BIOSORPTION POTENTIAL OF COCOMEAT AND FISH BONE IN THE REMOVAL OF COPPER (II) IN AQUEOUS SOLUTION

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BIOSORPTION POTENTIAL OF COCOMEAT AND FISH BONE IN THE REMOVAL OF COPPER (II) IN AQUEOUS SOLUTION Amerigo Bernardo Ramos Jr.*1 *1Bulacan

Agricultural State College, San Ildefonso, Bulacan, Philippines.

ABSTRACT Drinking clean water is a challenge and minimizing the effects of water pollution is a must. The use of underutilized materials like cocomeat waste and fish bone as biosorbent is one of the solutions to the pressing problems. The purpose of this study is to determine the biosorptive potential of cocomeat and fish bone in the removal of copper ions in water. The needs to ascertain the most effective biosorbent samples, cocomeat (C), fish bone (F) and combination (CF) as well as the contact time were investigated in the study. To test the biosorption potential of the samples, UV-Vis Spectrophotometer was used. After analyzing the results from all the samples (C, F, CF), the cocomeat (C) exhibited the highest adsorbance rate of copper ions in the solution.

However, other samples reacted to the solution resulting to low adsorption. Furthermore, contact time test result revealed that the longer the time of exposure of the biosorbent to the copper solution, the higher the rate of adsorbance.

Keywords: Biosorbent, Adsorption, Copper, Cocomeat, Fish bone.

I.

INTRODUCTION

One of the pressing issues of the environment in the past decades is water pollution. Industrial wastewaters loaded with heavy metals produce hazards to human and organisms. Grave consequences of hazards caused by metal toxicity cannot be easily removed.

In recent years, there is an increase in the awareness of the environment which led a need for the filtration of water pollution released from the different industries. Conventional methods in the removal of heavy metals from these wastewaters include different processes such as chemical precipitation, electrolytic recovery, ion exchange/ chelation and solvent extraction/ liquid membrane separation. Though very promising, these procedures are very costly and might cause inadequate efficiencies, this can also generate toxic sludge, and the disposal of which is an additional burden on the feasibility of treatment procedures [1].

Biosorbents are biological materials used to absorb heavy metals from industrial effluents through physicalchemical pathways of uptake [2]. One of the main advantages of biosorption is that it provides a significant amount of energy saving scheme from a more efficient industrial effluents treatment system which operates for fewer hours, it is economically wise because waste biomass is inexpensive and widely available [3].

Biosorption is an important substitute to available conventional copper removal methods. Many research studies have presented results that using organic products like fish scales, banana peel, eggshells and others as biosorbent were effective in absorbing lead, cadmium, and chromium in water. In this study, coconut meat and fish bone will be used as biosorbent in the investigation of copper sorption capabilities under different biosorbent to copper mas ration and contact time.

The need for alternative yet environmentally friendly material is of great importance to mankind. It is imperative to find ways to mitigate the issues on wastewater purification technology.

Background of the study. Copper is naturally deposited in rocks as mineral form, which is mostly associated with sulfur [4]. Examples of common mineral that contain copper are azurite, malachite, tennantite, chalcopyrite and bromite [5]. Anthropogenic sources of copper include the production of plastic material, copper and other nonferrous smelting, and steel blast furnaces [6]. The major sources of copper contamination in drinking water are from plumbing material, due to the corrosion of copper pipes from passing water through these pipes. Copper released into the environment indefinitely persist, circulate and accumulate in the food chain [7]. Higher plants and animals are exposed to copper by consuming contaminated food and water.

Although copper is an essential nutrient to humans, excess intake of copper would cause acute and chronic adverse health effects as stomach and intestinal distress, liver and kidney damage, and anemia [6]. Not only www.irjmets.com

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does toxicity of copper causes physical damages to the human body, but it can also worsen the symptom of mental disease. High levels of copper have been associated with people with mental illness, such as paranoia, obsessive-compulsive schizophrenia, and Alzheimer’s disease [8].

Examples of conventional copper removal methods are ion exchange, chemical precipitation, ultra-filtration, and electrochemical deposition [9]. 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 additional chemicals in the treatment [10].

