-5hrs on a mechanical shaker at 160 rpm. Themaximum amount of sorbent required was determined using spectrophotometer.
5.4Effect of Contact time: The effect of time on fish scale absorption of metal ion sample treatment was determined using 25 ml of water sample mixed with 0.2gm(optimum) of fish scale was incubated in a shaker for 2-5 hrs . The maximum absorption time was observed and determined.
5.5 Effect of shaking time: The effect of shaking time on the extraction efficiency of fish scales on heavy metals was studied using the batch experiment. For that purpose, 0.2 g of fish scale was added to 25mL of the samples containing 20μg the metal ions at the optimum pH and automatically shaking(120rpm to 180 rpm)for0-5hrs. The optimum rpm for the maximum absorption of biosorbent was observed and determined
Fig:7
6. Heavy metal Analysis-Fourier Transform Infrared Spectrometer (FTIR)
FTIR is most useful for identifying chemicals that are either organic or inorganic. It can be utilized to quantitate some components of an unknown mixture and for the analysis of solids, liquids, and gases. The term Fourier Transform Infrared Spectroscopy (FTIR) refers to a development in the manner in which the data is collected and converted from an interference pattern to a spectrum. It is a powerful tool for identifying types of chemical bonds in a molecule by producing an infrared absorption spectrum that is like a molecular "fingerprint". The wavelength of light absorbed is characteristic of the chemical bond as can be seen in this annotated spectrum.
6.1 INSTRUMENTATION
MAKE – BRUKER Optik GmbH, MODEL No - TENSOR 27, SOFTWARE - OPUS version 6.5
Acquisition and processing
Measurements:Resolution: 4 CM-1,Sample scan time: 64 scans,Background scanstime: 64 scans, Data from: 4000cm-1 - 400cm-1 Result spectrum:TransmittanceInterferogram Size: 14220 points, FT size: 16K
Optics: Source setting: Middle-infrared light (MIR), Beam splitter: Ge-based coating on KBR
Aperture setting: 6mm, Detector:RT DLaTGS, Spectral range: 370 to 7500 cm-1 Spectral resolution: 0.125 cm-1Scanner velocities: 10KHZ, Sample signal gain:Automatic Processing: Baseline correction-Automatic, Smoothness-25points, Normalisation-Done 6.2PRINCIPLE
Molecular bonds vibrate at various frequencies depending on the elements and the type of bonds. For any given bond, there are several specific frequencies at which it can vibrate. According to quantum mechanics, these frequencies correspond to the ground state (lowest frequency) and several excited states (higher frequencies). One way to cause the frequency of a molecular vibration to increase is to excite the bond by having it absorb light energy. For any given transition between two states the light energy (determined by the wavelength) must exactly equal the difference in the energy between the ground state and the first excited state
Fig:9
6.3PROCEDURE Before FTIR analysis begins, the sample is prepared for testing using either the attenuated total reflectance (ATR),enough sample is required to obtain an absorption spectrum.The first step is to collect a background spectra that can be subtracted from the test spectra. This will ensure that the actual sample is all that is analyzed. Then the sample is analyzed by LTI’s fully-computerized FTIR Spectrometer.The equipment generates a profile in the form of an absorbance spectrum, which shows the unique chemical bonds and the molecular structure of the sample material. This absorption spectrum will have peaks representing components in higher concentration. These absorbance peaks indicate functional groups (e.g. ealkans, ketones, acidchlorises). Different types of bonds, and thus different functional groups, absorb infrared radiation of different wavelengths.The analytical spectrum is then compared in a reference library program with cataloged spectra to identify components or to find a “best match” for unknown material using the cataloged spectra for known materials.Although the analysis is performed in absorbance, it can be easily converted to transmittance using a standard formula.
7. SEM (Scanning Electron Microscopy)and EDAX ANALYSIS The scanning electron microscope (SEM) uses a focused beam of high-energy electrons to generate a variety of signals at the surface of solid specimens. The signals that derive from electron-sample interactions reveal information about the sample including external morphology (texture), chemical composition, and crystalline structure and orientation of materials making up the sample. In most applications, data are collected over a selected area of the surface of the sample, and a 2-dimensional image is generated that displays spatial variations in these properties. Areas ranging from approximately 1 cm to 5 microns in width can be imaged in a scanning mode using conventional SEM techniques (magnification ranging from 20X to approximately 30,000X, spatial resolution of 50 to 100 nm). The SEM is also capable of performing analyses of selected point locations on the sample; this approach is especially useful in qualitatively or semi-quantitatively determining chemical compositions (using EDS), crystalline structure, and crystal orientations (using EBSD). The design and function of the SEM is very similar to the EPMA and considerable overlap in capabilities exists between the two instruments.
