REMOVAL OF HEAVY METALS BY PHYTOEXTRACTION USING SALVADORA PERSICA

J. Sc. & Tech., Univ. Peshawar, Removal of 20, Heavy 35 Metals (&2), by -2. Phytoextraction Using Salvadora Persica REMOVAL OF HEAVY METALS BY PHYTOEXTRACTION USING SALVADORA PERSICA FAZAL WAHID, IMDAD ULLAH MOHAMMADZAI, ADNAN KHAN, NAUMAN ALI, ZIARAT SHAH Institute of Chemical Sciences, University of Peshawar, 2520 Peshawar, Khyber Pakhtunkhwa, Pakistan Abstract: Salvadorapersica was converted into powdered form and characterized by using Infrared spectroscopy. It has various organic compounds and these compounds contain oxygen and nitrogen in their skeletons and behave superbly as coordinating ligands for cations present in the aqueous solution. The plant showed high sorption capacity for copper, lead and nickel from dilute aqueous solutions. Among these, the maximum sorption capacity was found for copper. The experimental data were adjusted to the Langmuir, Freundlich and Temkin sorption isotherms using both linear and non linear regression methods. All the four types of Langmuir linear equations were applied to linear and non linear regressions. The Langmuir model type provided the lowest error values and fit better to experimental data as compare to the Freundlich and Temkin models. Keywords: Salvadora persica, Freundlich, sorption, Langmuir, heavy metals. Introduction Rapid industrialization and various domestic activities have contributed largely towards introduction of heavy metals into the environment. Heavy metals pollution of aquatic medium is a major concern due to their non-biodegradability and toxicity (Brierley, 990). The most common heavy metals found in waste water are copper, lead and nickel. They are toxic at high concentration (Johns and Marshal, 998; Ngah and Fatinathan, 2008). Excessive intake of copper causes capillary damage, renal and hepatic damage and central nervous system irritation followed by depression (Ajmal, et al., 998). Exposure to nickel results in skin irritation and also causes damage to lungs, nervous system and mucous membrane (Oliver, 997). The presence of lead in drinking water causes various health disorders such as general metabolic poisoning and enzyme inhibition by inorganic lead while organic form is more dangerous (Volesky, 990; Lo et al., 999). Therefore, it is necessary to remove toxic metal ions from wastewater in order to protect aquatic, human and other forms of life. Much attention has been paid for remediation of toxic heavy metals ions from industrial effluents in recent years (Zdemir, et al., 2005; Meunier, et al., 2006). Heavy metals remediation from environment can be achieved either by biotic or aboitic method (Lothenbach, et al., 997; Ng, et al., 2002; Qin, et al., 2007). Conventional methods include chemical precipitation (Nourbakhsh, et al., 994), chemical oxidation/ reduction, ion exchange (Nourbakhsh, et al., 994), filtration, electrochemical treatment, reverse osmosis, membrane technologies and evaporation recovery (Nourbakhsh, et al., 994). These techniques may be ineffective or extremely