Biosorption is defined as the ability of biological materials to accumulate heavy metals from wastewater through metabolically mediated or physical-chemical pathways of uptake. The biological materials used in the process are usually inexpensive dead biomass that are naturally abundant or waste biomass [11].

Advantages of biosorption are the significant amount of energy savings from a more efficient wastewater treatment system operating for few hours. It is economically wise to use because the materials are inexpensive and widely available.

Waste materials from coconut products like the meat from the extraction of cocomilk are abundant in the market of San Ildefonso. Fish bone from fish vendors who sell deboned milkfish are also abundant in the market. These underutilized materials are of great potential as biosorbent. They are widely available and very inexpensive.

Statement of the Problem. The general problem of the study is: How effective do the cocomeat and fish bone as biosorbent of copper in aqueous solution?

Specifically, the study aims to accomplish the following objectives: 1.

to evaluate the biosorption potential of cocomeat and fish bone;

2.

to determine the effectiveness of cocomeat and fish bone under two variables; 2.1. adsorption to initial concentration of copper and, 2.2. contact time.

Hypothesis. The null hypothesis of the study is there is no significant effect of biosorption of copper in aqueous solution using cocomeat and fish bone.

Significance of the study. Drinking clean water in urban areas nowadays is a challenge. Water pollution is one of the problems our country is facing. Heavy metal poisoning and other related diseases have threatened the lives of people who are exposed to different pollutants in the water.

In a similar study [12], different natural products were used as biosorbent of heavy metals. The researcher used several organic materials like eggshell, coffee beans, fruit waste, and rice husk. A significant decrease in heavy metals was exhibited after the utilization of different biosorbents.

The present study utilized the use of underutilized materials like coconut meat and fish bone which are readily available and inexpensive.

The results of this study may contribute to the existing database of biomaterial with biosorptive ability. This aimed at developing a cost-effective way of solving water pollution in the Philippines. It can also help in the fast-growing industry and a steppingstone for more sophisticated analysis on water filtration and the use of underutilized materials.

Scope and limitations. This study was limited to the use of cocomeat and fish bone as cost effective biosorbent of copper in aqueous solution. Coconut meat and fish bone were obtained from the market of San Ildefonso, Bulacan. The copper stock solution was prepared by a chemist in the College of Chemistry at the University of the Philippines, Diliman, Quezon City. The biosorption capability of the cocomeat and fish bone and the contact time were tested in the study.

Review of Related Literature. Environmental pollution by toxic metal contamination due to rapid industrialization is a challenging problem that the country is facing nowadays. The discharges of industrial effluents into aquatic environment cause potential threat to aquatic life as well as human health. The need to mitigate the pressing concern is the main objective of this study. To fabricate biosorbent from underutilized materials which have great potential in water filtration. www.irjmets.com

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Fish scales of Atlantic cod, Gadus morhua Linn., can be a better alternative to reduce the level of lead, arsenic, and chromium in water [13]. Following this study will investigate the sorption capabilities not the scales but the bone of milkfish, Chanos chanos, and coconut meat in adsorbing copper in aqueous solution. Several studies investigated natural products as biosorbent of heavy metals.

Utilization of crab shell for biosorption of copper (II) and cobalt (II) was investigated. At optimum particle size (0.767 mm), biosorbent dosage (5g/l) and initial solution pH (6), crab shell recorded a maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively [7].

The capacity of raw rice bran for chromium and nickel removal from aqueous solutions was investigated. The Langmuir and Freundlich adsorption models, which are in common use for wastewater treatment applications were used to represent the experimental data. Results of the study revealed that Cr (VI) and Ni (II) were adsorbed due to strong interactions with active sites of the biosorbent [14].

A similar study of crushed eggshells was tested. The study revealed that eggshells possess relatively high sorption capacity of chromium ions. When compared with other sorbents, it was found that sorption capacity with the increase of chromium concentration, temperature and sorbent concentration. Egg shells were able to remove the Cr (III) ions below the acceptable level [15].

Papaya wood was evaluated as new biosorbent of heavy metals. On contacting with 10 mg/l copper (II), cadmium (II) and zinc (II) solutions with 5g/l papaya wood, during shake flask contact time of 1 hour. The respective metal removal was noted to be 97.8, 94.9, and 66.8%. Biosorption was most efficient at pH 5 and metal ion biosorption increased as the ration of metal solution to biomass quantity decreased [16].