7.1 PRINCIPLE:
Accelerated electrons in SEM carry significant amounts of kinetic energy, and this energy is dissipated as a variety of signals produced by electron-sample interactions when the incident electrons are decelerated in the solid sample. These signals include secondary electrons (that produce SEM images), backscattered electrons (BSE), diffracted backscattered electrons (EBSD that are used to determine crystal structures and orientations of minerals), photons (characteristic X-rays that are used for elemental analysis and continuum X-rays), visible light (cathodoluminescence–CL), and heat. Secondary electrons and backscattered electrons are commonly used for imaging samples: secondary electrons are most valuable for showing morphology and topography on samples and backscattered electrons are most valuable for illustrating contrasts in composition in multiphase samples (i.e. for rapid phase discrimination). X-ray generation is produced by inelastic collisions of the incident electrons with electrons in discrete ortitals (shells) of atoms in the sample. As the excited electrons return to lower energy states, they yield X-rays that are of a fixed wavelength (that is related to the difference in energy levels of electrons in different shells for a given element). Thus, characteristic X-rays are produced for each element in a mineral that is "excited" by the electron beam. SEM analysis is considered to be "non-destructive"; that is, x-rays generated by electron interactions do not lead to volume loss of the sample, so it is possible to analyze the same materials repeatedly.
7.2Sample preparation: Sample preparation can be minimal or elaborate for SEM analysis, depending on the nature of the samples and the data required. Minimal preparation includes acquisition of a sample that will fit into the SEM chamber and some accommodation to prevent charge build- up on electrically insulating samples. Most electrically insulating samples are coated with a thin layer of conducting material, commonly carbon, gold, or some other metal or alloy. The choice of material for conductive coatings depends on the data to be acquired: carbon is most desirable if elemental analysis is a priority, while metal coatings are most effective for high resolution electron imaging applications. Alternatively, an electrically insulating sample can be examined without a conductive coating in an instrument capable of "low vacuum" operation.
8. HEAVY METAL ANALYSIS BY ATOMIC ABSORBTION SPECTROSCOPY (AAS)
8.1 BACKGROUND
Atomic absorption spectroscopy (AAS) is a widely used technique for determining a large number of metals. In the most common implementation of AAS, an aqueous sample containing the metal analyte is aspirated into an air-acetylene flame, causing evaporation of the solvent and vaporization of the free metal atoms. This process is called atomization.
Fig:9 Atomic Absorption Spectroscopy
The line source(hallow cathode lamp) operating in the UV-line source as well as a high resolution monochromator. This helps to prevent interference from adjacent visible spectral region is used to cause electronic excitation of the metal atoms, and the absorbance is measured with a conventional UV-visible dispersive spectrometer with photomultiplier detector.
8.2 REAGENTS.
Certified 1000 ppm AAS standards (Pb, Zn, Cu, Hg) provided by instructor. Nitric acid (2% v/v), prepare 1 L. Unknown sample (solid) provided by instructor
8.3 PROCEDURE.
A. Preparation of Unknown.
The instructor will provide a solid unknown. Digest your sample by dissolving approximately 0.10 g (weigh accurately) in a mixture of 25 mL of concentrated nitric acid and 10 mL of concentrated sulfuric acid in a beaker. Do this operation in a fume hood. You may have to heat the sample (put a watch glass over the beaker) in order to get all material to dissolve. Once dissolved, add the mixture slowly to ~50 mL of distilled water in a 100 mL volumetric flask. Rinse the beaker several times to ensure that all material is transferred. Dilute to the mark with distilled water. B. Preparation of Standard Curves.
The instructor will describe the components and appropriate settings of the instrument and provide a list of which metals will be studied in the current laboratory session. The data table below provides relevant information for several metals that can be measured quantitatively with AAS and atomization by an air-acetylene flameLists stock solution (prepared from 1000 ppm reference standard) required to produce five 100 ml standards that span the working range. Using the provided 1000 ppm reference standards, prepare five calibration solutions that span the working ranges in the table above for the elements to be studied in the current laboratory session. Use 100 ml volumetric flasks for these standards and perform all dilutions with volumetric pipettes. The solvent for all dilutions should be 2% (v/v) nitric acid. Note: this procedure will produce a total of five solutions (i.e., each calibration standard will be a mixture of the metals being studied). Verify your solution preparation scheme with the instructor before you begin. Zero the instrument while aspirating 2% (v/v) nitric acid into the flame. Aspirate each Atomic Absorption Spectroscopy, standard into the flame and record the absorbance; repeat three times.
