REMOVAL OF FLUORIDE FROM GROUND WATER BY USING MODIFIED BARK OF TERMINALIA CHEBULA (HARITAKI)

International Journal of Civil Engineering and Technology (IJCIET) Volume 7, Issue 6, November-December 216, pp. 21 3, Article ID: IJCIET_7_6_3 Available online at http://www.iaeme.com/ijciet/issues.asp?jtype=ijciet&vtype=7&itype=6 ISSN Print: 976-638 and ISSN Online: 976-6316 IAEME Publication REMOVAL OF FLUORIDE FROM GROUND WATER BY USING MODIFIED BARK OF TERMINALIA CHEBULA (HARITAKI) Ranjit N. Patil Research Scholar, G. H. Raisoni College of Engineering, Nagpur, Maharashtra, India P. B. Nagarnaik Dean Academics, G. H. Raisoni College of Engineering, Nagpur, Maharashtra, India D. K. Agrawal Professor, B.D. College of Engineering, Sevagram, Maharashtra, India ABSTRACT In this research investigation, the Modified bark of Terminalia Chebula (MTC) was found a predominant promising bio-adsorbent for the removal of fluoride content from aqueous solution. The method of adsorption used in batch experimental analysis for ph (2-12), dose (.5-5. g/l), time interval (6-72 Min.), initial concentration (2.5-15 mg/l),particle size (15-6µm). The maximum removal obtained at ph range 6-8 for the optimal conditions of other parameters. The data fitted well in the Langmuir and Freundlich isotherm. Key words: Fluoride, Bio-adsorbent, Langmuir & Freundlich Isotherm. Cite this Article: Ranjit N. Patil, P. B. Nagarnaik and D. K. Agrawal, Removal of Fluoride from Ground Water by Using Modified Bark of Terminalia Chebula (Haritaki). International Journal of Civil Engineering and Technology, 7(6), 216, pp.21 3. http://www.iaeme.com/ijciet/issues.asp?jtype=ijciet&vtype=7&itype=6 1. INTRODUCTION Lot many research has been performed by researchers on defluoridation from synthetic solution because of its ill effect on to human body [1]. The quantity of fluoride ions more than the limit in drinking water causes dental and skeletal fluorosis [2]. The World Health Organization provides the limiting guideline values for fluoride in drinking water is 1.5 mg/l and 1. mg/l. The important action is to provide the safe drinking water. In many parts of the country no alternative source is available for drinking purpose therefore it is necessary to provide the treatment for the removal of fluoride ions. The method of adsorption is considered a more efficient method for the removal of fluoride from drinking water with these comparisons of other methods such as Donnan dialysis, reverse osmosis, nano filtration and electrodialysis [3]. Terminalia Chebula (Haritaki) tree is the medicinal forest herb which is found in all around the country of India. It is also found in the countries such as Shri Lanka, Bangladesh, Nepal, Pakistan, and Turkey. In this research study, the fluoride adsorption capacity of synthesized Terminalia Chebula (Haritaki) were studied in detailed batch adsorption method which includes the parameters such as effect of dose of Terminalia Chebula, initial concentration of fluoride ions, ph, time of contact and particle size of http://www.iaeme.com/ijciet/index.asp 21 editor@iaeme.com

Removal of Fluoride from Ground Water by Using Modified Bark of Terminalia Chebula (Haritaki) adsorbent, adsorption isotherms Freundlich and Langmuir have also been studied and checked from experimental data. 2. MATERIAL AND METHODS All the chemicals used in this study were analytical (AR) grade. Fluoride stock solution was prepared by dilution of 2.21 g of sodium fluoride in 1 ml of double distilled water and the working samples were prepared by using appropriate dilution of stock solution in to double distilled water [4]. 2.1. Preparation of Adsorbent The bark of Terminalia Chebula (Haritaki) was collected from near the forest area of Chandrapur district, Maharashtra State, India. The collected bark was cuts in required size pieces (1-1.5 inch) and washes with water for the easy removal of trash and dust [5]. Then it was kept in to the contact with sunrays for 3 days time period. Well dried bark washed with deionized water and sun dried for a day. 2.2. Modification of Bark Aluminium sulphate (AR grade) was used as a medium for the modification of Terminalia Chebula Bark. By weight 4.5 g of Aluminium sulphate mixed in double distilled water of 2 ml. The weighted bark of Terminalia Chebula (Haritaki) of 2.5 g was added in the mixed. Complete mixed kept in incubator with agitation for three hours at 15 rpm speed. Then it was dried at 15 C for 2.5 hrs. and kept in muffle furnace (Temp.-75 C; Time-3 hrs.).washed the calcined coke by using 1: 2 ratio (coke and distilled water) and allow for shaking for a period of 24 hrs. at 15 rpm agitation. Extra washed provides for 1 hrs and then dried at 15 C for 24 hrs. [6].The modified bark of Terminalia Chebula (MTC) kept in plastic made air tight container for the experimental study. 2.3. Experimental Method Adsorption is a low cost effective method used for the estimation of fluoride ions by observing various parameters i.e. dose, ph, initial concentration, particle size and agitation. The batch experimental study performed in 25 ml plastic made bottles containing 1 ml of test sample. The working laboratory ph adjusted by.1 N HCl or.1 N NaOH. Estimation of Fluoride was done by using UV beam spectrophotometer [7]. 2.4. Plant Description Terminalia chebula is the species of Terminalia (Haritaki or Harda).This tree is found in forest and near the forest area mostly. Terminalia Chebula is also used as a forest herb which is native at India, Nepal, China, Shri Lanka, Malaysia, Vietnam, Bhutan, Bangladesh, Myanmar and Pakistan mostly. These trees are found in medium to tallest in height. The leaves are oval in shape and found small and medium in size (Figure1). [8] http://www.iaeme.com/ijciet/index.asp 22 editor@iaeme.com