The biosorption of Zn from aqueous solution by composite adsorbent (chitosan-coated acid treated coconut shell carbon) was tested. Coconut shell carbon was modified with chitosan and oxidizing agent to produce a composite adsorbent. The removal efficiency was controlled by solution pH, adsorbent concentration and agitation times, initial ion concentration and particle size. The result revealed that 90% of Zn was adsorbed by the biosorbent [17].

II.

METHODOLOGY

Research Model INPUT  Copper stock solution  Coconut meat  Fish bone

OUTPUT  Cocomeat  Fish Bone Biosorbent

PROCESS  Preparation of biosorbent

OUTCOME Cocomeat and fish bone Biosorbent Tested for its efficiency in adsorbing copper in aqueous solution

Fig.-1. Paradigm of the study Biosorbents. Coconut meat and fish bone of milkfish (Chanos chanos) were used in the study. It was collected from the market of San Ildefonso, Bulacan. These materials were soaked in distilled water for 24 hours and were rinsed three times with distilled water. The cocomeat and the fish bones were placed in a container and were air dried for 24 hours. Then it was placed inside a regular microwave oven at 80°C for 4 hours until the materials were completely dry. The dried materials were finely pulverized using a laboratory mortar and pestle then it was screened through a metal sieve of cut size 150-212µm.

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Fig.-2: Cocomeat and Fish Bone Biosorbent Preparation Copper Stock Solution. All copper solution that was used in the study was prepared by a chemist from the College of Chemisty Laboratory, University of the Philippines, Diliman, Quezon City. The stock solution was be prepared by adding 62.83g of copper (II) Cupric sulfate pentahydrate (CuSO 4.5H2O) in 5 liters of deionized water, which resulted in an initial concentrations of 5g Cu/L. A 20ml of the copper stock solution was placed inside 9 vials with 30ml capacity.

Fig-3. Copper Solution Batch Method. The biosorption experiment was carried out by batch method which was adopted on the study conducted on the treatment of industrial wastewater by using banana peels and fish scales. 1gram of coconut meat biosorbent was contacted with 20 ml of copper solution under shaking of 360 rpms for a time interval at room temperature. The vials were labeled C1, C2, C3 (Cocomeat). The supernatant was separated by centrifugation for 10 mins. The copper concentration of the solution was measured using UV-Vis spectrophotometer [18].

The same procedure was used for the fish bone biosorbent F1, F2, F3 (Fish bone) and finally the same steps were used for the combination of both biosorbent the Cocomeat and the fish bone CF1, CF2, CF3.

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Fig.-4: Testing the Biosorbent Varying Contact Time. After the most effective biosorbent was determined, varying contact time test was conducted. Each sample was treated under constant amount of biosorbent while at different time (30 mins., 1hr., 6hrs., 12hrs., 24hrs.,) with a platform shaker at 250 rpm. The biosorbent in the samples were filtered out and the final copper filtrate was determined. The percentage and the removal rate were then calculated after.

All the treatments were done in triplicate to test the validity and reliability of the experiment. The data gathered were tabulated and analyzed using MS Excel.

Fig.-5. Biosorbent tested based on the contact time.

III.

MODELING AND ANALYSIS

For the Coconut meat and Fish bone Biosorbent

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IV.

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RESULTS AND DISCUSSION

Biosorption Activity of the Materials Tested

Table 1. Calibration Curve Data A Concen Abso tration (M) rbance* 0.001 0.005 0.003 0.008 0.005 0.012 0.01 0.021 0.02 0.042 0.03 0.065 Absorbance measured at 635 nm which is the wavelength of maximum absorbance of copper solution.

Absorbance

Calibration Curve 0.1 y = 2.0725x + 0.0017 0.05 R² = 0.9978 0 0

0.01

0.02

0.03

0.04

Concentration (M)

Fig.-6. Calibration curve.

