Adsorption of Cd(II) and Pb(II) from aqueous solutions on Saw dust and neem bark

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Abstract The ability of saw dust and neem bark as natural adsorbent was investigated for adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied. The optimum solution pH for adsorption of Cd(II) and Pb(II) from aqueous solutions was found to be 5. Kinetics data were best described by pseudosecond order model. The effective particle diffusion co-efficient of Cd(II) and Pb(II) are of the order of 10-10 m2/s. The equilibrium adsorption data for Cd(II) and Pb(II) were better fitted to Langmuir adsorption isotherm model. The thermodynamic studies indicated that the adsorption was spontaneous and exothermic for Cd(II) adsorption and endothermic for Pb(II). The sorption energy calculated from Dubinin-Radushkevich isotherm were 9.6855 kJ/mol and 10.1015 kJ/mol for the adsorption of Cd(II) and Pb(II) respectively which indicated that both the adsorption processes were chemical in nature. Key words: Saw dust, Neem bark, Pseudo second order, Effective diffusivity, Langmuir, Desorption, Sorption energy Introduction Environmentalist is primarily concerned with the heavy metals due to their toxicity and impact on human health and environment. These heavy metals introduced into natural water resources by waste water discharged from industries such as metal plating, cadmium-nickel and lead storage batteries, mining, galvanizing, paints, pigments, insecticides, cosmetics, stabilizer and alloy manufacturing. The health effects of Cd(II) on human include nausea, vomiting, diarrhea, muscle cramp, salivation, reduction of red blood cells, damage of bone marrow, hypertension, kidney failure following oral ingestion, lung irritation, chest pain, and loss of sense of smell after inhalation [1-3]. Pb(II) is a highly toxic substance, exposure to which can produce a wide range of adverse health effects for both adults and children. At high levels of exposure, a child may become mentally retarded, fall into a coma, and even die from lead poisoning. In adults, lead can increase blood pressure and cause fertility problems, nerve disorders, muscle and joint pain, irritability, and memory or concentration problems [4]. The tolerance limits for heavy metal concentration in potable water and discharge into inland surface waters is shown in Table 1 [5-7]. Precipitation, ion exchange, electrochemical precipitation, solvent extraction, membrane separation, concentration, evaporation, reverse osmosis and bio-sorption and emulsion per traction technology are the conventional methods for the removal of heavy metals from the aqueous solution [8-11]. These technologies suffer from cost effectiveness and ineffectiveness when the metals are dissolved in large volume of solution of relatively low concentration. Adsorption process seems to be most versatile and effective method for removal of heavy metal