Ranjit N. Patil, P. B. Nagarnaik and D. K. Agrawal Figure 1 [https://www.flickr.com/photos/dinesh_valke/33917 7397] 3. RESULTS AND DISCUSSION 3.1. Physical Characterization Table 1 Proximate & Ultimate analysis of MTC % MC % VM % AC % FC % H % N 1.9 28.1 31.24 38.76 3.22.48 Proximate analysis of MTC shows the results of percentage of moisture content, volatile matter, ash content and fixed carbon while in ultimate analysis resulted percentage of hydrogen and Nitrogen obtained in modified bark of Terminalia Chebula. The modified bark has efficient characteristics required for the defluoridation process from ground water (Figure 2). Proximate Analysis of MTC 1 8 Values in % 6 4 2 % MC % VM % AC % FC Figure 2 Proximate analysis of MTC http://www.iaeme.com/ijciet/index.asp 23 editor@iaeme.com

Removal of Fluoride from Ground Water by Using Modified Bark of Terminalia Chebula (Haritaki) 3.2. Fourier Transform Infrared (FTIR) All the spectras were compared according to the assignments given to the peaks so as to see the structural changes occur in natural material during thermal degradation.the comparative study of IR shows almost flattering of maximum peaks in aluminium sulphate modified coke obtained on thermal degradation. After Carbonization all peaks related to C-OH, CH. CH 2,CH 3,CO and C=O groups are considerably reduce in the MTC coke. The spectra show that many peaks are lost, few peaks are shifted and there is flattering of remaining peaks [9] (Figure 3 A& B). Figure 3 [A] FTIR of Precursor of MTC Figure 3 [B] FTIR of MTC 3.3. Scanning Electron Microscopy (SEM) Figure 4 [A] Unloaded Figure 4 [B] Loaded The study of surface morphology was performed to analyze the uptake capacity of MTC. In this study the effect of aliuminium sulphate treated and modified by calcinations process the surface morphology of loaded and unloaded samples of MTC were obtained adsorbent shown in fig.4a & B. The SEM images of loaded and unloaded MTC were obtained and show its complex and porous surface texture. SEM images show the clear porous morphology of MTC and grainy surface. These may results the enough surface area requires for the fluoride removal [1]. http://www.iaeme.com/ijciet/index.asp 24 editor@iaeme.com

Ranjit N. Patil, P. B. Nagarnaik and D. K. Agrawal 3.4. Effect of Adsorbent Dose This study evaluated the optimum dose required for the removal of fluoride ions from the aqueous solution contained initial fluoride concentration of 5 mg/l.[11] The result shows that the removal efficiency of Modified Terminalia Chebula barks (MTC) charcoal used in different quantity of doses.5-5 g/l is an effective low cost bio adsorbent in the process of adsorption shown in fig.5. The dose of adsorbent increases the percentage of fluoride uptake also increases. The maximum removal observed 94.86% and a dose of 2 g/l was required to achieve prescribed limit of 1 mg/l. The obtained dose (2 g/l) of MTC was used for further study. The quantity adsorbentof Terminalia Chebula shows the good uptake capacity of fluoride ions. 1 8 Dose Vs. qe 3 3 6 4 2 2 2 1 1.5 1 1.5 2 2.5 3 3.5 4 4.5 5 Dose (mg/l) Figure 5 Dose of adsorbent Vs. % removal Initial fluoride concentration 5 mg/l; ph 7; agitation 15 rpm; temp.3 C; Volume of sample 1 ml 3.5. Effect of ph In the method of adsorption ph plays an important role. The research proves that the defluoridation of water by using MTCT was highly dependent on the ph of the test solution. The range of ph selected for this study was 2-12. The fluoride uptake capacity was increased with increase up to ph 8 but it was suddenly down after ph 8 and then after uptake capacity of fluoride ions decreased with increase in ph [12] as shown in figure 6. The result shows that in lower rangep H the adsorption rate of fluoride ions decreased slightly, it may be due to the formation of weak hydrofluoric acid. The drop of ph recorded due to the competition of the hydroxyl in the process of fluoride adsorption [13]. 1 ph Vs. 8 6 4 2 2 4 6 8 1 12 ph Figure 6 ph Vs. % removal http://www.iaeme.com/ijciet/index.asp 25 editor@iaeme.com

