International Journal of Civil Engineering and Technology (IJCIET) Volume 9, Issue 4, April 2018, pp. 993–999, Article ID: IJCIET_09_04_112 Available online at http://iaeme.com/Home/issue/IJCIET?Volume=9&Issue=4 ISSN Print: 0976-6308 and ISSN Online: 0976-6316

© IAEME Publication Scopus Indexed

DEFLUORIDATION OF GROUNDWATER’S OF DARSI MANDAL, , BY USING NATURAL ADSORBENTS

G. Babu Rao Assistant Professor, Department of Civil Engineering, Narasaraopeta Engineering College, Guntur, Andhra Pradesh,

A.V. Rama Raju Assistant Professor, Department of civil Engineering, Bapatla Engineering College, Guntur, Andhra Pradesh, India

S. Kanakambara Rao Associate Professor, Department of Civil Engineering, Narasaraopeta Engineering College, Guntur, Andhra Pradesh, India

ABSTRACT The study area is a mandal in the Prakasam District lies between 150.76’67’’ N and 79068’33’’ E long. The study area is bounded in the by Mundlamuru and mandals in the North, and konakanamitla mandals in the south, Kurichedu and Donakonda mandals in the west and by Talluru and Chimakurthy mandals in the east directions respectively. Fluorine is the most electronegative element present in the earth’s crust. It is present in the form of fluorides in a number of minerals and in many rocks. Fluoride enters into the groundwater mainly by geogenic and anthropogenic actions. Fluoride in drinking water has dual effects (beneficial and harmful) on human health. It is essential in minute quantities for proper growth of bones and teeth in humans. Keywords: Groundwater, Darsi Mandal, Natural Adsorbents Cite this Article: G. Babu Rao, A.V. Rama Raju and S. Kanakambara Rao, Defluoridation of Groundwater’s of Darsi Mandal, Prakasam District, Andhra Pradesh by using Natural Adsorbents, International Journal of Civil Engineering and Technology, 9(4), 2018, pp. 993–999. http://iaeme.com/Home/issue/IJCIET?Volume=9&Issue=4

1. INTRODUCTION Fluorine is the most electronegative element present in the earth’s crust. It is present in the form of fluorides in a number of minerals and in many rocks [1]. Fluoride enters into the

http://iaeme.com/Home/journal/IJCIET 993 [email protected] Defluoridation of Groundwater’s of Darsi Mandal, Prakasam District, Andhra Pradesh by using Natural Adsorbents groundwater mainly by geogenic and anthropogenic actions [2]. Fluoride in drinking water has dual effects (beneficial and harmful) on human health. It is essential in minute quantities for proper growth of bones and teeth in humans. When its concentration is high, it may lead to dental and skeletal fluorosis. It even leads to damage the brain, liver, and kidney, headache, skin rashes, bone cancer, and even death in extreme cases. The maximum permissible limit of fluoride in water may vary depending up on climatic condition. In India it is 1.5 mg/L as per WHO standards [3, 4]. It is estimated that around 260 million people around the world (in 30 countries) are effected by consuming Fluorinated water (>1.0 mg/L; [5]). In India alone, endemic Fluorosis is thought to affect around one million people and is a major problem in 17 of the 29 states, especially Rajasthan, Andhra Pradesh, Tamil Nadu, Gujarat and Uttar Pradesh. Approximately, 62 million people, including 6 million children suffer from fluorosis in the country due to consumption of F--contaminated water [6]. In Andhra Pradesh, the highest F-- affected villages are approximately 195 in Prakasam district of Andhra Pradesh [7]. The first case of endemic fluorosis in the country was reported as long as 1937 in the Prakasam district (a part of erstwhile Guntur district; [8]. There are so many unnoticed F--contaminated groundwater areas in the district. Defluoridation techniques can be broadly classified into two types. They are i) Additive methods, and ii) Adsorptive methods. The methods which are in existence are can be classified into adsorption, Ion exchange, Precipitation and Miscellaneous methods. Adsorption methods by using different adsorbents like sunflower plant dry powder, steam of phytomass, Holly Oke, neem bark powder, activated cotton jute carbon, bagasse ash, burnt bone powder, phosphate-treated saw dust, bone char, etc. came into existence [9]. The present study aims in identifying the fluoride levels of the groundwater in the study area and also effective de-fluoridation by using different natural and low cost-materials.