if combined with appropriate regeneration steps. It solves the problem of sludge disposal and renders the system more viable. Considering the cost economics, recent research has focused on the development of low-cost readily available alternatives using various agricultural, industrial, natural/biological waste materials including synthetic, modified model adsorbents. Several contributions have made in this area utilizing number of materials like sunflower stalks, spent grain, oak sawdust, cassava waste, baggage fly ash, wheat bran, olive pomace, carrot residues, tree fern, sugar beat pulp, grape stalk waste etc. Present study deals with a series of batch adsorption experiments to investigate the capability of sawdust and neem bark as low cost natural biosorbent for removal of metal ions from aqueous solutions. Saw dust and neem bark contain lingo-cellulose based materials, readily available and found to have potential surface adsorption properties. 2. Materials and methods Sawdust of teakwood origin was collected from a saw mill at Dum Dum near Kolkata, West Bengal, India. Neem bark was collected from a local Neem tree near Kolkata, West Bengal, India. Sawdust was collected from a local sawmill. It was of teakwood origin. After collection it was washed thoroughly with distilled water to remove muddy materials and then with 0.1N NaOH to remove lignin based color materials followed by 0.1N H2SO4. Finally it again washed with distilled water several times and dried in an oven at 105 50 C for 6 hr and cooled to room temperature in desiccators. Particle size of 250-350 m were used for adsorption studies. Neem bark after collection washed thoroughly with distilled water to remove muddy materials and then sun dried. Then it was cut into small pieces, ground and homogenized. It was then dried in an air oven at 105 5 0C for 5-6 hr to remove the adherent moisture. Then after cooling to room temperature it was washed several times with distilled water to remove dust and color. Finally it was dried again in the air oven at 105 5 0C and cooled in a desiccators. All the necessary chemicals used in the study were of analytical grade and obtained from Merck Limited, Mumbai, India. Stock solution of Cd(II) and Pb(II) were made by dissolving exact amount of respective metal salt. The range of concentration of the metal components prepared from stock solution was varied between 3 mg/L to 300 mg/L. The test solutions were prepared by diluting 1 g/L of stock metal solution with double distilled water. Atomic adsorption spectrophotometer (Varian Spectra AA 55, USA) was used to determine the Cd(II) and Pb(II) content in standard and treated solutions after adsorption experiments. The pH of the solution was measured with a 5500 EUTECH pH Meter using FET solid electrode calibrated with standard buffer solutions. Required amount of adsorbent was taken in a 250 ml stopper conical flask containing 100 ml of desired concentration of the test solution for the batch adsorption studies at the desired pH value. pH of the solution was monitored in a 5500 EUTECH pH Meter using FET solid electrode calibrated with standard buffer solutions. Necessary amount of adsorbent was then added and contents in the flask were shaken for the desired contact time in an electrically thermo stated reciprocating shaker at 300C. The contents of the flask were filtered through filter paper and the filtrate was analyzed for remaining metal concentration in the sample using Atomic Absorption Spectrophotometer (VARIAN SPETRA AA 55, USA) as per procedure laid down in APHA, AWWA standard methods for examination of water and wastewater, 1998 edition [12]. 3. Results and discussion 3.1 Effect of pH The effect of pH on the adsorption of Cd(II) by saw dust and neem bark were studied by varying pH of the solution over the range of 1-8. Suitable range for adsorption of Cd(II) was evaluated from the studies of solubility product. The solubility product equilibrium constant 2

(Ksp) demonstrated that the best pH range of 2-8 for Cd(II) for adsorption [13]. Removal efficiency increased with increase pH for the adsorption of Cd(II) on saw dust and neem bark (Figure 1). Although a maximum uptake was noted at a pH of 8, as the pH of the solution increased to >7, Cd(II) started to precipitate out from the solution. Therefore experiments were not conducted over pH 7. The increased capacity of adsorption at pH >7 may be a combination of both adsorption and precipitation on the surface of the adsorbent. It can be inferred from the studies that both saw dust and neem bark had maximum adsorption capacity at pH 5, if the precipitated amount is not considered in the calculation. Therefore, the optimum pH for Cd(II) adsorption is 5. The same trend has also been reported in the removal of Cd(II) ions by other adsorbent materials such as Chitosan-Coated Perlite Beads [14]. The pH range for adsorption of Pb(II) on saw dust and neem bark was chosen as 3-7 in order to avoid precipitate in the form of lead chloride and lead hydroxides, which has been estimated to occur at pH<2.0 for PbCl2 and pH>6.5 for Pb(OH)2 [15]. The effect of pH on adsorption efficiencies are shown in Figure 1. Removal of Pb(II) increases with increasing solution pH and a maximum value was reached at an equilibrium pH of around 5 in each of the cases if the precipitated amount is not considered. The same trend has also been reported in the removal of Pb(II) ions by other vegetable materials such as spent grain [16] and crop milling waste [17]. The metal ions in the aqueous solution may undergo solvation and hydrolysis. The process involved for metal adsorption is as follows [18], M2+ + nH2O = M (H2O)n2+ (1) M(H2O)n 2+ = [M(H2O)n-1(OH)]+ + H+ (2) M 2+ + nH2O [M(H2O)n-1(OH)]+ + H+ (3) The pKa value for Cd(II) and Pb(II) are 10.1 and 7.7 respectively. Perusal of the literature on metal speciation shows that the dominant species is M(OH)2 at pH > 6.0 and M2+ and M(OH)+ at pH < 6.0. Maximum removal of metal was observed at pH 5 for adsorption. On further increase of pH adsorption decreases probably due to the formation of hydroxide of cadmium and lead because of chemical precipitation [19]. The optimum pH value for adsorption was found to be 5. 3.2 Effect of adsorbent type and its concentration Experiments have been conducted using constant initial pH 5 for adsorption of both Cd(II) and Pb(II) and constant equilibrium contact time (240 min and 180 min for adsorption of Cd(II) and Pb(II) respectively). The effect of adsorbent dosage on adsorption of Cd(II) on saw dust and neem bark are shown in Figure 2. It is observed that the adsorbed amount of metal ions was increased by increasing the adsorbent dosage for each case. As the adsorbent dosage increases, the number of adsorbent particles surrounded by metal ions or ratio of the number of the adsorbent particles to metal ions increases in the solutions result more ions attached to the adsorbent surfaces. It is clear that, the optimum removal efficiency have been achieved at an adsorbent dosage level of 10 g/L for the adsorption on both the adsorbents. The variation in sorption capacities between the two adsorbents could be related to the type and concentration of surface group responsible for adsorption of metal ions from solution [20]. Different magnitude of attraction power of the metal ions by saw dust and neem bark, and different ability of complex formation of Cd(II) with the functional groups present on the surface of the adsorbents surfaces are responsible [21]. Effect of adsorbent dosage on the percent removal of Pb(II) are shown in Figure . These figures indicated that the adsorption increases from 1g/L adsorbent dosage to 7.5 g/L adsorbent dosage for adsorption on both saw dust and neem bark. It is also seen from the figure (Figure 2) that a further increase in the adsorption dosage (greater than 7.5 g/L) does not affect the adsorption greatly on the adsorption on both the adsorbents. These results can be explained on a
Ka