Removal of Fluoride from Ground Water by Using Modified Bark of Terminalia Chebula (Haritaki) Initial fluoride concentration 5 mg/l; agitation 15 rpm; temp.3 C; Dose 15 g/l;volume of sample 1 ML 3.6. Effect of Contact Time In the method of adsorption, the study of time of contact plays an important role in the process of fluoride removal from ground water. The results obtained that the fluoride removal capacity of MTC increases with increase in contact time. The maximum required fluoride uptake obtained at 36 Min. shown in figure 7 [14]. 1 Contact Time Vs. 8 6 4 2 12 24 36 48 6 72 Time (Min) Figure 7 Time Vs. Initial fluoride concentration 5 mg/l ; ph 8 ; agitation 15 rpm ; temp.3 C ; Dose 15 g/l; Volume of sample 1 ml 3.7. Effect of Initial Metal Ion Concentration Worldwide the higher fluoride concentration was observed in various countries, India is one of them were the maximum range of fluoride observed in many state. This study also covered the uptake capacity of MTC for the removal of higher fluoride concentration from aqueous solutions. The initial fluoride concentrations 2.5 mg/l-15 mg/l were studied and recoded the percentage removal and the nature of removal. The initial fluoride concentration increases with decreased in percentage removal uptake capacity [15] shown in figure 8. 1 Initial Concentration Vs. 8 6 4 2 5 1 15 Initial Concentration (mg/l) Figure 8 Initial Concentration Vs. http://www.iaeme.com/ijciet/index.asp 26 editor@iaeme.com

Ranjit N. Patil, P. B. Nagarnaik and D. K. Agrawal Initial fluoride conc. 5 mg/l; ph 8; agitation 15 rpm; temp.3c; Dose 15 g/l; Volume of sample 1 ml 3.8. Effect of Particle Size Particle size of adsorbent affects the process of adsorption. In this research particle size ranges of 75-3µm was used for the analysis. The obtained results prove that the removal capacity of adsorbent is also depend on the particle size of adsorbent [16]. The maximum removal of fluoride ions obtained at lower particle size and the result shows the uptake of fluoride ions increases with decrease in particle diameter size [17] shown in Figure 9. It also shows the maximum uptake capacity of adsorbent was obtained at sieve size 75 µm but the smaller size creates a problem of clogging [18]. Particle Size Vs. 1 8 6 4 2 1 2 3 4 5 6 Particle Size (Micron) Figure 9 Particle Size Vs. Initial fluoride conc. 5 mg/l ; ph 8 ; agitation 15 rpm ; temp.3c ; Dose 15 g/l; Volume of sample 1 ml 4. ADSORPTION MODELS The isotherm study focused on the interaction of adsorbate with adsorbent. The data were observed in related in Langmuir and Freundlich adsorption isotherms. The Langmuir isotherm is a presumption depends that the removal due to monolayer sorption happens on a homogeneous surface of adsorbent without any collaboration between adsorbed particles were as Freundlich is equilibrium sorption based adsorption on the heterogeneous surfaces. Following are the linear equations of Langmuir and Freundlich isotherms shown in equation (a) & (b) respectively [19]. 1 = 1 1 + 1 ( ) Equation (a) In the above equation, the fluoride adsorbed capacity is denoted by qe in mg/g and qmax is the maximum amount adsorbed in mg/g; the equilibrium fluoride concentration is denoted by Ce in mg/l; Langmuir isotherm constant is denoted by KL in L/mg. log =log + 1 log Equation (b) http://www.iaeme.com/ijciet/index.asp 27 editor@iaeme.com

