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HEAVY METAL REMOVAL

Investigations on the removal of

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chromium (VI) from wastewater by sugarcane bagasse


An effort has been made in the present study to evaluate the potential of raw sugarcane bagasse (RSB) for the elimination of chromium (VI) from the synthetic wastewater. The effects of various parameters such as adsorbent dosage, solution pH, contact time, and initial Cr (VI) concentration on adsorption efciency were studied during batch experiment. The removal was effective at low pH values and low chromium (VI) concentrations. Cr (VI) removal efciency was found to be 70.2% at initial Cr (VI) concentration of 10 mg/L at pH 1 and 4 hours contact time. An adsorbent dose of 7 g/L was sufcient for the removal of Cr (VI) from wastewater. The adsorption data obtained during the study tted well with the Freundlich isotherm

nvironmental pollution due to the development in technology is one of the most important problems of this century. Heavy metals like chromium, copper, lead, cadmium, etc. in wastewater are hazardous to the environment. These metals cannot be degraded or readily detoxied biologically and have tendency to accumulate in living material. Beside that, heavy metals discharge in the wastewater can be toxic to aquatic life and render natural waters unsuitable for human consumption. Chromium is priority metal pollutant introduced into water bodies from many industrial processes such as tanning, metal processing, paint manufacturing, steel fabrication and agricultural runoff. Chromium is also used in explosive, ceramics and photography. Chromium occurs in the aquatic environment as both trivalent and hexavalent states. Hexavalent chromium, which is primarily present in the form of chromate (Cr2O4-) and dichromate (Cr2O7-), possesses signicantly higher levels of toxicity than the other valency states (Sharma and Forster, 1995). The toxicity of Cr (VI) is well documented and it is considered a hazard to health of man and animals. The various compounds of chromium are found to be both corrosive to esh and carcinogenic (Ajmal et al., 1996). The presence of Cr (VI) in the aquatic environment at high concentrations is lethal to marine species. Hexavalent chromium can affect the reproduction of sh and can accumulate in the tissue of sh even if it is present at low concentrations (Haung et al 1978). Various treatment techniques available for the removal of Cr (VI) from wastewater include reduction, precipitation, ion exchange and solvent extraction. Most of these methods require high investment of capital and also expensive chemicals, making them unsuitable for treating chromiumcontaining wastewater. Adsorption is by far the most effective

and widely used technique for the removal of toxic heavy metals from wastewater. (Selvi et al., 2001). Owing to the high cost and difficult procurement of activated carbon, efforts are being directed towards nding efcient and low cost adsorbent materials. A variety of low cost materials like y ash (Narayanswamy., 1982), wood charcoal (Deepak and Gupta., 1991), bituminous coal (Kannan and Vanangamudi., 1991), bagasse and coconut jute (Chand et al., 1994), rice husk carbon (Srinivasan et al., 1998), peat (Brown et al., 2000) and red mud (Gupta et al., 2001) and have been tried. Bagasse is a waste product from sugar rening industry. It is the name given to the residual cane pulp remaining after the sugar has been extracted. Bagasse is composed largely of cellulose, pentosan and lignin (Dinish and Kumar., 2002). The present study is undertaken with a view to assess the feasibility of raw sugarcane bagasse as an adsorbent for the Cr (VI) removal. The effects of various parameters such as adsorbent dose, pH, contact time and initial metal concentration on the adsorption process have been studied. Adsorption studies will also be carried out to evaluate the adsorptive capacity of the adsorbent.

Materials and methods

Raw sugarcane bagasse was collected from a night market in Kampong Kerinchi, Kuala Lumpur, Malaysia. It was cut into small pieces, washed several times with distilled water and kept in an oven maintained at 100C for a period of 24 hours. Then the material was ground and sieved to get desired particle size of 300 to 425 m. For the preparation of synthetic wastewater, all the chemicals used were of analytical reagent grade. Stock chromium (VI) solution (1,000 mg/L) was prepared by dissolving 2.828 g potassium dichromate (K2Cr2O7) in 1,000ml double-distilled water. All working solutions of different

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HEAVY METAL REMOVAL

Figure1: Variation of Cr (VI) removal versus adsorbent dose at different metal concentrations

Figure 2: Variation of Cr (VI) removal versus pH at different metal concentrations

concentrations were prepared by diluting the stock solution with distilled water. The pH of the test solutions was adjusted using reagent grade dilute sulphuric acid and sodium hydroxide. Glassware was cleaned by overnight soaking in nitric acid and multiple rinsing with distilled water. A pH meter (Model: HI

