World Journal of Fish and Marine Sciences 4 (1): 73-77, 2012

ISSN 2078-4589
© IDOSI Publications, 2012
DOI: 10.5829/idosi.wjfms.2012.04.01.56237

A Biosorption of Heavy Metal Ions from

Aqueous Solutions Using Fish Scale (Catla catla)

K. Prabu, S. Shankarlal and E. Natarajan

Centre of Advanced Study in Marine Biology, Annamalai University, Parangipettai - 608 502, India

Abstract: In recent years, heavy metals pollution has become one of the most serious environmental problems.
With rapid development of many industries, wastes containing heavy metals are directly or indirectly being
discharged into the environment. Biosorption is a cost effective excellent tool for removing heavy metals from
the wastewater aqueous solutions. In this study, freshwater fish scale, inexpensive biowaste offers potential
for the removal of metal ions by biosorption.

Key words: Fish scale % Wastewater % Biosorption % Heavy metals % Biosorbent

INTRODUCTION have shown levels of metal uptake high enough to

warrant further research [19]. In the present work, Catla
Biosorption is a physico-chemical adsorption catla fish scales are used as the biosorbent. More
whereby metal ions become attached to the biomass amounts of these scales are being generated from fish
surface [1]. The ability to adsorb metals has been markets everyday and are thrown away as it is. This paper
investigated for many materials, including wool, rice, reports the potential of this biosorbent for removing the
straw, coconut husks, peat moss [2], fungi [3], algae [4] heavy metals from the synthetic wastewater aqueous
and yeast [5]. The feasibility of using fish scale as a solution. The biosorption activity of the fish scales was
biosorbent to remove heavy metals was examined by studied under various parameters such as effect of
Mustafiz [6]. Biological effects on adsorption of heavy dosage, effect of time and the effect of pH. FTIR
metals such as lead, arsenic and chromium were spectroscopy and SEM was used to find out the various
studied using Atlantic cod scale [7]. Biosorption of Pb functional groups present on the cell wall of the
(II) by fish scale was studied by Raziya Nadeem et al., biosorbent as well to study the surface morphology of
[8]. Metals are non-biodegradable and are considered biosorbent.
as major environmental pollutants [9]. Literature
survey reveals that several biological materials such MATERIALS AND METHODS
as non living biomass like bark, lignin, peanut hulls as
well as living biomass like fungi, bacteria, yeast, moss, All the chemicals reagents used in these studies were
aquatic plants and algae, were investigated for the of Analytical Reagent Grade, including concentrated
removal of heavy metals [10-16]. Biosorption utilizes reagents; HNO3, H2SO4, HCl, H3PO3 and Ca (OH) 2, NaoH
the ability of biological materials to accumulate (Merck) and Al (OH) 3.
heavy metals from waste streams by either
metabolically mediated or purely physico-chemical Preparation of Biosorbent: Catla catla fish scales were
pathways of uptake. Heavy metals released into the collected from the local fish market, Chidambaram. Mature
environment by technological activities tend to persist fish scales were washed repeatedly with water to remove
indefinitely, circulating and eventually accumulating adhering dust and soluble impurities from their surface.
throughout the food chain, becoming a serious threat to The fish scales were allowed to dry in sunshine for 2
the environment [17]. Biosorption is proven to be quite days. The scales were then kept in an oven at 70°C till the
effective for the removal of metal ions from contaminated fish scales became crispy. The dried scales were then
solution in a low cost and environment friendly manner converted into 100-150 mesh by grinding in a mechanical
[18]. Various biomaterials have been examined for their grinder. Then preserve the sample in polythene container
biosorptive properties and different types of biomass for further use as biosorbent.