Fazal wahid, Imdad Ullah Mohammadzai, Adnan Khan, Nauman Ali, Ziarat Shah expensive (Nourbakhsh, et al., 994). Sorption of heavy metal ions from aqueous solutions by various types of plant wastes is beneficial, because biomasses are readily available in large quantities to support potential demand. Different types of biomaterials have been used to sorb heavy metal ions from the wastewater (Rome, and Gadd, 99; Tiemann, et al., 999), such as papaya wood (Saeed, et al., 2005), maize leaf (Babarinde, et al., 2006), leaf powder (Hanafiah, et al., 2007), rubber (Hevea brasiliensis) leaf powder (Hanafiah, et al., 2006b; Hanafiah, et al., 2006c), peanut hull pellets (Johnson, et al., 2002), sago waste (Quek, et al., 998), tree fern (Ho, and Wang, 2004; Ho, et al., 2004; Ho, 2003), rice husk ash and neem bark (Bhattacharya, et al., 2006), grape stalk wastes (Villaescusa, et al., 2004), Seaweed, mold, bacteria, and yeast (Volesky, and Holan, 995).The advantages of using biomaterials for wastewater treatment include simple technique, good sorption capacity, low cost, availability and easy regeneration (Gaballah, et al., 997). The purpose of the present study was to test the sorption capacity of salvadora persica for cations such as copper, lead and nickel ( Cu 2+, Pb 2+ and Ni 2+ ) from aqueous solution. Infrared spectroscopy is used to identify different Lewis basic centers present in the plant material. The three most commonly used equilibrium models (Langmuir, Freundlich and Temkin) were applied for sorption studies. Both linear and nonlinear regression techniques were used. Four different linear forms of Langmuir models were applied to have better comparison between linear and nonlinear regression techniques. 2 Experimental/ Materials and Methods Materials Salvadora Persica roots were obtained from the local market in Peshawar, Pakistan. Hydrochloric acid (Merck), sodium hydroxide (Merck), lead (Merck), nickel (Merck) and copper (Merck) nitrates were all of analytical grade. Characterization Fourier transformed infrared spectra of samples were obtained in KBr pellets by accumulating 32 scans, Bomem Spectrophometer, MB-series, range 4000 400 cm, resolution 4 cm. The amount of cation sorbed was determined by Perkin Elmer 700 AAS apparatus, keeping in mind the difference between the initial concentration and the concentration after sorption at equilibrium,.the reproducibility was checked at least through one duplicate run for each experimental point. Preparation of sorbent from salvadora persica Salvadora persica roots were cleaned and washed thoroughly with deionized water. The cleaned roots were dried in an oven at 05 C for 4 hours and was powdered with a grinder and kept in a desiccator for further use. Sorption experiments Sorption experiments were carried out by adding approxmately 20 mg of the powdered salvadora persica into a series of polyethylene flasks containing 20.0 cm 3 of metallic cation solution having concentrations ranging from 4.0 0-4 to 8.0 0-3 mol dm -3 to evaluate the sorption capacity. All

Removal of Heavy Metals by Phytoextraction Using Salvadora Persica experiments were performed in duplicate in a batch wise process in an orbital bath at 25 ± o C. In order to obtain the time needed to reach isotherm saturation, kinetic experiments were assayed using similar cation solutions at ph 5.6 for copper, nickel and lead. For this determination, the amount of cation removal as a function of time defined a plateau at 4 h. However, the chosen time was 6 h to ensure the best equilibrium conditions as shown in Fig. 7. The supernatant solutions were separated from the solid through decantation and aliquots of supernatant were taken to determine the quantity of cation remaining through atomic absorption spectrophotometer. The amount of the cation sorbed onto sorbent was calculated by Eq., ni ns m = () Where is the number of mmoles sorbed on sorbent (mmol g - ), ni are the number of moles in the initial solution and ns the number of moles in the supernatant after equilibrium. m is the mass in g of the the sorbent used in each sorption process (Khan et al., 20). Isotherm models Equilibrium isotherm equations are used to portray the experimental sorption process. The equation parameters and the equilibrium models provide information about the sorption mechanisms, the surface properties and affinities of the sorbent. The three most common isotherms for describing sorption systems are the Langmuir, the Freundlich and the Temkin isotherms. Langmuir isotherm model The mathematical expression of modified Langmuir isotherm model is expressed in Eq. 2. Cs Cs + Ns Nsb = (2) where is the sorption capacity at equilibrium, Cs is the equilibrium concentration, Ns and b are the Langmuir constants related to the maximum sorption capacity and the sorption energy, respectively. Maximum sorption capacity Ns represents the monolayer coverage of sorbent species with sorbate and b represents the energy of sorption (Badshah and Airoldi, 20; Allen et al., 2004). Freundlich isotherm model The sorption parameters can be obtained from Freundlich isotherm in linear form as shown in Eq. 3: log = log KF + logcs (3) n Where K F and n are constants and related to the sorption capacity of the sorbent and the sorption intensity. The plot of log versus logcs for the sorption was employed to generate K F and n from the intercept and the slope values, respectively. Temkin isotherm model The Temkin isotherm can be used in linear form as shown in Eq. 4: = nt ln KT + nt ln Cs (4) A plot of lncs versus enables determination of K T, n T and b values. The constant b is related to the heat of sorption, which can be calculated using the following Eq. 5: RT nt = (5) b 3

