1.

Introduction The presence of various contaminants in the water system, arising from the discharge of industrial effluents containing different toxic substances, is one of the major environmental issues in the field of waste management. The quality of both surface and ground water is deteriorating day by day with rapid industrialization and increasing population all around the world. Typical industrial contaminants such as various dyes, heavy metals, pharmaceutical compounds etc. in excess of their respective tolerance limits, can be detrimental to aquatic life and pose potential health hazard (Zadaka et al., 2007). It therefore becomes necessary to remove such pollutants from the effluent streams before discharging to any water body. Different techniques are used for removal of pollutants for water but adsorption process is worth mentioning amongst all as it can be applied for the removal of pollutants even if they present at very low concentration. Adsorption by activated carbon has been widely used for the removal of various pollutants due to its simplicity of operation. But the widespread use of activated carbon is however restricted due its high cost. Therefore, development of low cost adsorbents as an alternative of commercial activated carbon and application of this low cost adsorbent for the removal of various pollutants has become a growing field of research. 2. Literature Survey Activated carbon can be prepared from various agricultural wastes by physical, chemical or microwave activation method. Generally, a physical process such as, the carbonization process or the adsorption process is optimized by statistical approach such as, the response surface methodology (RSM) to determine the optimum process conditions. The response surface methodology (RSM) is a statistical design procedure that optimizes a process by correlating the process variables through regression analysis (Lee, et al., 2000). The RSM optimization can be done through Box-Behnken design (BBD) or central composite design (CCD). Activated carbon prepared from various sources by carbonization method was used to remove wide verities of pollutants from water. Nemr et al. (2009) and Khan and Chaudhuri (2009) investigated the adsorption of Direct Blue 86 from the aqueous solution by using orange peel derived activated carbon and coconut coir based activated carbon respectively. In another study, the adsorption of 1

ibuprofen was studied by using activated carbons derived from sisal waste (Mestre et al. 2011). Issabayeva et al. (2006) investigated the adsorption of Pb(II) by using activated carbon derived from palm shell (Issabayeva et al. 2006) and Sea-buckthorn stones (Mohammadi et al., 2010) respectively. It was observed in the previous literature that Gaikwad (2011) used coconut shell based activated carbon for the adsorption of Cu(II). In another investigation the adsorption of fluoride was investigated by using activated carbon derived from plant materials (Emmanuel et al., 2008). Recent research reviews show that exploiting or utilizing local resources to be a current trend. This leads to developing of technology based on availability of local raw material and its use for water pollution. Therefore, in the present research an activated carbon was prepared from a waste scrap wood available locally and then prepared adsorbent was applied to remove different pollutants from their aqueous phases. 3. Objective of the present research The objective of the present research is therefore set as- development of activated carbon from locally available scrap wood, its characterization and its application for adsorption of different pollutants from aqueous phase. 4. Steps to achieve the objectives The following steps were carried out in order to achieve the objective.
i).

Selection of suitable raw material from waste scrap wood available locally. This is carried out by evaluating the quality of the chars produced through carbonization of various scrap woods in different cases. Optimization of the carbonization process for the selected raw material (Acacia Auriculiformis scrap wood). The activation of the char through microwave treatment to produce activated carbon and its physiochemical characterization.

ii).

Adsorption studies with synthetic and real pollutants to establish the applications of the activated carbon produced.

5. Work done The experimental work comprises of experimental work for preparation of Char by carbonization of raw material. Microwave activation of the char to produce activated carbon. Adsorption studies with different pollutants in aqueous phase. 5.1 Experimental Carbonization The activated carbon was prepared by carbonization of scrap wood followed by microwave activation. The carbonization was carried out in a 65-mm i.d tubular furnace where the wood scraps were heated from ambient temperature to the carbonization temperature at the rate of 4 C/min in a continuous flow of N2. Then the temperature was kept constant for 1h. The product was then allowed to cool to ambient temperature in presence of N2 flow. Microwave activation The prepared char sample was then activated in a microwave oven (IF20PG3S) for five minutes at a constant input power of 800 W and at a frequency of 2450 MHz to develop the activated carbon. The activated carbon was characterize to determine the following properties such as, surface area, total pore volume, average pore size, surface morphology, apparent density, ash content and point of zero charge (pHZPC) property etc. Adsorption study The batch adsorption study was carried out by adding 0.1 g of adsorbent into a series of 250 mL conical flasks containing 100 mL adsorbate solution. The flasks were shaken in an incubator shaker at a constant speed of 200 rpm for 2 h. The aliquots were collected at predetermined time intervals and centrifuged for 5 min. The supernatant liquids were analyzed for determining the residual adsorbate concentration. The amount of adsorbate uptake at any time t can be calculated from the relationship:
qt (C 0 C t ) V w