consequence of a partial aggregation, which occurs at higher adsorbent dosage [22]. Therefore, adsorbent dosage is selected as 7.5 g/L for both the adsorbent during further experiments. 3.3 Effect of contact time Experiments have been conducted using constant adsorbent dosage (7.5 and 10 g/L for adsorption of Cd(II) and Pb(II) respectively) and constant initial pH 5. Variation of percentage removal of metal ion with contact time was studied in this section. Figure show the effect of contact time on the adsorption of Cd(II) on saw dust and neem bark. It is seen from figures (Figure 3) that the adsorption yield of Cd(II) steeply increases with rise in time up to 60 min. Between 60 min to 120 min there is no considerable increase in adsorption. After 120 min of contact time major adsorption process has been completed. Accordingly, all further batch experiments have been conducted for a contact time of 3 h to ensure the equilibrium is reached. Effect of contact time on adsorption is depicted in Figure. The curve rose steeply within 45 min and reached almost constant after the 90 min of contact time in case of both the adsorbents. After 90 min of contact time major adsorption processes have been completed. Accordingly all the batch experiments have been conducted for a contact time of 2 h to ensure equilibrium is achieved. 3.4 Adsorption kinetics study The rate kinetics of Cd(II) and Pb(II) adsorption on the saw dust and neem bark have been analyzed using pseudo first-order [23], pseudo-second order [24] and intraparticle diffusion models [25]. The conformity between experimental data and the model predicted values is expressed by correlation coefficients, r2 and chi square, 2. Lagergren model The integral form of the Lagergren (1898) model generally expressed in Equation (3.3) as follows, K t log ( q e q ) = log q e ad (4) 2.303 The plot of log(qe qt) versus t give a linear relationship from which Kad and qe can be determined. The values of rate constants, r2 and 2 which can be obtained from equation (Equation 5) for both the adsorbents are shown in Table 2. 2 ( qt qtm ) 2 (5) t = qet Pseudo second order model The kinetics of adsorption process may also be analyzed by pseudo second order rate equation (Ho and McCay, 1998). The linearized form of Equation (3.7), which represents the pseudo second order model, is expressed as t 1 1 = + t (6) 2 qt k 2qe qe Figure 1 show pseudo second order plots. The values of pseudo second order rate constants along with correlation coefficients, r2 and chi square, 2 are shown in Table 2. The pseudo second order rate constant, k2 is decreased while h2 and qe values increase with increase in initial Cr(VI) ion concentration. Intraparticle diffusion model The intraparticle diffusion model is based on the theory proposed by Weber and Moris (1963). According to this theory the model Equation 7 can be expressed as qt = K id t 0.5 + C (7) Data points are related by two straight lines - first straight portion depicting the macropore diffusion and second representing the micropore diffusion. The deviation of straight