C. Unknown Determination.
With identical instrument settings as for preparing the calibration in Part A, aspirate the unknown and record the absorbance for each metal. Repeat the measurement three times. Note that serial dilutions may be required to obtain an absorbance reading within the working range for each metal.
RESULTS AND DISCUSSION
1.PREPARTION OF FISH SCALE AS BIOSORBENT
The mature fish scales (Lethrinus lentjan) were washed repeatedly with water to remove dust and soluble impurities from their surface. The fish scales were allowed to dry in sunshine in 2 days. The fish scales were kept in an oven at 750 C till the fish scales become a crispy.The dried scales were ground to fine powder usinga grinder and sieved to a constant size in 90 microns using a mesh size range from 90-110 and stored in air tight bottle for further experiments
Fig:1 Powdered form of Biosorbent
2. QUALITATIVE (PREMILINARY) WATER ANALYSIS The below table shows the levels of various physical and chemical parameters tested an around R.S.Mangalamarea water samples.
Table:1 Preliminary Water analysis:
BIS LIMIT Permissible Sample Sample Sample Sample S. Physical limit in the Acceptable 1 2 3 4 No Examination absence of Limit (Mg/l) (Mg/l) (Mg/l) (Mg/l) alternative source TURBIDITY 1 1 5 0 0 0 0 NT UNITS TOTAL 2 DISS.SOLIDS 500 2000 11039 10540 9700 10340 mg/l ELECTRICAL 3 CONDUCTIVI - - 15770 12300 11000 9200 TY CHEMICAL EXAMINATION
4 pH 6.5-8.5 6.5-8.5 7.10 6.0 6.5 7.5
pH Alkalinity as 5 - - 0 0 0 0 CaCo3
6 Total Alk as CaCo3 200 600 500 450 395 470
Total hardness as 7 200 600 5200 4500 4000 3900 CaCo3
8 Calcium as Ca 75 200 1300 900 850 1000
9 Magnesium as Mg 30 100 520 350 460 300
10 Iron as Fe 0.1 1.0 0 0 0 0
11 Manganese 0.1 0.3 0 0 0 0.1
Free Ammonia as 12 0.5 0.5 1 0 0 0.5 NH3
13 Nitrate as No2 - - 1 0 0.5 1 14 Nitrite as No3 45 45 80 55 70 40
15 Chlorite as Cl 250 1000 10000 8000 7500 9400
16 fluoride as F 1.0 1.5 0 0 0 0
17 sulphate as So4 200 400 800 590 670 400
18 . Phosphate as Po4 - - 0 0 0 0
Tidys test 4 hrs as 19 - - 0.4 0.4 0.3 0.3 02
This table shows result of the chemical and physical parameters of water samples collected from four different areas, in and around R.S.Mangalam .From the results it was observed that the sample 1 was found to be more pH, TDS, conductivity, Hardness, chloride, sulphate, calcium carbonate, alkaline, calcium, magnesium, iron, free ammonia, nitrate, nitrite, manganese chloride, fluoride, phosphate when comparing to other water samples. Therefore water sample from Pallivasal Street (sample 1) was selected for further study.
2.1 SAMPLE (1) TREATED WITH BIOSORBENT
Table:2shows the result of water sample after treatment (biosorbent)
BIS LIMIT Permissible
PHYSICAL limit in the WATER BIOSPRBENT S. Acceptable EXAMINAION absence of SAMPLE TREATED No Limit alternative 1 SAMPLE 1 source
1 TURBIDITY NT UNITS 1 5 0 0
TOTAL DISS.SOLIDS 2 500 2000 11039 9184 mg/l
ELECTRICAL 3 - - 15770 13120 CONDUCTIVITY
CHEMICAL EXAMINATION
4 pH 6.5-8.5 6.5-8.5 7.10 6.81
5 pH Alkalinity as CaCo3 - - 0 0
6 Total Alk. as CaCo3 200 600 500 300
7 Total hardness as CaCo3 200 600 5200 4000
8 Calcium as Ca 75 200 1300 1000
9 Magnesium as Mg 30 100 520 400
10 Iron as Fe 0.1 1.0 0 0
11 Manganese 0.1 0.3 0 0
12 Free Ammonia as NH3 0.5 0.5 1 0.5
13 Nitrate as No2 - - 1 0.5
14 Nitrite as No3 45 45 80 70
15 Chloride as Cl 250 1000 10000 9200 16 Fluoride as F 1.0 1.5 0 0.0
17 Sulphate as So4 200 400 800 600
18 Phosphate as Po4 - - 0 0.0
19 Tidys test 4 hrs as 02 - - 0.4 0.4
From the above table the results shows that sample 1 when treated with biosorbent 0.2 gm the value of pH, TDS, conductivity, Hardness, chloride, sulphate, calcium carbonate, alkaline, calcium, magnesium, iron, manganese free ammonia, nitrate, nitrite chloride, fluoride, phosphate were found to be less when comparing to normal sample before treatment.