(1)

Where, qt (mg/g) is the amount of adsorbate adsorbed per gram of adsorbent at any time t (min), V is the volume of solution (L), w is the weight of adsorbent (g), C0 and Ct are the initial adsorbate concentration and adsorbate concentration at any time t (mg/L). The equilibrium study was performed by varying the temperatures (10-50 C). In the equilibrium study, the adsorbate solutions containing fixed amount of adsorbent were shaken in an incubator shaker till the equilibrium was attained and then the samples were centrifuged for 5 minutes and were analyzed to determine the residual adsorbate concentration in the solution. After the equilibrium study the saturated activated carbon was then washed with distilled water, dried in an oven and finally was used for the desorption study. 5.2 Preparation of the activated carbon from Acacia Auriculiformis scrap wood The char prepared from Acacia Auriculiformis showed high surface area (442.40 m2/g) and total pore volume (0.320 cm3/g) with a high carbon yield (29.50%) in comparison to the char prepared from other wood species such as, Ziziphus Jujube, Cedrus Deodara, Albizzia Lebbek, Anthecephalus Kadamba. Hence, Acacia Auriculiformis was selected as raw material for the present study. The surface area, total pore volume and average pore size of the prepared char were found to increase with increase in temperature up to 700 C but as the temperature was increased further these values were observed to decrease. Besides, the surface area and total pore volume increased with the increase in carbonization time and decrease in N2 flowrate. The carbonization process was optimized statistically by using three level Box-Behnken design (BBD) with three input variables such as, carbonization temperature (x1,C), carbonization time (x2, min) and nitrogen flow rate (x3, mL/min) and three output variables such as, surface area (Y1, m2/g), total pore volume (Y2, cc/g) and the carbon yield (Y3, %). Using analysis of variance (ANOVA), the model F-value for surface area, total pore volume and carbon yield were found to be 121.03, 55.16 and 128.03 respectively. The overall determination coefficient for surface area, total pore volume and carbon yield were observed to be 0.9954, 0.99 and 0.9957 respectively. The regression equation for surface area was: Y1 = 514.20 + 89.29x1 + 8.55x2 67.41x3 + 17.58x1x2 -29.45x1x3 -25.72x2x3 140.35x12 21.07x22 + 4.05x32 The regression equation for total pore volume (Y2) was: 4 (2)

Y2 = 0.36 + 0.052x1 + 0.019x2 0.009x3 + 0.018x1x2 + 0.006x1x3 +0.019x2x3 0.079x12 0.01 x22 0.004 x32 The regression equation for carbon yield was: Y3 = 20.32 6.99x1 1.91x2 +1.32x3-0.94x1x2-0.24x1x3+1.50x2x3+1.25 x12 - 2.09 x22 + 0.87 x32 (4) The optimum values of carbonization temperature, time and nitrogen flow rate were found to be 750 C, 3.5 h and 300 mL/min respectively. The char prepared under this optimum condition (C750N) was found to have surface area, total pore volume and average pore size of 514.2 m2/g, 0.36 cc/g and 27.99 . The prepared char was further treated in a microoven to prepare the activated carbon (AC750NMW5) which had surface area, total pore volume and average pore size of 695 m2/g, 0.50 cc/g and 28.55 . The ash content, density and point of zero charge (pHZPC) of the prepared activated carbon were found to be 2 %, 2.4 g/cc and 7.92 respectively. The maximum Methylene Blue adsorption capacity of the microwave assisted activated carbon (AC750NMW5) was fond to be 413 mg/g which was close to the adsorption capacity of commercial activated carbon (414.3 mg/g). 5.3 Adsorption studies to evaluate the activated carbon prepared The prepared activated carbon was used to adsorp different pollutants from their aqueous phase. 5.3.1 Application of microwave assisted activated carbon for the removal of DB 86 Through the batch adsorption study, the DB 86 adsorption capacity of 85.71 mg/g was obtained with solution pH of 2, initial concentration of 100 mg/L, adsorbent concentration of 1.00 g/L, particle size and agitation speed of 61-150 m (average size 105.5 m) and 200 rpm. The Langmuir isotherm was found to be best correlated with high values of regression coefficient (R2=0.99) and lower value of chi-squared (2 < 2.6) among various isotherms investigated. The monolayer adsorption capacity increased from 184.98 to 487.81 mg/g with increase in temperature from 283-313K. The adsorption data was best fitted to the pseudo second-order model (R2>0.99). The DB 86 adsorption process was found to be endothermic in nature. The DB 86 adsorption capacity of AC750NMW5 (484.57 mg/g ) was found to comparable with the adsorption capacity of the commercial activated carbon (497.93 mg/g).The activated carbon was found to have a desorption efficiency of 48.93%. 5 (3)