lines from the origin may be due to difference in rate of mass transfer in the initial and final stage of adsorption. Further, such deviation of straight line from the origin indicates that the pore diffusion is not sole rate-controlling step. The values of rate constants and correlation coefficients for each model are shown in Table 2. It is observed from the Table 2 that pseudo second order model fits best with the experimental data than the other models. 3.5 Determination of effective diffusion coefficient for adsorption Adsorption data obtained from kinetic study could be described well by the models given by Boyd et al. [26]. Diffusion found to be rate controlling in the adsorption of Cd(II) and Pb(II) onto the particles of spherical shape. Effective diffusion co-efficient for the solution of divalent exchangeable ion can be determined using the equation (Equation) 2 1 ln (8) = 2 Det 2 1 F ( t ) Ra Where plot of ln[1/(1-F2(t))] versus t provide a line from whose slope 2De /r2 the diffusion coefficient, De can be calculated. The value of diffusion co-efficient as calculated from the equation is tabulated in Table 3. The value of De, fall well within the values reported in literature, especially for chemisorptions system (10-9 - 10-17 m2/s) [27]. 3.5 Adsorption isotherms The adsorption isotherm for the removal of metal ion was studied using initial concentration of between 10 and 300 mg/L at an adsorbent dosage level of 5.0 g/L for Pb(II) 30oC. Langmuir isotherm Equilibrium adsorption of Pb(II) assuming monolayer adsorption onto a surface with a finite number of indentical sites is represented by Langmuir adsorption isotherm model [28] Ce C 1 = + e (9) qe q max b q max Linear plots of Ce/qe vs. Ce (Figure 5) were employed to determine the value of qmax (mg/g) and 2 b (L/mg). The data obtained with the correlation coefficients (r2) and e obtained using equation (Equation) are listed in Table 4. 2 ( qe qem ) 2 (10) e = qem Freundlich isotherm The Freundlich adsorption isotherm [29] is an empirical equation employed to describe heterogeneous systems, in which it is characterized by the heterogeneity factor, n. The linear form of Freundlich adsorption isotherm takes the following form
log q e = log K f + 1 log C e n

(11)

2 The values for Freundlich constants and correlation coefficients (r2) and e for the adsorption process are presented in Table 4. The values of n between 1 and 10 (i.e.1/n less than 1) represent a favorable adsorption The values of n, which reflects the intensity of adsorption, also reflected the same trend. The n values obtained for the adsorption process represented a beneficial adsorption.From the Table 4, it is seen that experimental data for both Cd(II) and Pb(II) adsorption are better fitted to Langmuir than Freundlich adsorption isotherm. Therefore uptake of both Cd(II) and Pb(II) ion preferably follows the monolayer adsorption process.