From the equation of the line, the concentration of the remaining copper ions may be computed based on the measured absorbance of the samples. (where x = concentration and y = absorbance)

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Table-2: Absorbance of the Different Samples Sample Name

Absor bance

C1

0.023

C2

0.019

C3

0.02

CF1

0.078

CF2

0.087

CF3

0.079

F1

0.17

F2

0.13

F3

0.15

Concent ration (M) 0.01061 7761 0.00868 7259 0.00916 9884 0.03716 2162 0.04150 5792 0.03764 4788 0.08156 3707 0.06225 8687 0.07191 1197

Only samples C1-C3 yielded good results. For samples CF1-CF3, calculated concentrations are much higher (>0.02M) because of increased absorbance due to the presence of particulates in the solution. This particulate may have come from fish bones. For F1-F3, unsatisfactory results were obtained also due to the presence of particulates.

Test for Contact Time Absorbance measured at 635 nm which is the wavelength of maximum absorbance of copper ions. An R squared value almost equal to 1 indicates very good correlation between the absorbance and concentration.

This is indicative that the copper solutions follow Beer’s Law and are suitable in the determination of unknown copper ion concentration through absorbance measurement.

Absorbed Cu ions (M)

Effect of Time on the Concentration of Absorbed Cu Ions 0.0150 0.0100 0.0050 0.0000 0

5

10

15

20

25

30

Time (hour) Figure -7: Contact time results.

As can be deduced from the graph, a significant increase in the amount of absorbed copper ions is observed after 1 hour of incubation with the sample. After which, incremental but relatively smaller increase in copper uptake can be seen after prolonged exposure of the solution to the cocomeat sample. Hence, exposure for 1 hour appears to be the most optimal time for a significant amount of copper ions to be absorbed.

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The biosorption potential of two underutilized materials were given emphasis on this study. Cocomeat which was used in the extraction of cocomilk and fish bone from household and market scraps were tested as biosorbent of copper in aqueous solution.

The data revealed that among the three samples prepared, cocomeat (C1, C2, C3), fish bone (F1, F2, F3), and combination (CF1, CF2, CF3) the cocomeat is the most effective in adsorbing copper ions in the solution. A similar result was obtained from the study conducted on copra meal; it was used as biosorbent of cadmium ion in an aqueous solution. Results revealed that cadmium uptake was very evident using the isotherm tests. Both results revealed that the high surface area of the biosorbent contributed to the high adsorbance rate of the metal ions in the solution [19].

However, the fish bone and the combination biosorbents did not exhibited effective adsorbance rate because of the crystals and particulate matters produced after the experimentation. The substance present in the fish bone reacted to the copper ions resulting to the formation of crystals. This result is different from the findings on the use of fish scale as biosorbent of copper. 33 % of the copper ions were removed after the application of fish scale from Tilapia nilotica [20]. The present study revealed that the fish bone is not a good biosorbent compared to fish scales.

Comparing the contact time of the cocomeat biosorbent (30m., 1h., 6hrs., 12hrs., 24hrs.) revealed that the longer the time of exposure of the biosorbent to the copper solution, the higher the adsorbance rate. Cocomeat biosorbent with the contact time of 1hr. exhibited high biosorptive potential. This supports the findings of Huang (2007) that the maximized sorption percentage would occur with the application of biosorbent and a longer contact time.

V.

CONCLUSION

To drink clean water and to minimize the effects of water pollution are the main goals of this study. The fabrication of a biosorbent from coconut meat and fishbone as filter provides practical and economical ways to solve the pressing problems. Coconut meat obtained from the market and fishbones from the households were utilized in the study. They were dried and pulverized to increase their surface area and then placed in the copper solution as biosorbent. Comparison on the effectivity between the cocomeat and fishbone was done and afterwards, contact time was analyzed. The fabricated biosorbent was tested using the UV-Vis spectrophotometer.

Based on the results, it can be concluded that between the coconut meat, fishbone, and combination as biosorbents, the coconut meat is the most effective in adsorbing copper in the water. On the other hand, the fishbone biosorbent reacted to the copper solution forming crystals which made the solution more contaminated.

Contact time between the samples of coconut meat was tested and the results revealed that the longer the time of contact of biosorbent to the copper solution, the higher the copper ions uptake. However, the most optimal time of absorbance is within 1 hour.

VI.

[1] [2] [3] [4] [5] [6] [7] [8]

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