8417, HANNA Instruments) was used to measure the pH of solutions. The effect of agitation rate was studied by shaking the solution in a HOTECH orbital shaker (Model: Gyromax 720). After agitation, the adsorbate and adsorbent were separated using a 0.45 m membrane lter (Schleicher &

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Figure 3: Variation of Cr (VI) removal versus contact time at different metal concentrations

Figure 4: Effect of initial metal concentration on adsorption of Cr (VI)

Schuell, Fed. Rep. of Germany). The chromium concentrations were analysed by a Perkin Elmer model 3100, atomic absorption spectrophotometer. All the analyses were performed according to Standard Methods for the examination of water and wastewater (1992).

The adsorption studies ware carried out by batch technique. For this investigation, a series of ask containing equal volume (50 ml in each case) of adsorbate solutions of varying concentration were employed, at desired pH and temperature. A suitable dose of adsorbent was added into each

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Figure 5: Freundlich isotherm for adsorption of Cr (VI) by raw sugarcane bagasse

conical ask. The samples were adjusted to the desired pH by using reagent grade sulphuric acid and sodium hydroxide solution. The samples were then agitated in a shaker at 165 rpm at room temperature (261C) for pre-selected contact time. After agitation, the solutions were ltered and the concentrations of Cr (VI) in the solution were analysed by atomic absorption spectrophotometer. The effect of adsorbent dose, pH, contact time and initial Cr (VI) concentration on the adsorption efciencies were studied.

Results and discussions

Effect of adsorbent dose The effect of adsorbent dose on removal of Cr (VI) at different metal concentrations (10 and 50 mg/L) has been shown in Figure 1. The results shown in the gure indicate that the percentage removal of Cr (VI) increases with an increase in adsorbent dose. This is due to increase in the surface area of sugarcane bagasse and hence more active sites are available for the adsorption of the metal ion. It is also evident from the gure that at an adsorbent dose of 7 g/L the removal efciency of Cr (VI) is found to be 70.2% at an initial metal concentration of 10 mg/L at pH 1 and 4 hours contact time. But the removal efciency drops to 30.18% when the Cr (VI) concentration is increased to 50 mg/L at above experimental conditions. Effect of pH Variation of Cr (VI) removal versus pH at different metal concentrations is depicted in Figure 2. The percentage removal of Cr (VI) increases with decrease in pH value. At an initial Cr (VI) concentration 10 mg/L the percentage removal is 70.2% as compared to its adsorption at higher concentration (50 mg/L) which is recorded as 30.18% at pH 1. While at pH 4 the percentage removal efciencies were found to be 20.18% and 16.52% at an initial Cr (VI) concentration of 10 and 50 mg/L

respectively. The value of optimum pH is found to be 1. To study the effect of contact time on Cr (VI) removal from wastewater at different initial Cr (VI) concentration (10 and 50 mg/L), the experiments were carried out at different contact time (1, 2, 3, and 4 hours) with a xed adsorbent dose (7 g/L) and pH 1 at room temperature (261C). The response of contact time on Cr (VI) removal is shown in Figure 3. The percentage removal increased from 38.2% to 70.2% when the contact time was increased from 1 to 4 hours for initial metal concentration of 10 mg/L at pH 1. While an increased in the removal efciency was noted from 18.5% to 30.18% when the contact time was varied from 1 to 4 hours at initial metal concentration of 50 mg/L at pH 1.

The sugarcane bagasse has a great potential to remove chromium (VI) from wastewater