Fazal wahid, Imdad Ullah Mohammadzai, Adnan Khan, Nauman Ali, Ziarat Shah To evaluate the fitness of the isothermal equation to the experimental equilibrium data, an error function is required to enable the optimization procedure. Three parameters, correlation coefficient (R), chisquare χ 2 and the standard error (SE) of the estimated values were used to determine the validity of each model. The mathematical equation that represents the standard error Table. Langmuir Isotherm and their linear and nonlinear forms NsbCs Cs Cs Cs = = + VsCs + bcs Ns Nsb = + Nsb Cs Ns Vs Cs Table 2. Number of moles sorbed (), Langmuir parameters (Ns and b), coefficient of determination (R 2 ) and standard error (SE) for the interaction of divalent metals with salvadora persica at 25 ± o C, using different linear form of Langmuir isotherm. 4 = Ns + b Cs Isotherm Parameter Type I Type II Type III Type IV (mmol g - ).75.75.75.75 Ns (mmol g - ).84±0.8.93±0.5.92 ±.92.93±4.37 Cu 2+ b (g mmol - ) 2.94±0.54 2.26±0.22 2.32±0.4 2.26±2.26 R 2 0.998 0.99 0.97 0.97 SE 0.03 0.04 0.04 0.04 χ 2 0.009 0.0 0.0 0.0 (mmol g - ) 0.84 0.84 0.84 0.84 Ns (mmol g - ).0±0.8.3±0.87.08±.0.2±.02 Pb 2+ b (g mmol - ).2±0.98 0.88±0.99 0.98±.0 0.98±0.9 R 2 0.988 0.986 0.94 0.94 SE 0.036 0.043 0.040 0.04 χ 2 0.02 0.05 0.04 0.04 (mmol g - ).53.53.53.53 Ns (mmol g - ) 2.42±.62 2.69±0.37 2.5±2. 5 2.63±0.57 Ni 2+ b (g mmol - ) o.25±0.4 0.2±.74 0.23±4.2 0.2±0.2 Cs = bns b Vs Cs Vs Cs R 2 0.960 0.997 0.99 0.99 SE 0.06 0.08 0.07 0.08 χ 2 0.0 0.03 0.03 0.03

Removal of Heavy Metals by Phytoextraction Using Salvadora Persica (SE) and chi-square χ 2 are shown in Eq. 6 and 7: m SE = ( m P x = i= N i= i N cali (7) 2 2 ( f exp fcali) 2 exp i cali) (6) Where exp is the number moles, experimentally sorbed. calc is the number of calculated moles from each model, m is the number of points present in each isotherm and P is the number of parameters in each equation (Sousa et al., 2009; Basha et al., 2008). Results and Discussion Infrared spectroscopy FTIR spectrum of the plant (salvadora persica) showed a broad absorption band at about 3298 cm - reflects OH stretching vibrations, which can also overlaps with the possible stretching frequency of amino group in the same region as shown in Figure. The bands at 2927 and 2830 cm - are assigned to C H stretching vibrations. The band at 627 cm - is due to the C=C stretching vibration and band at 558 is due to C=O (Khan et al., 20). A band near 430 cm - is due to CH 3 deformation (Fatma, 2000). The spectrum of salvadora roots showed a band at 257 cm - is assigned to C O C and OH deformation. The band at 049 cm - is assigned to asymmetrical bridge C O C stretching and at 08 cm - is associated with the absorption of asymmetric in plane ring stretching (Fatma, 2000). The weak band appearing at 950 cm - is characteristic of C H bending vibration (Ashraf, 2006). Sorption study Salvadora persica contains different straight chain and aromatic compounds. These compounds have nitrogen and oxygen which can act as good chelating sites for cations sorption from aqueous solution. The quantity of cations sorbed, the maximum sorption capacity Ns, the interaction energy b and the coefficient of determination (R 2 ) obtained from the linear form of the Langmuir model type are summarized in Table 2. The plant showed greater sorption capacity for Cu 2+, Pb 2+ and Ni 2+ and its order of cations sorption is Cu 2+ > Ni 2+ > Pb 2+ as shown in Figs. 2 and 3. The Langmuir, Freundlich and Temkin are the three most common isothermal models that are applied to sorption study in equilibrium at solid/liquid interface. The linear forms of these three models, using Langmuir model type are shown in Fig. 4. The Langmuir isotherms transformed into four different linear forms and all of which were applied to the sorption study. The parameters of these equations and equilibrium models often lead us to understand the mechanisms of sorption, surface properties and affinity of the sorbent. The calculated values of Langmuir, Freundlich and Temkin isotherms for nickel are shown in Fig. 5. Both linear and nonlinear regression analysis were used to evaluate sorption process for better results. The Langmuir, Freundlich and Temkin isotherms obtained, using non linear regression techniques for sorption of copper onto Salvadora persica are shown in Fig. 6. 5