Dubinin-Radushkevich (D-R) isotherm The D-R isotherm [30] was employed in the following linear form: ln Cabs = ln X m 2 (12) The Polanyi potential [31], , can be expressed as, 1 = RT ln(1+ ) (13) Ce A plot of ln Cabs vs 2 in Figure 6 gave a straight line from which values of for Cd(II) and Pb(II) was evaluated. Using the calculated value of , it was possible to evaluate the mean sorption energy, E, from 1 E= (14) 2 The value of E for the adsorption (Table 5) are in the range of 9-16 kJ/mol which indicate that adsorption of Cd(II) and Pb(II) on both the adsorbents are to be chemical in nature [32]. 4. Conclusions The obtained results can be summarized as follows, (1) Maximum adsorption at pH 5-and at higher pH precipitation of hydroxyl species onto the adsorbents . (2) Maximum uptake was obtained at adsorbent dosage of 7.5 g/L and 10 g/L for adsorption of Cd(II) and Pb(II) respectively, which may be considered as optimum adsorbent dosage level at the specified conditions. (3) The equilibrium time for adsorption of Cd(II) and Pb(II) from aqueous solutions was achieved within 3 h and 2 h of contact time respectively. (4) The experimental data were better described by pseudo 2nd order model as evident from correlation co-efficient (r2) and 2 values. (5) The effective diffusivity calculated using Vermeulens approximation was indicate that the interaction between both Cd(II) and Pb(II) on saw dust and neem bark are chemical in nature. (6) Langmuir adsorption isotherm models were better fitted than Freundlich adsorption isotherm model for all the cases of adsorption. (7) Sorption energy calculated from Dubinin-Raduskevich (D-R) isotherm indicated that the adsorption processes are chemical in nature for both the metal ion. Nomenclature b = Langmuir constant (Lmg-1) C0 = Initial concentration of metal ion in solution, (mgL-1) Ct = Concentration of metal ion after time t, (mgL-1) E = Mean sorption energy, (kJmol-1) K2 = Pseudo-second-order rate constant of adsorption [(mg/g) min] Kad = Lagergren rate constant (min-1) Kf = Measure of adsorption capacity (mg/g) Kid = Intra-particle rate constant [(mg/g) min1/2] m = Amount of adsorbent added in gm n = Freundlich constants, intensity of adsorption q = Amount adsorb per gm of the adsorbent (mg/g) qe = Amount adsorb per gm of the adsorbent at equilibrium qmax = Maximum adsorption capacity(mg/g)

qt qtm qem r2 t V F(t)

= = = = = = =

Xm = Greek letter = constant related to energy (mol2/kJ2) = Polanyi potential (kJ 2/ mol2)

Amount adsorb per gm of adsorbent at time t (min) Amount of metal ion adsorbed per gm of adsorbent according to kinetic model (mg/g). Amount of metal ion adsorbed per gm of adsorbent according to isotherm model (mg/g). Correlation coefficient Time, minute Volume of the solution in mL Amount adsorbed per gm of adsorbent at time/Amount adsorbed per gm of adsorbent at equilibrium Maximum adsorption capacity, (mmol/g)

References [1] Cadmium an environment toxicant, New letter, Central Pollution Control Board, 2007, available at http://www.cpcb.nic.in/News%20Letters/Latest/cadmium/contentCADMIUM.html , dated 1.9.2007. [2] Chemical prpperties of cadmium Health effects of cadmium Environmental effects of cadmium, 2007, available at http://www.lenntech.com/periodic-chart-elements/cden.htm , dated 1.9.2007 [3] L.Jrup, M. Berglund, C. G. Elinder, G. Norberg and M. Vahter, Health effects of cadmium exposure a review of the literature and a risk estimate, Scand. J. Environ. Health, 24 Supppl. 1 (1998) 1-51. [4] Lead Poisoning,availablehttp://www.nsc.org/library/facts/lead.htmdated 1.9. 2007 [5] IS 10500 1992 Drinking water specification (Reaffirmed 1993), available http://www.hppcb.nic.in/EIAsorang/Spec.pdf date 8.9.2007 [6] http://www.epa.gov/safewater/contaminants/index.html dated 8.9.2007 [7] http://www.who.int/water_sanitation_health/dwq/gdwq3rev/en/index.html, dated 8.9.2007. [8] O. S. Amuda, A. A. Giwa, I. A. Bello, Removal of heavy metal from industrial waste water using modified activated coconut shell carbon, Biochem. Eng. J. 36 (2007) 174181 [9] M. Sekar, V. Sakthi, S. Rengaraj, Kinetics and equilibrium study of lead(II) onto activated carbon prepared from coconut shell, J. Col. Int. Sci. 279 (2004) 307-313 [10] A. Jusoh, L. S. Shiung, N. a Ali, M. J. M. M Noor, A simulation study of the removal efficiency of granular activated carbon on cadmium and lead, Desal. 206 (2007) 9-16. [11] D. C. K. Ko, J. F. Porter, G. Mckay, Mass transport model for the fixed bed sorption of metal ions on bone char, Ind. Eng. Chem. Res. 42 (2003) 3458-3469 [12] Standard methods for examination of water and wastewater, 1998. 20th edition, APHA, AWWA. Washington D.C., New York. [13] C. N. Sawyer, P. L. McCarty, G. F. Parkin, Chemistry of Environmental Engineering, 5th Edition, McGraw-Hill, NY, 2002. [14] S. Hasan, A. Krishnaiah, T. K. Ghosh, D, S. Viswanath, V. M. Buddu, E. D. Smith Adsorption of divalent cadmium Cd(II) from aqueous solutions onto chitosancoated perlite beads Ind. Eng. Chem. Res. 45 (2006) 5066-5077 [15] C. F. Baes, R.E. Mesmer, The hydrolysis of cations, Wiley, New York, 1976 7