Corresponding Author: K. Prabu, Centre of Advanced Study in Marine Biology,

Annamalai University, Parangipettai, 608 502, India.
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Chemical Pretreatment of Fish Scales: For chemical determine the metal ion concentrations using an ICP-OES,
pretreatment, 10 gm of sample was soaked in 150 ml of 0.1 Perkin Elmer (OPTIMA 2100 DV). This experiment is
M HCl, H2SO4, H3PO3, NaOH, Ca (OH)2 and Al (OH)3 for 2 carried out by different concentration of dosage, pH and
hr in rotary shaker in 100 rpm at room temperature. The incubation time.
fish scales were filtered and washed with generous
amount of deionised water until neutral pH was attained. Instruments: The FTIR spectrum of the biosorbent was
Resulting biomass is used for the biosorption study. measured by using Perkin Elmer spectrum -RX1 system in
the range of 400-4000 cm-1 and the scanning electron
Preparation of Synthetic Wastewater: The initial microscopy of the biosorbent was analyzed using
concentration used was 50 ppm for each of (chromium, JEOL-JSM-5610LV.
iron, cobalt, zinc, cadmium, manganese, nickel, lead) and
100 ml in the standard flask. The pH of the synthetic RESULTS AND DISCUSSION
wastewater was adjusted to a pH 5 to prevent hydrolysis.
Effect of Biosorbent Dosage in Wastewater
Heavy Metals Analysis: The experiments were carried out Treatment: Various dosages of the prepared fish
for measurement of adsorption capabilities. The bottles scales biosorbent have been used to treat the
with 500 ml capacity were filled with synthetic wastewater synthetic wastewater treatment. The parameters such
(50 ml) was mixed with fish scale. The bottles were shaken as chromium, iron, cobalt, zinc, cadmium, manganese,
at room temperature in a reciprocating shaker for 24 hr at nickel and lead has been decreased drastically with the
300 rpm. Then the separation of the biosrobent and increase in the biosorbent dosage. Hence 5 mg was found
solutions was carried out by filtration with Whatman filter to be the optimum dosage in treating the wastewater
paper No. 42 and the filtrate stored in sample cans for (Table 1).

Table 1: Effect of biosorbent dosage in synthetic wastewater (50 ml) treatment

Sample dose (mg/ml)
-------------------------------------------------------------------------------------------------------------------------
Parameter Initial concentration (mg/l) 1 2 3 4 5
Chromium (mg/l) 50 17.4 8.5 5.2 3.2 2.9
Iron (mg/l) 50 26 17 13 9 5
Cobalt (mg/l) 50 27 19 15 12 7
Zinc (mg/l) 50 26.7 22.5 12.5 8.4 5.5
Cadmium (mg/l) 50 29 21 15 9 7
Manganese 50 39 33 18 11 8
Nickel 50 44 35 31 26 22
Lead 50 41 32 26 22 17

Table 2: Effect of time in synthetic wastewater (50 ml) treatment

Time (hrs)
-------------------------------------------------------------------------------------------------------------------------
Parameter Initial concentration (mg/l) 1 2 3 4 5
Chromium (mg/l) 50 17.4 8.2 5.3 2.8 2.1
Iron (mg/l) 50 22 18 14 8 6
Cobalt (mg/l) 50 25 16 11 7 6
Zinc (mg/l) 50 25.6 21.2 13.8 7.6 3.4
Cadmium (mg/l) 50 44 33 26 17 8
Manganese 50 36 31 16 10 6
Nickel 50 42 33 30 24 17
Lead 50 44 37 24 20 16

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Table 3: Effect of pH in synthetic wastewater (50 ml) treatment

pH

Parameter Initial concentration (mg/l) 5 6 7 8 9

Chromium (mg/l) 50 27.4 20.3 9.3 12.2 18.3
Iron (mg/l) 50 33 21 6 12 18
Cobalt (mg/l) 50 26 15 8 11 14
Zinc (mg/l) 50 29.4 21.4 8.4 10.4 15.5
Cadmium (mg/l) 50 34 29 12 14 18
Manganese 50 42 36 15 18 20
Nickel 50 43 37 22 25 28
Lead 50 40 35 19 23 26

Effect of Time in Wastewater Treatment: Effect of time

on the treatment of wastewater treatment by the fish
scales. On increasing the time, the initial concentration
reduces. After the treatment for 5 hours all the heavy
metals concentration at significant level. Hence 5 hours
was found to be an optimum treatment time (Table 2).