Fazal wahid, Imdad Ullah Mohammadzai, Adnan Khan, Nauman Ali, Ziarat Shah Table 3. Number of moles sorbed (), the Freundlich (n and K f ), the Temkin (b and K T ) parameters, coefficient of determination(r 2 ), and the respective error for interaction of divalent metals with salvadora persica at 25 ± o C using linear method. Isotherm Constant Pb 2+ Cu 2+ Ni 2+ Freundlich K f (mmol g - ) 0.52±0.28.26±0.0 0.48±0.3 n 2.58±0.38 4.6±0.2.57±0.63 R 2 0.885 0.832 0.960 SE.34.4 0.65 χ 2 0.96 0.56 0.27 Temkin K T (mmol dm -3 ) 0.24±0.54 86.53±.30 2.49±0.59 b (kj mol - ) 0.578±0.23 0.723±0.29.33.46±0.53 R 2 0.923 0.879 0.973 SE 0.08 0.68 0.07 χ 2 0.04 0.06 0.05 Table 4. Number of moles sorbed (), the Freundlich (n and K f ), Temkin (K T and b) Parameters, coefficient of determination(r 2 ) and respective error for interaction of Cu 2+, Pb 2+ and Ni 2+ with salvadora persica at 25 ± o C, using non-linear method. Isotherm Constant Cu 2+ Pb 2+ Ni 2+ Langmuir (mmol g - ).75 0.84.53 Ns (mmol g - ).90±0.03.05±0.04 2.3±0.6 b (g mmol - ) 2.4 ±0.8.08±0.4 0.28±0.04 R 2 0.980 0.966 0.977 χ 2 0.002 0.00 0.005 Freundlich K f (mmol g - ).29±0.05 0.54±0.02 0.55±0.05 n 5.4±0.89 3.02±0.46.92±0.22 R 2 0.834 0.875 0.928 χ 2 0.08 0.005 0.00 Temkin K T (mmol dm -3 ) 9.04±58.82 0.29±3.03 2.53±0.30 b (kj mol - ) 0.76±0.43 0.723±0.43.34±0. R 2 0.888 0.932 0.973 χ 2 0.02 0.002 0.006 It is observed that the predicted values of constant and coefficient of determination for four linear forms of the Langmuir isotherm are quite different as shown in Table 2. The value of coefficient of determination obtained from the Langmuir isotherm type, is greater than those of other three linear equations. Error functions, SE, and chi-square χ 2 showed minimum values for the Langmuir model type, than for other three types, that suggests that Langmuir model type fits better to the experimental data. The excellent fitness of the Langmuir isotherm type to the experimental data confirms that the sorption occurs in monolayer, each 6

Removal of Heavy Metals by Phytoextraction Using Salvadora Persica molecule has the same activation energy and the sorbate/ sorbate interaction is negligible. The error functions for the Freundlich isotherm showed higher error values than the Langmuir type as shown in Table 3. The isothermal parameters of the three models were also determined by using non-linear regression analysis. It is to be noted that the values of constants of the Langmuir isotherm, determined by this method, are very close to the results of the Langmuir model Type. However, the values of different error functions corresponding to the non-linear Langmuir equation are smaller than those of the Freundlich and the Temkin models as shown in Table 4. Fig. 2. Experimental sorption isotherm for nickel ( ) and copper ( ) on salvadorapersica The non-linear regression analysis corresponds to the best way to select the isotherm that fits the experimental data. This method involves an attempt to minimize the distribution of errors between experimental data and the isotherm considered (Sousa et al., 2009). Both linear and non-linear regression analysis produce different models as the best fitting isotherm for the given set of data, thus indicating a significant difference between the analytical methods. Fig. 3. Experimental sorption isotherm for lead ( ) on salvadorapersica Fig.. Infrared spectrum of Salvadora Persica 7