[16]

K. S. Low, C.K. Lee, S.C. Liew, Sorption of cadmium and lead from aqueous solutions by spent grain, Process Biochem. 36 (2000) 1-5. [17] A. Saeed, M. Iqbal, M.W. Akhtar, Removal and recovery of lead (II) from single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black gram musk), J. Haz. Mat. B 117 (2005) 65-73. [18] G. Wulfsberg, Principles of descriptive chemistry, Brookes/Cole Publishing Montery CA, p-25 1987. [19] S. Schiewer, B. Volesky, Modelling of proton-metal ion exchange in biosorption, Environ. Sci. Technol. 29 (1995) 3049-3058. [20] Dakiky, M., M. Khamis, M. Manassra, and M. Mereb, Selective adsorption of Chromium (VI) in industrial waste water using low cost abundantly available adsorbents, Adv. Env. Res. 6 533-540 (2002). [21] Ucer, A., A. Uyanik and S. F. Aygun, Adsorption of Cu(II), Cd(II), Zn(II), Mn(II) and Fe(III) ions by tannic acid immobilized activated carbon, Sep. Purifn. Technol. 47 113-118 (2006). [22] Karthikeyan, S., R. Balasubramanian, C. S. P. Iyer, Evaluation of marine algae Ulva fascita and Sargassum sp. for the biosorption of Cu(II) from aqueous solution, Biores. Technol. 98 452455 (2007). [23] S. Lagergren, Zur theorie der sogenannten adsorption geloster stoffe. Kungliga Sevenska Vetenskapasakademiens, Handlingar 24 (1898) 1-39. [24] Y. S. Ho, G. Mckay, D. J. Wase, C. F. Foster, Study of the sorption of divalent metal ions on to peat, Ads. Sci. Tech. 18 (2000) 639 - 650. [25] W. J. Weber, J. C. Morris, Kinetics of adsorption on carbon from solution. J. Sanit. Eng. Div. Am. Soc. Civ. Eng. 89 (1963) 31-60. [26] Boyd, G. E., A. D. Anderson and L. S. Mayers, The exchange adsorption of ions from aqueous solutions on organic fly ash, Kinetic II, J. Am. Chem. Soc. 69 2836-2848 (1947). [27] V.C. Srivastava, I. D. Mall, I. M. Mishra, Adsorption of toxic metal ions onto activated carbon Study of adsorption behavior through characterization and kinetics, Chem. Eng. Proc. Online 22 Apr., 2007 [28] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica, and platinum, J. Am. Chem. Soc. 40 (1918) 1361-1368. [29] H. Freundlich, Adsorption in solution, Phy. Chem. Soc. 40 (1906) 1361-1368. [30] M. M. Dubilin, L.V. Radushkevich, Proc. Acad. Sci. USSR, Phys. Chem. Sec. 55 (1947) 331 [31] M. Polanyi, Theories of the adsorption of gases. A general survey and some additional remarks, Trans. Faraday Soc. 28 (1932) 316. [32] R. Ahmed, T. Yamin, M. S. Ansari, S. M. Hasany, Sorption behaviour of Lead(II) ions from aquous solution onto Harro River Sand, Ads. Sci. Tech. 24(6) (2006) 475-485

Table 1 Tolerance limits for heavy metal concentration in drinking water and discharge into inland surface waters Heavy Metal Drinking water mg/L Cd(II) Pb(II) 0.01 0.05 IS 10500 1992 [5] Discharge in Discharge inland surface in public water sewers mg/L mg/L 2.00 0.10 1.00 0.10 EPA [6] Drinking water mg/L 0.005 0.015 WHO [7] Drinking water mg/L 0.003 0.01