Effect of pHon Wastewater Treatment: The reduction of

all the heavy metals in the wastewater by the fish scale
biosorbent was found to be pH dependent. Results
showed that there was maximum adsorption of all the
parameter in the effluent by fish scale biosorbent at pH 7
and hence pH 7 was found to be better on treating the Fig. 1: Scanning electron microscopy structure of Catla
wastewater (Table 3). catla

Fig. 2: FTIR spectrum of Catla catla

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Table 4: FTIR spectrum represented functional group

S. No Band position Functional groups
1 3376 cmG1 Stretching vibration of O-H and N-H groups
2 2928 cmG1 C-H stretching vibrations of -CH3 and -CH2
3 2344 - 2362 cmG1 Carboxylic
4 1659 - 1559 cmG1 Carbonyl
5 1442 - 1341 cmG1 C-H, -CH3 and -CH2
6 1032 cmG1 C-O
7 873 cmG1 Sulphonate group
8 562 cmG1 Alkanes

Scanning Electron Microscopy: Scanning electron REFERENCES

microscopy has been used by many researchers for the
characterization of the biosorbent. SEM micrographs 1. Drake, L.R. and G.D. Rayson, 1996. Plant derived
obtained for catla scales as seen in the micrograph (Fig.1). materials for metal ion selective binding and
The white region is rich in inorganic material containing pre-concentration. Analytical Chemistry News and
high proportions of calcium and phosphorus whereas the Features, 1: 22-27.
dark region is rich in proteins, because it has a high 2. Macchi, G., D.D. Marconi and G. Tiravarthi, 1986.
proportion of carbon, oxygen and sulphur. Uptake of mercury by exhausted coffee grounds.
Environ. Technol. Lett., 7: 431-444.
Fourier Transforms Infrared (FTIR) Spectroscopy: 3. Mueler, M.D., D.C. Wolf, T.J. Beveridge and
Different chemical functional groups such as carboxyl, G.W. Bailay, 1992. Sorption of heavy metals by the
hydroxyl, amide etc. are responsible for biosorption of soil fungi Aspergillus niger and Mucor rouxii. Soil
metal ions [20-23]. These functional groups are the Biology Biochemistry, 24: 129-135.
potential sites for adsorption and the uptake of metal 4. De Carvalho, R.P., K.H. Chong and B. Volesky, 1995.
depends on various factors such as abundance of sites, Evaluation of the Cd, Cu and Zn biosorption in two
their accessibility, chemical state and affinity between the metal systems using an algal biosorbent.
adsorption site and metal. The FTIR spectroscopy is an Biotechnology Progress, 11: 39-44.
important analytical technique which detects the vibration 5. Dostalek, P., M. Patzak and P. Matejka, 2004.
characteristics of chemical functional groups present on Influence of specific growth limitation on biosorption
adsorbent surfaces. The biosorbent spectra were of heavy metals by Saccharomyces cerevisiae.
measured by using Perkin Elmer spectrum -RX1 system in International Biodeterioration and Biodegradation,
the range of 400-4000 cmG1. FTIR spectra of Catla catla 54: 203-207.
scale is shown in Figure (2). The represented functional 6. Mustafiz, S., 2003. The application of fish scales in
group in the FTIR spectrum was given in the Table (4). removing heavy metals from energy-produced
waste streams: The role of microbes, energy sources,
CONCLUSION 25: 905-916.
7. Nilanjana Das, P. Karthika, R. Vimala and Vinodhini,
This paper reports the potential of this fish scale 2008. Use of natural products as biosorbent of
(Catla catla) biosorbent for removing the heavy metals heavy metals an overview, Natural Product Radiance,
from the synthetic wastewater aqueous solution. The 7: 133-138.
biosorption activity of the fish scales was studied under 8. Raziya Nadeem, Tariq Mahmood Ansari, Ahmad
various parameters such as effect of dosage, effect of time Mukhtar Khalid and Fourier, 2008. Transform
and the effect of pH. At pH 7 in the dosage of 5 mg/l and infrared spectroscopic characterization and
at the time of 5 hour, the biosorbent show significant optimization of Pb (II) biosorption by fish
result has been found. FTIR spectroscopy and SEM was (Labeo rohita) scales, J. Hazardous Materials,
used to find out the various functional groups present on 156: 64-73.
the cell wall of the biosorbent as well to study the surface 9. More, T.G., R.A. Rajput and N.N. Bandela, 2003.
morphology of biosorbent. So the fish scale act as a Impact of heavy metals on DNA content in the whole
biosrobent and it can be used for wastewater treatment at body of freshwater bivalve, Lamelleiden marginalis.
industrial level. Environ. Sci. Pollut. Res., 22: 605-616.