2. STUDY AREA The study area is a mandal in the Prakasam District lies between 150.76’67’’ N and 79068’33’’ E long. The study area is bounded in the by Mundlamuru and Vinukonda mandals in the North, Podili and konakanamitla mandals in the south, Kurichedu and Donakonda mandals in the west and by Talluru and Chimakurthy mandals in the east directions respectively.

3. MATERIALS AND METHODS About 20 groundwater samples were collected in different locations of the study area in water tight plastic containers.

4. METHODOLOGY The fluoride in the water is measured by using following SPADNS method using a SYSTRONICS-105 spectrophotometer [10]. The fluoride standard sample was prepared in the range of 1 mg/L to 5 mg/L by taking appropriate quantities of standard fluoride solution with distilled water. Then pipette 5 ml each of SPADNS solution and zirconyl acid solution to each standard and mixed well. The spectrophotometer was set to zero absorbance with reference solution and absorbance readings of standard were obtained. Reference solution was used as a blank solution. The wave length of spectrophotometer is taken at 570 nm. The analysis was conducted at room temperature (290±20C).

http://iaeme.com/Home/journal/IJCIET 994 [email protected] G. Babu Rao, A.V. Rama Raju and S. Kanakambara Rao

4.1. Preparation of Adsorbents Four adsorbents were prepared individually by using natural and low cost materials. The adsorbents are 1. Mixture of the bark of moringa olifera and emblica officinalis (amla), the roots of vetiveria zizanoides (vattiveru) and the leaves of cyanodan tactylon (garika) 2. Rice husk powder 3. Tulasi leaves powder 4. Chalk powder

4.2. Preparation of Adsorbents A mixture of the bark of moringa olifera, emblica officinalis (amla), the roots of vetiveria zizanoides (vattiveru) and the leaves of cyanodan tactylon (garika) were collected, washed and dried. The dried material is made in to powder. Then it is passed through the standard sieve 150 and 300 micron and finally it is collected at bottom and is used as adsorbent. Rice husk obtained after sieving through the IS 150 and 300 micron sieves are used as another adsorbent. Tulasi leaves powder collected from plants was used as another adsorbent. Before powdering they were pre-washed with water and dried at room temparature. Then the leaves are crushed by using domestic blender and sieved through 600 micro meter stain–less steel sieve. Chalk powder, form of calcium carbonate with minor amount of silt and clay is collected from classrooms is used as an adsorbent. After the addition of adsorbent, the coagulant activity with one minute of rapid mixing and 15 minutes of slow mixing for flocculation and 60 minutes of settling is done [11]. Then it is followed by rough filtration, rapid sand filter and double filtration that mainly reduces the fluoride content.

5. RESULTS AND DISCUSSION

Table 1 Concentration of Fluoride in the study area S.No Viilage Fluoride(mg/L) 1 Mareddypelem 2.0 2 Pothavaram 3.20 3 Pulimivaripalle 14.0 4 Rajampalli 1.40 5 Ganesh puram 3.40 6 East Venkatapuram 3.0 7 Kattasingannapalem 3.60 8 Lankojanapalli 2.60 9 East Chowtapalem 2.20 10 Yerraobanapalli 2.0 11 Bandiveligandla 4.60 12 Battuvaripalli 12.0 13 Ramachandrapuram 1.20 14 Sai nagar 5.20 15 Darsi 1.60 16 Thummedalapadu 7.0 17 Samanthapudi 1.40 18 V.C.palli 3.60 19 Chandaluru 5.6

http://iaeme.com/Home/journal/IJCIET 995 [email protected] Defluoridation of Groundwater’s of Darsi Mandal, Prakasam District, Andhra Pradesh by using Natural Adsorbents