Table 2 Rate Kinetics for adsorption of Cd(II) and Pb(II) by sawdust and neem bark Adsorbents Metal ion Lagergren 1st Order Kad x102 (min-1) Saw Dust Saw dust Neem bark Neem bark Cd(II) Pb(II) Cd(II) Pb(II) 4.09 4.145 3.63 6.190 0.995 0.996 0.991 0.997 10.765 2.111 8.976 0.989 r2 2 Pseudo 2nd Order K2 (g.mg1 .min-1) 0.0448 0.1077 0.156 0.125 r2 2 Weber and Moris Kid x102 (mg.g1 .min-1/2) 6.31 15.35 6.77 19.32 r2 2

0.995 0.997 0.999 0.996

0.001 0.042 0.014 0.092

0.961 0.996 0.991 0.971

0.199 0.538 0.335 0.843

Table 3 Determination of effective diffusion coefficient Metal Cd(II) Pb(II) De 1012 m2/s 369.433 239.269 Saw dust r2 0.998 0.995 Neem bark De 1012 r2 m2/s 260.399 0.9897 249.403 0.9912

Table 4 Langmuir and Freundlich adsorption isotherm constants for adsorption ________________________________________________________________________ Langmuir Freuindlich Adsorbents Metal ion qmax b (mg g-1) (L mg-1) r2 2 Kf n r2 2 Sawdust Cd(II) 26.73 0.053 0.990 0.090 1.62 1.54 0.977 0.805 Sawdust Pb(II) 88.49 0.025 0.978 0.179 2.13 1.18 0.997 0.355 Neem bark Cd(II) 25.57 0.056 0.984 0.438 1.65 1.52 0.975 0.632 Neem bark Pb(II) 83.33 0.023 0.988 0.084 2.03 1.16 0.996 0.468 ________________________________________________________________________ Table 5 Dubinin-Radushkevich (D-R) isotherm parameter and activation energy for adsorption Metal ion Cd(II) Cd(II) Pb(II) Pb(II) Adsorbents DubininRadushkevich Constant -0.00533 -0.00488 -0.0049 -0.0051 Activation energy kJ/mol 9.415 9.911 9.911 9.950 Correlation coefficient r2 0.9989 0.9907 0.9907 0.9967

Saw dust Neem bark Saw dust Neem bark

10

100

100

Percentage removal of metal ion, %

80

Percentage removal of metal ion, %

60

80

40

Symbol Adsorbents Metal Ion Sawdust Cd(II) Neembark Cd(II) Sawdust Pb(II) Neembark Pb(II)

Symbol Adsorbents Metal Ion Sawdust Cd(II) Neembark Cd(II) Sawdust Pb(II) Neembark Pb(II)

20

4 initial pH

10

60

14 21 Adsorbent dosage (g/L)

28

35

Figure 1 Effect of pH on adsorption

Figure 2 Effect of adsorbent dosage on adsorption

100 400 Percentage removal of metal ion, %

Symbol Adsorbents Sawdust Neembark Sawdust Neembark Metal Ion Cd(II) Cd(II) Pb(II) Pb(II)

80 300

60 t/q 40
Symbol Adsorbents Metal Ion Sawdust Zn(II) Neembark Zn(II) Sawdust Cd(II) Neembark Cd(II)

200

100

20

80

160 contact time, min

240

320

80

Figure 3 Effect of contact time on adsorption

160 time,min

240

320

Figure 4 Pseudo scond order plot for adsorption

5
Symbol Adsorbents Sawdust Neembark Sawdust Neembark Metal Ion Cd(II) Cd(II) Pb(II) Pb(II)

-8
Symbol Adsorbents Sawdust Neembark Sawdust Neembark Metal Ion Cd(II) Cd(II) Pb(II) Pb(II)

-9

-10

ln Cabs

Ce/qe

-11

-12

-13 0 20 40 Ce 60 80 100

300

600

900

1200

2
Figure 6 D-R plot for adsorption

Figure 5 Langmuir plot for adsorption

11