Removal of Fluoride from Ground Water by Using Modified Bark of Terminalia Chebula (Haritaki) In equation 2, the equilibrium fluoride concentration is denoted by Ce and qe is the amount adsorbed in mg/g; KF is the empirical constant of Freundlich in mg/g and 1/n is the Freundlich exponent. The linear plot shows the Langmuir and Freundlich isotherm application in Figure 1 & 11. 1 vs. 1 The data plot in both the adsorption shows the good correlation coefficients for Freundlich isotherm as compare to Langmuir. The R 2 value obtained in Freundlich (R 2 =.93) is more than the Langmuir (R 2 =.962). The equilibrium data followed the Freundlich isotherm than the Langmuir. Figure 1 shows the Langmuir isotherm. Langmuir Isotherm 2.5 2. y =.769x -.81 R² =.962 Ce/qe (g/l) 1.5 1..5...5 1. 1.5 2. 2.5 3. Ce (mg/l) Figure 1 Langmuir isotherm The study predicted that the nature of surface adsorbent was heterogeneous and suitable for adsorption. Figure 11 shows the Freundlich isotherm. Freundlich isotherm 1.4 1.2 y = -.156x +.937 R² =.93 Ln(qe) 1..8.6.4.2. 313K -2. -1.5-1. -.5..5 1. Ln(Ce) Figure 11 Freundlich isotherm The adsorption model was prepared and found the data was well fitted in Langmuir than Freundlich isotherm and found the adsorption experiment achieved good adsorption capacity shown in figure 1 & 11[2]. http://www.iaeme.com/ijciet/index.asp 28 editor@iaeme.com

Ranjit N. Patil, P. B. Nagarnaik and D. K. Agrawal 5. CONCLUSION The results conclude that the Modified bark of Terminalia Chebula (MTC) has the good fluoride removal capacity in the process of adsorption. The optimum dose of MTC was found 2 g/l for an initial fluoride concentration of 5 mg/l. Adsorption capacity was obtained more in the ph range of 6-8.The optimal contact time was found 36 minutes. The maximum uptake capacity of (MTC) adsorbent found in lower mesh size IS sieve of 75 µm (passing). The adsorption equilibrium data follows the Langmuir and Freundlich isotherms. REFERENCE [1] A.M. Raichur, M.J. Basu, Adsorption of fluoride onto mixed rare earth oxides, Sep. Purif. Technol. 24 (21) 121 127. [2] I. Abe, S. Iwasaki, T. Tokimoto, N. Kawasaki, T. Nakamura, S. Tanada, Adsorption of fluoride ions onto carbonaceous materials, J. Colloid Interface Sci. 275 (1) (24) 35 39. [3] X.M.Wu, Y. Zhang, X.M. Dou, M. Yang, Fluoride removal performance of a novel Fe Al Cetrimetal oxide adsorbent, Chemosphere, 69 (11) (27) 1758 764. [4] Ranjit N. Patil, DR. P. B. Nagarnaik, DR. D. K. Agrawal, Removal of fluoride from water by using bioadsorbents: a state of art. International journal of pure and applied research in engineering and technology Vol. 3 (9): 272-279 [5] R. Simons, Trace element removal from ash dam waters by nano filtration and diffusion dialysis, Desalination 89 (1993) 325 341. [6] Sanghranta S. Waghmare, Tanvir Arfin, Nilesh Manwar, Dilip H. Lataye, NitinLabhsetwar & Sadhana Rayalu, Preparation and Characterization of Polyalthialongifolia Based Alumina,as a Novel Adsorbent for Removing Fluoride from Drinking Water, Asian J. Adv. Basic Sci.: 215, 4(1), 12-24 [7] Onyango M S, Matsuda H, Alain T. Chapter 1 Fluoride Removal from Water Using Adsorption Technique. Adv. Fluor. Sci. 26; 2:1-48. [8] Ranjit N. Patil, DR. P. B. Nagarnaik, DR. D. K. Agrawal, An Experimental Analysis of Adsorption Behavior of HTB for the Removal of Fluoride. International journal of Engineering Research & Technology special issue 89-9. [9] NatrayasamyViswanathan a, S. Meenakshi, Selective fluoride adsorption by a hydrotalcite/chitosan composite, journal of Applied Clay Science 48 (21) 67 611 [1] Sudhakar M. Rao, B.V. Venkatarama Reddy, S. Lakshmikanth, N.S. Ambika, Re-use of fluoride contaminated bone char sludge in concrete, Journal of Hazardous Materials 166 (29) 751 756 [11] WHO Report, Fluoride and Fluorides: Environmental Health Criteria, World Health Organisation, 1984. [12] M. Rao, A. V. Parwate and A.G. Bhole, Uptake of Nickel from aqueous solution using low cost adsorbent, Enviromedia, 2 (4), (21) 669-675. [13] D. Mangrulkar, R.M.Dhoble, R.N.Kirakate, Defluoridation from Groundwater by Seed Coat of Tur: International J. of Env. Research and Development. Vol. 1, (211), pp. 17-3 [14] Shihabudheen M. Maliyekkal, Sanjay Shukla, Ligy Philip, Indumathi M. Nambi, Enhanced fluoride removal from drinking water bymagnesia-amended activated alumina granules, Chemical Engineering Journal 14 (28) 183 192 http://www.iaeme.com/ijciet/index.asp 29 editor@iaeme.com

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