The DB 86 adsorption process was optimized by using Box Behnken design (BBD) with five input variables namely the solution pH (x1), initial adsorbate concentration (x2), adsorbent concentration (x3), contact time (x4) and temperature (x5) and one output variable as the amount of DB 86 adsorbed per gram of adsorbent (Y, mg/g). Using ANOVA, the model F value and determination coefficient value were found to be 59.89 and 0.979 respectively. The regression equation for DB 86 adsorption capacity was: Y = 14.25 9.73x1 + 7.18x2 11.18x3 + 3.13x4 + 4.85x5 - 9.63x1x2 + 5.34x1x3 + 3.18x1x4 +1.06x1x5 -12.05x2x3 + 1.23x2x4 +0.26x2x5 4.4x3x4 5.12x3x5 + 0.03x4x5+ 8.02x12 +0.02x22 (5) + 4.56x32 1.31x42 + 2.06x52 The optimum condition for DB 86 adsorption was obtained at pH of 2, initial concentration 100 mg/L, adsorbent concentration 1 g/L, contact time 120 min and temperature of 30 C. At this optimum condition, the model predicted (85.95 mg/g) and experimental (85.71 mg/g) DB 86 adsorption capacity were found to be close to each other. 5.3.2 Application of microwave assisted activated carbon for the removal of ibuprofen The batch adsorption study revealed that the ibuprofen adsorption capacity of 59.98 mg/g was obtained at pH, initial concentration and adsorbent concentration of 2, 60 mg/L and 1 g/L respectively and with particle size of 61-150 m (average size 105.5 m), agitation speed of 200 rpm. In comparison to other isotherm models, Langmuir isotherm exhibited a better fit (R2=0.99 and 2 <3.61). The monolayer adsorption capacity was found to decrease from 198.65 to 186.64 mg/g when the temperature was increased from 283 to 323 K. According to Langmuir isotherm the monolayer adsorption capacity was found to be 198.42 mg/g at 303K which was comparable with the adsorption capacity of commercial activated carbon (199.34 mg/g). Among the various kinetic models, it was observed that the kinetic data exhibited a better fit to pseudo second order model. The ibuprofen desorption efficiency of the activated carbon was found to be 84.19%. The ibuprofen adsorption process was successfully optimized by using a three level BoxBehnken design (BBD) with solution pH (x1), initial adsorbate concentration (x2), adsorbent concentration (x3), contact time (x4) and temperature (x5) as input variables and amount of ibuprofen adsorbed per gram of adsorbent or ibuprofen adsorption capacity Y (mg/g) was chosen

as the output variable. The model F value and overall determination coefficient value were found to be 55.55 and 0.9780 respectively. The regression equation for ibuprofen adsorption was Y = 17.59- 3.18x1 + 9.60x2 - 11.34x3 + 0.79x4 - 1.40x5 - 1.71x1x2 + 0.28x1x3 - 0.81x1x4 1.95x1x5 - 5.94x2x3 + 0.076x2x4 - 0.20x2x5 + 0.90x3x4 + 0.19x3x5 -0.35x4x5 - 1.37x12 -0.83x22 (6) + 6.31x32 - 1.29x42 - 2.62x52 The optimum ibuprofen adsorption condition was found to be at pH 2, initial concentration 60 mg/L, adsorbent concentration 1g/L, contact time 110 min and temperature 30 oC. The experimental (59.9 mg/g) and model-predicted (54.00 mg/g) ibuprofen adsorption capacity at optimum conditions were found to be in reasonable agreement with each other. 5.3.3 Application of microwave assisted activated carbon for the removal of Pb(II) From the batch adsorption study, the Pb(II) adsorption capacity of 117.55 mg/g was obtained at pH, initial concentration and adsorbent concentration of 6, 120 mg/L and 1g/L respectively and with particle size of 61-150 m (average size 105.5 m), agitation speed of 200 rpm. The equilibrium analysis showed that the data exhibited a better fit to Langmuir isotherm and the monolayer adsorption capacity was found to be 199.90 mg/g at 303K which was pretty close to the adsorption capacity of commercial activated carbon (200 mg/g). The monolayer adsorption capacity decreased from 199.98 to 191.04 mg/g when the temperature increased from 283 to 323 K. The experimental data best fitted to pseudo second order model. The Pb(II) desorption efficiency of the activated carbon was found to be 75.04%. The Pb(II) adsorption process was successfully optimized by using a central-composite design (CCD) with solution pH (x1), adsorbent concentration (x2), initial adsorbate concentration (x3), contact time (x4) and temperature (x5) as input variables and amount of Pb(II) adsorbed per gram of adsorbent or Pb(II) adsorption capacity Y (mg/g) was chosen as the output variable. The model F value and overall determination coefficient were found to be 228 and 0.998 respectively. The regression equation for optimization of Pb(II) adsorption process was: Y = 60.17+ 7.57x1 5.84x2 + 6.61x3 + 1.43x4 12.83x5 + 3.56x1x2 2.82x1x3 1.83x1x4 4.59x1x5 2.31x2x3 1.50x2x4 + 8.42x2x5 + 3.37x3x4 3.12x3x5 -0.94x4x5 4.11x12 2.71x22 2.79x32 5.51x42 7.15x52 7 (7)