76
 World J. Fish & Marine Sci., 4 (1): 73-77, 2012

10. Mohanty, K., M. Jha, B.C. Meikap and M.N. Biswas, 17. Vijayaraghavan Kuppusamy, Joseph Raj Jegan,
2006. Biosorption of Cr (VI) from aqueous solutions Kandasamy Palanivelu and Manickam Velan, 2004.
by Eichhornia crassipes, Chem. Eng. J., 117: 71-77. Copper removal from aqueous solution by marine
11. Veglio, F. and F. Beolchini, 1997. Removal of green alga Ulva reticulate. Electronic J. Biotechnol.,
metals by biosorption: a review, Hydrometallurgy, 7(1): 61-71.
44: 301-316. 18. Volesky, B., 1990. Biosorption and biosorbents:
12. Nourbakhsh, M., Y. Sag, D. Ozer, Z. Aksu, T. Kutsal In Biosorption of heavy metals. CRC Press, Florida,
and A. Caglar, 1994. A comparative study of various pp: 3-44.
biosorbents for removal of chromium (VI) ions from 19. Volesky, B. and Z.R. Holan, 1995. Biosorption
industrial wastewaters, Process Biochem., 29: 1-5. of heavy metals. Biotechnol. Progress,
13. Prakasham, R.S., J. Sheno Merrie, R. Sheela, 11(3): 235-250.
N. Saswathi and S.V. Ramakrishna, 1999. Biosorption 20. Han, X., Y.S. Wong, M.H. Wong and N.F.Y. Tama,
of chromium (VI) by free and immobilized Rhizopus 2007. Biosorption and bioreduction of Cr (VI) by a
arrhizus, Environ. Pollut., 104: 421-427. microalgal isolate Chlorella miniata, J. Hazard. Mater.
14. Sudha, B.R. and T.E. Abraham, 2002. Studies on 146: 65-72.
enhancement of Cr (VI) Biosorption by chemically 21. Arica, M.Y. and G. Bayramoglu, 2005. Cr (VI)
modified biomass of Rhizopus nigricans, Water Res., biosorption from aqueous solutions using free
36: 1224-1236. and immobilized biomass of Lentinus sajor-caju:
15. Loukidou, M.X., A.I. Zouboulis, T.D. Karapantsios Preparation and kinetic characterization, Colloids
and K.A. Matis, 2004. Equilibrium and kinetic Surf. A: Physicochem. Eng. Aspects, 253: 203-211.
modeling of chromium (VI) biosorption by 22. Jain, M., V.K. Garg and K. Kadirvelu, 2009. Chromium
Aeromonas caviae, Colloids Surf. A: Physicochem. (VI) removal from aqueous system using
Eng. Aspects, 242: 93-104. Helianthus annuus (sunflower) stem waste, J.
16. Wang, X.S., Y.P. Tang and R.T. Sheng, 2008. Hazard. Mater., 162: 365-372.
Kinetics, equilibrium and thermo dynamics study on 23. Tunali, S., K. Ismail and T. Akar, 2005. Chromium (VI)
removal of Cr (VI) from aqueous solutions using biosorption characteristics of Neurospora crassa
low cost adsorbent Alligator weed, Chem. Eng. J., fungal biomass, Miner. Eng., 18: 681-689.
148: 217-225.

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