2.Characterization of biosorbent such as effect ofpH,Biosorbent Dosage, Contact time.
In this section the effect of different experimental variables like solution pH, agitation speed, biosorbent dosage, contact time and initial metal ion concentrations which are conventionally being used to optimize the suitable experimental conditions for the maximum metal uptake by Lethrinus lentjanscales were described comprehensively.
2.1 Effect of pH
Table 3: shows the effect of pH
Heavy Metals pH Contact Removal percentage(%) time
Cu,Pb,Zn,Hg 2 62
Cu,Pb,Zn,Hg 3 64
Cu,Pb,Zn,Hg 4 67 3hrs Cu, Pb, Zn, Hg 5 70
Cu,Pb,Zn,Hg 6 69
Cu,Pb,Zn,Hg 7 68
Cu,Pb,Zn,Hg 8 69
Fig:2
Effect of pH 80 70 60 50 40 30 20
10 Removal Percentage(%) Removal 0 0 2 4 6 8 10 pH Range
Solution pH was an important governing parameter in biosorption processes. Therefore, in the present investigation, the effect of pH on the removal efficiency heavy metal by fish scales was studied at different pH (2.0 to 8.0). As expected, pH significantly affects the extent of biosorption of heavy metals. The percentage removal of the heavy metals increases appreciably with the increase up to pH 5.0. Further increase in pH does not significantly change the biosorption yield. Maximum removal of heavy metals was noted at pH 5.0, respectively.The maximum percentage removals were observed at pH 6, 5.5, 4.5 and dosage 0.02 g, 0.001 g, 0.8 g at concentration 10 ppb, 0.3 ppb, 300 ppb for zinc, plumbum, and ferum ions, respectively. Maximum removal achieved at 3 hours contact time for ferum and zinc while 2 hours for plumbum.The results indicate that Tilapia fish scale is a promising method in removing ferum, zinc, and plumbum ions from aqueous solution. (Nabilahzayadi et al., 2013)
2.2 Effect of Biosorbentconcentration
Batch Experiments were carried out to find the effect of biosorbent dose on the removal of Cu, Pb, Zn, Hg. The results shows that the amount of absorbent required for the removal of the heavy metals ions on the water sample increases with increase of biosorbent
Table-4Effect ofBiosorbentconcentration
Heavy Metals Dosage(gm) Removal Percentage (%)
Cu,Pb,Zn,Hg 0.2 48
Cu,Pb,Zn,Hg 0.4 51
Cu,Pb,Zn,Hg 0.6 54
Cu, Pb, Zn, Hg 0.8 53
Cu, Pb, Zn, Hg 1 53
Fig:3
Biosorbent Dosage 60
50
40
30
20 Removel Percentage(%) Removel 10
0 0 0.2 0.4 0.6 0.8 1 Biosorbent Dosage (gm)
Biosorbent dose is an important parameter influencing the sorption processes since it determines the sorption capacity of a biosorbent for a given initial concentration of the adsorbate under the operating conditions. The effect of biosorbent dosage in the range of 0.2– 1 g on the biosorption removal of the textile dyes by fish scales is illustrated. Dye removal efficiency increased with increasing biosorbent dose, reaching a maximum at around 1.0 g for CV and 2.0 g for MB. Such behaviour is a result of an increase in biosorbent surface area and the availability of more biosorbtion sites with increasing biosorbent dose (Nasuha et al. 2010). In the present study various concentrations fish scales biosorbent(0.2-1gm) have been used to treat the water sample. The result obtained was shown in fig: 11. From the result it was observed that the maximum absorption for the removal of metal ions efficiency increased by biosorbent dosage in an optimum of 0.6 gms concentration.It indicates that the specific heavy metal uptake values decreased with increase in biosorbentdose. Higher uptake at low biosorbent concentrations could be dueto an increased metal-to-biosorbent ratio, which decreases upon anincrease in dry biomass dose. Further it indicates that the percentageremoval of heavy metals increases with the increase in biosorbent dose, but beyond a certain value the percentage removal reaches a saturationlevel. Experiments were carried out to find the effect of biosorbent dose on the removal of Mn(II) and Cd(II) by the batch method. The results demonstrated that the removal of the tested ions on the detergent treated scales and Sod. Acetate treated fish scales is maximum at sorbent dose 0.2and 0.1 g for Mn(II) and Cd(II), respectively as shown in Figs.(3a & b). Therefore, the dose 0.2 g/ 25 mL for Mn(II) and0.1 g/ 25 mL for Cd(II) were selected as the optium dose of the biomass for the rest of the study. (N. Burham1and M.E. Aly2,2014).It is obvious that with increasing the fish scales weight from 0.05 to 0.1 g more binding sites are available and thus, the removal efficiency increase for the modified scales then decrease. This decrease could be explained by the formation of aggregates of the biomass at higher doses, which decreases the effective surface area for biosorption(Sari and Tuzen, 2008 and Karthikeyan et al., 2007).