20 Tanamchintala 6.3 The F- concentration in the study area varies from 1.20 to 14 Mg/L, with an average of 4.30 mg/L The highest F- concentration 14.0 mg/L is observed in Pulimivaripalle Village, where as the lowest concentration 1.20 mg/L is noticed in Ramachandrapuram village (Table1). The experimental analysis was carried out by treating the groundwater with different adsorbents separately. The F--content in the groundwater is measured after specific contact time (15 m, 30 m, 1 hr, 3 hrs, 6hrs, 12 hrs and 24 hrs) with the adsorbent. F- concentration is also measured by increasing the adsorbent dosage (1 gm, 3 gm, 5 gm, 10gm). For experimental analysis highest F- (14 mg/L) concentration water sample was utilized.

5.1. Mixture A mixure of the bark of moringa olifera and emblica officinalis(amla), the roots of vetiveria zizanoides( vattiveru) and the leaves of cyanodan tactylon ( garika) was used because moringa Oleifera as an added advantage over the chemical treatment of water because it is biological and has been reported as edible. Powdered sample of mixture is collected after passing through the sieve is utilized for experimental work. Previous research works suggest that the pores present in the organic and inorganic pollutants from aqueous solution with adsorbent mixture [12]. After 15 mints, 30 mint, 1 hr, 3 hr, 6 hr, 12 hr and 24 hrs of contact time with the mixure of the bark of moringa olifera and emblica officinalis(amla), the roots of vetiveria zizanoides( vattiveru) and the leaves of cyanodan tactylon ( garika), the F- value has reduced from 14 mg/L to 12.2, 11.2, 10.4, 9.7, 8.1, 7.6 and 6.4 mg/L respectively. There was gradual decrease in the efficiency of fluoride % from 13 to 54 with increase in contact time (Table 2). This may be due to chemical constituents present in the Moringa oleifera like 4-(4'- O-acetyl-a Lrhamnopyranosyloxy) benzylisothiocyanate,4-(a-Lrhamnopyranosyloxy) benzylisothiocyanate, niazimicin, pterygospermin, benzyl isothiocyanate, and 4-(a-L- rhamnopyranosyloxy) benzylglucosinolate [13, 14].

Table 2 Variations of fluoride in different contact times with different adsorbents Contact time Mixture Rice husk Tulasi powder Chalk powder 1 2 3 1 2 3 1 2 3 1 2 3 15 m 12.2 1.8 13 13.1 0.9 6 13.2 0.8 6 13.4 0.6 4 30 m 11.2 2.8 20 12.8 1.2 9 12.3 1.7 12 13.1 0.9 6 1 hr 10.4 3.6 26 10.8 3.2 22 10.2 3.8 27 12.7 1.3 9 3 hr 9.7 4.3 31 8.6 5.4 38 8.9 5.1 36 10.5 3.5 25 6 hr 8.1 5.9 42 6.9 7.1 51 7.5 6.5 46 8.6 5.4 38 12 hr 7.6 6.4 46 5.4 8.6 61 6.4 7.6 54 7.2 6.8 48 24 hr 6.4 7.6 54 4.3 9.7 70 5 9 64 6.5 7.5 53 1, 2 and 3 indicates Final Fluoride (mg/L), Reduction fluoride (mg/L) and % removal fluoride respectively in Table 2

5.2. Rice Husk Rice husk along with its ash separately is used as an adsorbent for treating waste water because it is an abundant and low-cost material. The pollutants such as dyes, organic compounds, pesticides, inorganic anions, and heavy metals can be removed very effectively with rice husk.After 15 mints, 30 mint, 1 hr, 3 hr, 6 hr, 12 hr and 24 hrs of contact time with the rice husk, the F- value has reduced from 14 mg/L to 13.1, 12.8, 10.8, 8.6, 6.9, 5.4 and 4.3 mg/L respectively. There was gradual decrease in the efficiency of fluoride % from 6 to 70 with increase in contact time (Table 2). This may be due to rice husk contains abundant

http://iaeme.com/Home/journal/IJCIET 996 [email protected] G. Babu Rao, A.V. Rama Raju and S. Kanakambara Rao floristic fiber, protein and some functional groups such as carboxyl, hydroxy and amidogen, etc. which makes adsorption processes possible [15].