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Effect of initial concentration The effect of initial metal concentrations (10 70 mg/L) on Cr (VI) removal by raw sugarcane bagasse is depicted in Figure 4. The adsorption of Cr (VI) decreases from 68 to 19% when the initial metal concentration was increased from 10 to 70 mg/L at an absorbent dose of 7 g/L for 4 hours contact time at pH 1. Sugarcane bagasse adsorbed chromium ions best at lower Cr (VI) concentrations in the range 10 to 20 mg/L. At lower concentration, the ratio of initial number of moles of metals ions to the available surface area is larger and subsequently the fractional adsorption becomes independent of its minimum initial concentration (Yu et al., 2002). Adsorption isotherm In order to model the adsorption behaviour and calculate the adsorption capacity, the adsorption data obtained during the present study is analysed by the Freundlich isotherm. Freundlich isotherm is expressed as follows: qe = x/m = KfCe1/n (1) References 1. Ajmal M., Roa R. A. K. and Siddiqui B.A., (1996) Studies on removal and recovery of Cr (VI) from electroplating waste Water Research Vol. 30, No. 6, 1478 - 1482. 2. Brown P. A. and Allen S. J., (2000) Metal removal from wastewater using peat, Water Research, Vol. 34, No. 16, 3907 3916. 3. Chand S.J Agarwal V.K and Kumar P., (1994) Removal of hexavalent chromium from wastewater by adsorption, Ind .J. Environ. Health, Vol. 36, No. 3, 151-158. 4. Deepak, D. and Gupta, A. K, (1991) A study on removal of chromium (VI) by adsorption lignite coal, Ind. J. Environ. Pollut., Vol. 11, 241 245. 5. Dinish M. and Kumar P. S., (2002) Single and multi component adsorption of cadmium and zinc using activated carbon derived from bagasse an agricultural waste, Wat. Research, Vol. 36, 2304 2318. 6. Grover, M. and Narayanswamy, M.S., (1982) Removal of hexavalent chromium by adsorption on y ash, Institution of Engineers Indian J. Environ. Engg., Vol. 63, 36 39. 7. Gupta V. K, Gupta M. Sharma S., (2001) Process development for the removal of lead and chromium from aqueous solution using red mud an aluminium industry waste, Wat.Research, Vol. 35, No. 5, 1125- 1134. 8. Haung, C.P. Bowers, A.R, The use of Activated carbon for Chromium (VI) removal, Prog.Water Tech.,10,5/6, pp. 45-64, 1978. 9. Kannan, N and Vanangamudi, A., (1991) Astudy on removal of chromium Cr (VI) by adsorption by adsorption lignite coal, Ind. J. Environ. Pollut., Vol. 11, 241 245. 10. Selvi, K., Pattabhi S. and Kardivelu K., (2001) Removal of Cr (VI) from aqueous solution by adsorption onto activated carbon, Bioresour.Technol., Vol. 80, 87 89. 11. Sharma, D. C., Forster, C. F., (1995) Column studies into the adsorption of chromium (VI) using sphagnum moss peat, Bioresour. Technol., Vol. 52, 261 267. 12. Srinivasan K., Balasubramaniam N. and Ramakrishna T. V., (1998) Studies on Chromium Removal by Rice Husk Carbon, Ind. J. Environ. Health, Vol. 30, 376 387. 13. Yu L.J, Dorris K.L., Shukla A and Margrave J.L., (2003) Adsorption of chromium from aqueous solutions by maple dust, J.Hazard.Materials, Vol. 100, 53 63.

The logarithmic form of Freundlich model is represented by the following equation: log qe = log Kf + (1/n) log Ce (2)

where qe is the mass of the adsorbate adsorbed per unit mass of adsorbent (mg adsorbate/g adsorbent), while Ce is the equilibrium concentration of the adsorbate (mg/L). Kf and 1/n are Freundlich constants related to adsorption capacity and adsorption intensity respectively. The values of constant Kf and 1/n are obtained from the plot of log (x/m) against log Ce, for the adsorption data of Cr (VI), which is shown in Figure 5. It is evident that the data is well tted to the Freundlich isotherm and can be represented by the following mathematical expression: x/m = 0.0086 Ce4.380

Conclusion

From the present study, it can be concluded that the sugarcane bagasse has a great potential to remove chromium (VI) from wastewater. The percentage removal of Cr (VI) depends on adsorbent dose, pH, contact time, and initial Cr (VI) concentration. At 4 hours contact time and initial metal concentration of 10 mg/L, 70.2% Cr (VI) removal was observed but when the metal concentration was increased to 50 mg/L the removal efciency dropped to 30.8%. Sugarcane bagasse adsorbed chromium ions best at lower Cr (VI) concentration in the range of 10 to 20 mg/L but the removal efciency dropped to 19% when the metal concentration was increased to 70 mg/L. The adsorption data for Cr (VI) tted well to the Freundlich isotherm. WWA
Enquiry No: 006

This paper is written by Dr Nasim Ahmad Khan (department of civil engineering, Aligarh Muslim University, Aligarh, India) and Mr Hapsah Mohamad (department of civil engineering, University of Malaya, Kuala Lumpur, Malaysia).

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