2.3 Effect of contacttime: Effect of contact time on the treatment of water sample with the biosorbent shows that at the initial concentration, therewas no significant changes, but on increasing time the absorption was significant after the treatment for3hrs. Hence3hours was found to be an optimum treatment time. Table:5
Removal Heavy Metals Contact Time percentage (%)
Cu, Pb, Zn, Hg 1 40
Cu, Pb, Zn, Hg 2 53
Cu, Pb, Zn, Hg 3 67
Cu, Pb, Zn, Hg 4 65
Cu, Pb, Zn, Hg 5 63
Fig:4
Effect of Contact time 80 70 60 50 40 30 20
Removal Percentage (%) Percentage Removal 10 0 0 1 2 3 4 5 6 Contact Time (Hours)
NabilahZayadi et al., explained that in their work Biosorption efficiency of ferum, zinc, and plumbum removal anduptake capacity by Tilapia scales as a function of contact time. Increase in contact time lead to an increase in metal removal and uptake capacity. The optimum ferum, zinc, and plumbum removal of 64.2%, 91%, and 86% is achieved at 3 hours (Fe & Zn), and 2 hours of contact time while uptake capacity reach equilibrium at state 24.07 μg/g, 45.5 μg/g and 25.8 μg/g respectively.(NabilahZayadi and Norzila Othman,2013) To estimate the sorption capacity of the biosorbent, it is important that the experimental solution be allowed significant time to attain equilibrium. Fig. 12 shows that the effect of contact time for five different initial concentrations of with biosorbent dose (0.6 g) at pH 5 of the solution. The figure shows that percentage removal of heavy metal adsorption increases with time from 0 to 5 hrs or more and then becomes almost constant up to the end of the experiment. It can be concluded that the rate of binding heavy metal with biosorbent was more at initial stages, which gradually decreases and become almost constant after an optimum period of 3 hrs.
4.FTIR ANALYSIS (Fourier Transform Infrared)
Fig:5
100
95
90
85
80
75
Transmittance [%] Transmittance
70
65
3858.66 3425.14 2959.06 2372.58 1664.07 1549.64 1453.44 1022.78 602.06 560.19
3500 3000 2500 2000 1500 1000 500 Wavenumber cm-1
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Fig: 6
873.23 603.46 560.84
3855.85 3422.16 2965.62 2374.32 1665.91 1552.10 1453.75 1022.89
2.0
1.5
1.0
Absorbance Units Absorbance
0.5 0.0 3500 3000 2500 2000 1500 1000 500 Wavenumber cm-1
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FREQUENCY RANGE FUNCTIONAL GROUP
3422.16 N-H aliphatic primary amine
2965.22 C-H Alkene
2374.32 S-H Thiol
1665.91 C=C Alkene
1552.91 N-O Nitro compound
1453.75 C-H alkene Methyl group
1022.89 C-O Primary alcohol
873.23 C=C Alkene Vinylidene
The result shows the presence of different functional groups present in the absorption surfaces of biosorbent. The functional group was found to be N-H aliphatic primary amine, C-H Alkane, S-H Thiol, C=C Alkene, N-O Nitro compound, C-H alkene Methyl group, C-O Primary alcohol, C=C Alkene Vinylidene.Different chemical functional groups such as carboxyl, hydroxyl, amide etc. are responsible for biosorption of metal ions These functional groups are potential sites for adsorption and the uptake of metal depends on various factors such as abundance of sites, their accessibility, chemical state and affinity between adsorption site and metal.KondapalliSrividya, Kaustubha Mohanty,2009explained that FTIR analysis that thepossible mechanism of adsorption of Cr (VI) on C.catla scales maybe due to physical adsorption, ion exchange, surface precipitation,complication with functional groups and chemical reactions with surface