The optimum Pb(II) adsorption condition was found to be at pH 6, initial concentration 120 mg/L, adsorbent concentration 1.5 g/L, contact time 80 min and temperature 20oC. The experimental (79.43 mg/g) and model-predicted (76.60 mg/g) Pb(II) adsorption capacity at optimum conditions were found to be in reasonable agreement with each other. 5.3.4 Application of microwave assisted activated carbon for the removal of fluoride The fluoride adsorption capacity of 8.8 mg/g was obtained at pH, initial concentration and adsorbent concentration of 4.4, 10 mg/L, and 1g/L respectively and with particle size of 61150 m (average size 105.5 m), agitation speed of 200 rpm. The equilibrium analysis showed that the data exhibited a better fit to Langmuir isotherm and the monolayer adsorption capacity was found to be 18.95 mg/g at 303K which was comparable with adsorption capacity of commercial activated carbon (19.30 mg/g). The monolayer adsorption capacity increased from 18.95 to 19.26 mg/g when the temperature increased from 303 to 323 K. The experimental data best fitted to pseudo second order model (R2=0.99). The fluoride adsorption process was endothermic in nature having enthalpy of 6.094 kJ/mol. The fluoride desorption efficiency of this activated carbon was found to be 80.54%. 5.3.5 Application of microwave assisted activated carbon for the removal Cu(II) Through the batch adsorption study, the Cu(II) adsorption capacity of 99.96 mg/g using synthetic solution was obtained at pH, initial concentration and adsorbent concentration of 6, 100 mg/L, and 1g/L respectively and with particle size of 61-150 m (average size 105.5 m), agitation speed of 200 rpm. Langmuir isotherm exhibited better fit to the equilibrium data and monolayer adsorption capacity of Cu(II) was found to be 398.52 mg/g which was quite close to the adsorption capacity of commercial activated carbon (399.74 mg/g). The equilibrium Cu(II) adsorption capacity decreased from 398.52-386.29 mg/g as the temperature was increased from 303-323 K. Pseudo second order model exhibited a better fit (R2 =.99) in comparison to other studied kinetic models. The Cu(II) desorption efficiency was found to be 81.60%. An effluent from copper plating industry consisting of a Cu(II) concentration of 250 mg/L and chemical oxygen demand (COD) of 160 mg/L was also selected for the study. It was observed that the Cu(II) adsorption capacity of 99 mg/g (99% removal) was achieved at pH, initial concentration and adsorbent concentration of 6, 100 mg/L, and 1g/L respectively and with 8