Fazal wahid, Imdad Ullah Mohammadzai, Adnan Khan, Nauman Ali, Ziarat Shah Fig. 4. Linear Langmuir sorption isotherm for copper ( ), lead ( ) and nickel ( ) on Salvadorapersica Fig.6. Calculated Langmuir ( ), Freundlich ( ), Temkin ( ) and experimental sorption isotherms ( ) for nickel on salvadorapersica Fig. 5. Nonlinear Langmuir ( ), Freundlich ( ), Temkin ( ) and experimental sorption isotherms ( ) for copper on salvadorapersica Fig 7. Effect of contact time on sorption of copper onto salvadorapersica 8

Removal of Heavy Metals by Phytoextraction Using Salvadora Persica Conclusion Salvadora persica was applied for copper, lead and nickel sorption from dilute aqueous solutions. The maximum sorption capacity was found for copper, obtained through the Langmuir sorption isotherm.the experimental data were adjusted to the Langmuir, the Freundlich and the Temkin sorption isotherms using both linear and non linear regression methods. Four types of Langmuir linear equations were used for better comparison of linear and non linear regression methods. The Langmuir model type provided the lowest error values and fits better to the experimental data as compared to Freundlich and Temkin models. Acknowledgement The authors thank to Centralized Resource Laboratories (CRL) for providing instrumental assistance in research work. References Ajmal, M., Khan, A. H., Ahmad, S., Ahmad, A., 998. Role of sawdust in the removal of copper (II) from industrial wastes. Water Res., 32: 3085 309. Allen, S. J., Mckay, G., Porter, J. F., 2004. Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. J. Colloid Interface Sci., 280: 322 333. Babarinde, N. A. A., Oyebamiji, B. J., Sanni, A. R., 2006. Biosorption of lead ions from aqueous solution by maize leaf. Int. J. Phys. Sci., : 23 26. Badshah, S., Airoldi, C., 20. Layered organoclay with talclike structure as agent for thermodynamics of cations sorption at the solid/liquid interface. J. Chem. Eng., 66: 420 427. Basha, S., Murthy, Z. V. P., Jha, B., 2008. Sorption of Hg (II) from aqueous solutions onto carica papaya: Application of isotherms. Ind. Eng. Chem. Res., 47: 980 986. Bhattacharya, A. K., Mandal, S. N., Das, S. K., 2006. Adsorption of Zn (II) from aqueous solution by using different adsorbents. Chem. Eng. J., 23: 43 5. Brierley, C. L., 990. Bioremediation of metal-contaminated surface and groundwater. J. Geromicrobio., l8: 20 223. Fatma, S. B., 2000. Application of spectroscopic techniques for the identification of organic and inorganic constituents of salvadora persica from Saudi Arabia. Physica A 276: 346-35. Foo, K. Y., Hameed, B. H., 200. Insights into the modeling of adsorption isotherm systems. Chem. Eng. J., 56: 2 0. Gaballah, I., Goy, D., Allain, E., Kilbertus, G., Thauront, J., 997. Recovery of copper hrough decontamination of synthetic solutions using modified barks. Met. Metall. Trans., 28: 3 23. Hanafiah M, A. K. M., Ngah, W. S. W., Ibrahim, S. C., Zakaria, H., Ilias, W. A. H. W., 2006b. Kinetics and thermodynamic study of lead adsorption onto rubber (Hevea brasiliensis) leaf powder. J. Appl. Sci., 6: 2762 2767. Hanafiah, M. A. K., Ngah, W. S. W., Zakaria, H., Ibrahim, S. C., 2007. Batch study of liquid-phase adsorption of lead ions using Lalang (Imperata 9

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