sites. The cell wall surface of fish scale contained several of functional group such as carbonyl, nitro, and amine groups for metal ions attached onto fish scale and the porous layer may provide a good possibility of metal ions to be adsorbed on its surface (Kumar et al., 2008; Nadeem et al., 2008; Vieira et al., 2011).Different functional groups such as were responsible for the sharp peak observed at 1478 cm-1 (N=O stretch) and shows a strong bands in the infrared spectrum. Besides, the peaks at 1176cm-1 in the region of wave number 1244 cm-1 to 1032 cm-1 are representative of ethers (C-Ostretch). Fig. 1b shows FTIR spectra of ferum loaded with fish scale. Band ranging from 1554 cm-1to 1432 cm-1 shows peak at 1490 cm-1 refer to C=C ring stretch of aromatic rings while peak at 1168cm-1 produced from 1250 cm-1 to 1022 cm-1 are due to amines (C-N stretch). Fig. 1c shows FTIRspectra of zinc loaded with fish scale. The peak at 1498 cm-1 in the region 1550 cm-1 to 1434 cm-1shows the present of nitro compounds (N=O). This spectrum also shows C-N stretching adsorption atpeak 1186 cm-1 occurs in the region 1246 cm-1 to 1022 cm-1 as medium to strong band for amines.(NabilahZayadi andNorzila Othman2,b,2013)
5. SCANNING ELECTRONS MICROSCOPY(SEM)
The result shows the SEM micrographs of fish scale. Native biosorbent was shown in different magnifications types in Figure 1A, B, C and D. The fish scale appears to have a rough surface and are characterizedby having two regions, one being darker and the other being white. The white region is rich inInorganic material containing high proportion of heavy metals that bind to the biosorbent surface whereas the dark region isrich in protein because it has high proportionof carbon and oxygen. Figure:7 Native Biosorbent
A (1000x) B (3000x)
C (5000x) D (10000x)
Figure 2, A,B,C and D Represents the micrograph of heavy metal loaded biosorbent. This micrograph clearly shows that the presence of new shiny bulky particles over thesurface of heavy metals loaded biosorbent which are absent in the native biosorbent. Theseresults confirm the binding of metal ion in fish scale through biosorption.
Figure:8HeavyMetal loaded Biosorbent
A (1000x) B (3000x)
C(5000x) D (1000x)
5.1 EDAX ANALYSIS:
Energy Dispersive X-ray Analysis(EDAX) is an analytical technique used for the elemental analysis or chemical characterization of a sample.
Fig: 9
cps/eV 5
4
3 Hg Cl Cl Cu Pb S O Zn S Cu Zn Hg Pb Hg Pb
2
1
0 2 4 6 8 10 12 14 Spectrum: Acquisition 7327 keV
El AN Seriesunn. C norm. C Atom. C Error (1 Sigma) K fact. Z corr. A corr. F corr. [wt.%] [wt.%] [at.%] [wt.%] ------
O 8 K-series 16.94 39.08 65.63 2.36 0.250 1.564 1.000 1.000
Cl 17 K-series 14.88 34.34 26.03 0.53 0.101 3.365 1.000 1.009 Cu 29 K-series 4.12 9.51 4.02 0.23 0.044 1.939 1.000 1.106
Pb 82 M-series 2.45 5.65 0.73 0.13 0.031 1.642 1.000 1.097
Hg 80 M-series 2.35 5.42 0.73 0.13 0.031 1.651 1.000 1.073
Zn 30 K-series 2.20 5.07 2.08 0.18 0.027 1.715 1.000 1.110 S 16 K-series 0.40 0.93 0.78 0.05 0.003 3.350 1.000 1.038 ------Total: 43. 34 100.00 100. 00
Table:7
Element Wt%
O 39 %
Cl 34.34
Cu 9.51
Pb 5.65
Hg 5.42
Zn 5.07
In the present study, the native fish scale and andbiosorbent loaded fish scale was subjected EDAX analysis it was identified that after absorption the biosorbent shows the presence of Oxygen 39%, chlorine 34.34%, Lead 5.65%, Copper 9.51% , Mercury 5.42 % and Zinc 5.07%. The result indicate that the biosorbent was absorbed the heavy metal from the water sample.