particle size of 61-150 m (average size 105.5 m), agitation speed of 200 rpm. The kinetic data exhibited better fit to pseudo-second-order model. 6. Conclusion In the present research an activated carbon activated carbon (AC750NMW5) was developed by microwave activation of the char prepared through carbonization of Acacia Auriculiformis scrap wood at a temperature of 750 oC for 3.5 h in presence of nitrogen (N2) flow (300 mL/min). The prepared activated carbon was used to remove a textile dye (Direct Blue 86), a pharmaceutical compound (ibuprofen), an inorganic pollutant (fluoride) and heavy metals (Pb(II) and Cu(II)) through batch adsorption study. The prepared activated carbon was found to have a DB 86 and ibuprofen adsorption capacity of 85.71 mg/g and 59.98 mg/g respectively. The activated carbon was also found to have good adsorption capacity for fluoride (8.8 mg/g) and various heavy metals such as, Pb(II) and Cu(II). The Pb(II) and Cu(II) adsorption capacity of the prepared activated carbon were found to be 117.55 mg/g and 99.96 mg/g. The activated carbon also exhibited good adsorption capacity (99 mg/g) for removal of Cu(II) from industrial effluent. 7. Contribution made by scholar Development of an effective adsorbent by carbonization of locally available scrap wood is studied in detail. The adsorption efficiency of the prepared activated carbon for different pollutants is also explored for the first time. The optimization of the adsorption process is also investigated. The publications resulted from this research work are given bellow. 8. Publication Basu, J.K., Dutta, M., 2011. Application of statistical design approach to develop a low cost activated carbon for the removal of textile dye Direct Blue 86. Int. J. Environ. Dev. 8 (2), 217239. Dutta, M., Ghosh, P., Basu, J.K., 2012. Statistical optimization for the prediction of ibuprofen adsorption capacity by using microwave assisted activated carbon. Arch. Appl. Sci. Res. 4 (2), 1053-1060. Dutta, M., Ray, T., Basu, J.K., 2012. Batch adsorption of fluoride ions onto microwave assisted activated carbon derived from Acacia Auriculiformis scrap wood. Arch. Appl. Sci. Res. 4 (1), 536-550. 9

Dutta, M., Basu, J.K., 2011. Application of response surface methodology for the removal of Methylene Blue by Accacia Auriculiformis scrap wood char. Res. J. Environ. Toxic. 5 (4), 266278. Dutta, M., Basu, J.K., 2012. Statistical optimization for the adsorption of Acid Fuchsin onto the surface of carbon alumina composite pellet: an application of response surface methodology. J. Environ. Sci. Technol. 5 (1), 42-53. Dutta, M., Basu, J.K., 2012. Application of Artificial Neural Network for Prediction of Pb(II) Adsorption Characteristics. Environ. Sci. Pollut. Res., [Published, DOI 10.1007/s11356-0121245-x]. 8.1 References Emmanuel, K.A., Ramaraju, K.A., Rambabu, G., Veerabhadra Rao, A., 2008. Removal of fluoride from drinking water with activated carbons prepared from HNO3 activation - a comparative study. Rasayan J. Chem., 1 (4), 802-818. Gaikwad, R.W., 2011. Mass transfer studies on the removal of copper from wastewater using activated carbon derived from coconut shell. J. University Chem. Technol. Metallurgy 46 (1), 53-56. Gurses, A., Yalcin, M., Dogar, C., 2001. Electrocogulation of some reactive dyes: a statistical investingation of some electrochemical variables. Waste Manage. 491499. Issabayeva, G., Aroua, M.K., Sulaiman, N.M.N., 2006. Removal of lead from aqueous solutions on palm shell activated carbon. Bioresour. Technol. 97 (18), 23502355. Khan, T., Chaudhuri, M., 2009. Adsorptive removal of Direct Blue 86 by coconut coir activated carbon. Environ. Sci. Technol. Conf. 7-8, 237-241. Lee, J., Ye, L., Landen Jr, W.O., Eitenmiller, R.R., 2000. Optimization of an extraction procedure for the quantification of vitamin E in tomato and broccoli using response surface methodology. J. Food Comp. Anal. 13 (1), 4557. Mestre, A.S., Bexiga, A.S., Proena, M., Andrade, M., Pinto, M.L., Matos, I., Fonseca, I.M., Carvalho, A.P., 2011. Activated carbons from sisal waste by chemical activation with K2CO3: kinetics of paracetamol and ibuprofen removal from aqueous solution. Bioresour. Technol. 102 (17), 82538260. Mohammadi, S.Z., Karimi, M.A., Afzali, D., Mansouri, F., 2010. Removal of Pb(II) from aqueous solutions using activated carbon from Sea-buckthorn stones by chemical activation. Desalination 262 (1-3), 8693. Nemr, A.E., Abdelwahab, O., El-Sikaily, A., Khaled, A., Removal of direct blue-86 from aqueous solution by new activated carbon developed from orange peel. J. Hazard. Mater. 161 (1), 102110. 10

Zadaka, D., Mishael, Y.G., Polubesova, T., Serban, C., Nir, S., 2007. Modified silicates and porous glass as adsorbents for removal of organic pollutants from water and comparison with activated carbons. Appl. Clay Sci. 36 (1-3), 174181.

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