6.ATOMIC ABSORBTION SPECTROSCOPY RESULTS
6.1 COPPER (Cu)
Calibration Parameters-Cu
Table:8
Samples Signal Rsd % Concentration of standard Absorbance Series(mg/L)
Cu Blank -0.001 46.6 0.0000
Cu Standard1 0.077 0.2 0.5000
Cu Standard2 0.167 0.4 1.0000
Cu Standard3 0.331 0.3 2.000
Sample 1 0.042 0.3 0.272
Sample 2 0.785 0.7 4.7685
Sample 3 1.356 0.2 8.2450
.Copper is an essential nutrient, but at high doses it has been shown to cause stomach and intestinal distress, liver, kidney damage, and anemia (US EPA, 2003)The maximum permissible limit by WHO is (2.0 mg/L). In the present study sample 1(borehole water)
The concentration of copper was found to be 0.272 mg/l. In the case of synthetic water(borehole water mixed with heavy metal ion) is found to be 4.7685 mg/l. In sample 3 biosorbent (fish scale powder) after treatment with water the value was found to be very high. It may be due to the presence of other metal present Along with the copper
6.2 Lead (Pb)
Calibration Parameters-Pb Table-9
Samples Signal Rsd % Concentration of standard Absorbance Series(mg/L)
Pb Blank -0.000 12.8 0.0000
Pb Standard1 0.020 1.2 0.5000
Pb Standard2 0.096 0.4 2.000
Pb Standard3 0.211 0.7 5.000
Sample 1 -0.000 48.2 0.0009 Sample 2 0.133 1.3 2.8942
Sample 3 0.676 0.2 7.1800
Lead is both toxic and non essential metal having no nutritional value. In the present study in sample 1 the concentration it was found to be 0.0009 mg/L.In the case of synthetic water(borehole water mixed with heavy metal ion) is found to be 2.8942 mg/L. In sample 3 biosorbent (fish scale powder) after treatment with water the value was found to be very high. (7.1800). It may be due to the presence of other metal present along with the lead.But the recommended value of lead 0.05 mg/L(WHO) 0.10 mg/L(ISI,ICMR). When comparing to this value sample 1 lead was found to be not detectable limit. The presence may not does be significantly related to the health effects but the contamination may be from the lead pipe used.
6.3 ZINC (Zn)
Calibration Parameters-Zn
Table-10
Signal Concentration of standard Samples Rsd % Absorbance Series(mg/L)
Zn Blank -0.002 37.1 0.0000
Zn Standard1 0.197 0.5 0.5000
Zn Standard2 0.329 0.3 1.000
Zn Standard3 0.518 0.2 2.000
Sample 1 -0.000 50.1 0.0030
Sample 2 0.781 0.1 3.3904
Sample 3 1.405 0.1 6.6937
In the present study in sample 1 the concentration of zinc found to be 0.0030 mg/l.In the case of synthetic water(borehole water mixed with heavy metal ion) is found to be 3.3904 mg/l. In sample 3 biosorbent (fish scale powder) after treatment with water the value was found to be very high. (6.6937). It may be due to the presence of other metal present along with the zinc.But the recommended value of zinc 4 mg/L(WHO) 5 mg/L(ISI,ICMR). Desirable limit 15 mg/L (IS 10500:1991).When comparing all the sample, in Sample 1 concentration ofzinc was found to be very less amount (not detectable limit)
6.4 MERCURY (Hg)
Calibration Parameters-Hg
Table-11
Signal Concentration of standard Samples Rsd % Absorbance Series(mg/L)
Hg Blank 0.001 27.0 0.0000
Hg Standard1 0.002 20.6 0.5000
Hg Standard2 0.004 18.7 1.000
Hg Standard3 0.007 12.9 2.000
Sample 1 0.004 30.3 0.9651
Sample 2 0.009 18.3 2.6078
Sample 3 0.019 9.0 6.1679
In the present study in sample 1 the concentration was found to be 0.9651 mg/l.In the case of synthetic water(borehole water mixed with heavy metal ion) is found to be 2.6078 mg/l. In sample 3 biosorbent (fish scale powder) after treatment with water the value was found to be very high (6.1679).But the recommended value of Mercury 0.002 mg/l (WHO) 0.001 mg/l (ISI,ICMR). When comparing allthe sample, Mercury was found to be above the normal level in sample 1. It significantly affect the health of living organism. (Eg). Kidney impairment, loss of vision, Nervous disorder etc.,
Table 12: Comparative analysis of heavy metals ( Cu, Zn, Pb, Hg)
SAMPLE 3 CONC.OF SAMPLE 1 SAMPLE 2
STANDARD Conc. Mg/l Conc. Mg/1 Conc. Mg/1 HEAVY SERIES Abs. (Borehole (synthetic (Biosorbent) METALS (PPM) water) water)
COPPER (Cu) 0.0281 0, 0.5, 1, 2, 0.272 4.7685 8.2450
LEAD(Pb) 0.000 0, 0.5,2,5 0.0009 2.892 7.1800
ZINC(Zn) 0.197 0, 5, 1 0.0030 3.3904 6.6937
MERCURY(Hg) 0.002 0, 0.5, 1 0.9651 2.6078 6.1679
In the present study the above results shows that Samples 1 contain detectable amount of copper and Mercury when comparing to WHO value for Copper (2.0 mg/L) Mercury (0.002 mg/L).The concentration of Zinc(0.0030 mg/L) and lead (0.0009 mg/L) was found not to be in detectable limit.Khalid Siraj and ShimelesAddisu Kitte,2013 reported that From their results obtained, none of the samples analyzed for Copper (0.025 mg/L) and Zinc (0.15 mg/L) concentration was found above the MCL but for Lead (0.02202 mg/L) concentration found above the MCL. However, the metals were present in 82.86% and 91.23% of the samples analyzed respectively. Almost 86.01% of the sample had detectable level of Lead. All the Lead concentration was above the MCL. In general, 86.70% of all samples analyzed contained one or more of three heavy metals. The results obtained from this study suggest significant risk to this population given for toxicity of these metals, well and borehole water are the only source of their water supply in this environment.Based on these results it can be concluded that fish scales are effective green and alternative biomasses for the removal of heavy metals from aqueous solutions because of its good Biosorption capacity
CONCLUSION
From the study, it was concluded that fish scales are an environmentally friendly potential biosorbent for heavy metals in water samples. In the present study fish scale of lenthrinus lentjan was used as a biosorbent. In this work examined the efficiency of this sorbent in removal of Cu. Pb, Zn and Hg from water sample.
In the preliminary water analysis, the results indicated that several factors including Total Dissolved solids, (11,039mg/l) Electrical conductivity 15,770, Hardness (as
CaCo3) (5200), Concentration of chlorite (10000mg/l)calcium (1300), shows higher value. After the treatment with biosorbent (fish scale powder) the value was found to be very less, the concentration of Total dissolved solids (9184mg/dl) Electrical conductivity (13120),
Hardness (as CaCo3) (4000) Concentration of chlorite (9200) and calcium (1000) .In the characterization of heavy metal using biosorbent various parameters were analysed, pH of solution, (pH- 5) and bioabsorbent concentration (0.6 g) and flow rate 3hrs at 160 rpm affect the biosorption process. In heavy metal analysis such as AAS (Atomic Absorption Spectroscopy), FTIR (Fourier transform InfraRed Spectroscopy), SEM (Scanning Electron Micorscope), EDAX (Energy Dispersive –X-RAY ANALYSIS) were carried out. The results of the above work showed that lead and zinc were within the acceptable limits respectively for the heavy metals measured. While copper was found to be detectable amount (0.272 mg/dl) when comparing to the maximum permissible limit as recommended by WHO (0.05). In the case of mercury it exceeds the normal limit (0.9651mg/dl) recommended by WHO (0.002). Finally the result shows the presence more amount other heavy metals also interfere with normal metals. All the above results confirmed the high pollution of ground water sources and hence, they are not suitable for consumption without prior treatment. Based on these results it can be concluded that fish scales are effective green and alternative biomasses for the removal of heavy metals from aqueous solutions because of its good Biosorption capacity, renewable and low-cost nature. In future more work is needed for validating the same results.
REFERENCES
1. A Witek-Krowiak, RG Szafran, S Modelski - Desalination, 2011 Biosorption of heavy metals from aqueous solutions onto peanut shell as a low-cost biosorbent 2. Ahalya, N. et al. (2003). Biosorption of heavy metals. Res. J. Chem. Environ 7:71-78. Vol.7(4) 3. Al-Asheh, S. and Duvnjak Z. (1997). Sorption of cadmium and other heavy metals by pine bark, J. Hazard. Mater. 56: 35–51. 4. Asheh, A. and Duvnakz, S. (2007). Adsorptrion of copper and chromium by AspergillusCarbonarius, Biotechniol. Prog. 11: 638–642. 5. BurhamN., M.E. Aly Modification of Nile tilapia fish scales as one of the best biosorbent for the determination, Preconcentration and removal of Mn(II) and Cd(II) from Bahr Yousief ISSN 2320-5407 International Journal of Advanced Research (2014), Volume 2, Issue 7, 318-339 6. Casciani, D. (2014). "Did removing lead from petrol spark a decline in crime?".BBC News. Retrieved 30 January 2017 7. Chojnacka, K. (2010). Biosorption and bioaccumulation in practice" Nova Science Publishers. 8. Das, N., Vimala, R. and Karthika, P. 2008. Biosorption of heavy metals – An overview, Indian journal of biotechnology. 7, 159-169 9. Environmental Protection Agency-EPA. 2006 Feb. Technical Factsheet on: copper. EPA ground water & drinking water page.