5.3. Tulasi Powder Tulasi is used in Ayurvedic medicine as it contains a number of beneficial compounds such as phytochemicals which possess antibacterial, antiviral, anti-oxidative and adaptogenic properties [16]. Studies proved that the Tulasi powder can be used as effective adsorbent for Defluoridation [17]. After 15 mints, 30 mint, 1 hr, 3 hr, 6 hr, 12 hr and 24 hrs of contact time with the tulasi powder, the F- value has reduced from 14 mg/L to 13.2, 12.3, 10.2, 8.9, 7.5, 6.4 and 5 mg/L respectively. There was gradual decrease in the efficiency of fluoride % from 6 to 64 with increase in contact time (Table 2). This may be due to antibacterial, antiviral, anti-oxidative and adaptogenic properties present in the tulasi leave extracts. [18].

5.4. Chalk Powder Chalk powder contains calcium content which will attract the fluoride ions present in the water and finally help in the defluoridation process. This is a low cost material in nature and has biocompatibility with the human body [2]. After 15 mints, 30 mint, 1 hr, 3 hr, 6 hr, 12 hr and 24 hrs of contact time with the chalk powder, the F- value has reduced from 14 mg/L to 13.4, 13.1, 12.7, 10.5, 8.6, 7.2 and 6.5 mg/L respectively. There was gradual decrease in the efficiency of fluoride % from 4 to 53 with increase in contact time (Table 2). This may be due to chalk is the form of calcium carbonate with minor amount of silt and clay [19].Contact time experimental analysis suggests that maximum defluoridation in water takes place at 24 hrs duration. It is observed maximum in rice husk (70%), tulasi powder (64%), mixture of molinga olifera, garika and amla (54%) followed by chalk powder (53 %; fig.1)

ide

r uo l

F

f mixture o

l a

v rice husk o

m tulasi e r

% chlak Contact Time

Figure 1 contact time vs. Fluoride removal (%)

5.5. Concentration Based The adsorbents removal efficiency was tested by increasing the concentration of adsorbents (ie. 1 gm, 3 gm, 5 gm and 1 gm). The removal efficiency was also tested by increasing the concentration of mixture of the bark of moringa olifera and emblica officinalis (amla), the roots of vetiveria zizanoides (vattiveru) and the leaves of cyanodan tactylon ( garika), (ie. 1gm, 3 gm, 5 gm and 10 gm). The percent reduction efficiency values in 1g, 3g, 5g and 10g are 31%, 44%, 53% and 58% respectively (Table 3). The removal efficiency was also tested

http://iaeme.com/Home/journal/IJCIET 997 [email protected] Defluoridation of Groundwater’s of Darsi Mandal, Prakasam District, Andhra Pradesh by using Natural Adsorbents by increasing the concentration of rice husk, (ie. 1gm, 3 gm, 5 gm and 10 gm). The percent reduction efficiency values in 1g, 3g, 5g and 10g are 34%,44%,61% and 70% respectively (Table 3) The removal efficiency was also tested by increasing the concentration of tulasi powder, (ie. 1gm, 3 gm, 5 gm and 10 gm). The percent reduction efficiency values in 1g, 3g, 5g and 10g are 31%, 42%, 52% and 63% respectively (Table 3). The removal efficiency was also tested by increasing the concentration of chalk powder, (ie. 1gm, 3 gm, 5 gm and 10 gm). The percent reduction efficiency values in 1g, 3g, 5g and 10g are 15%, 31%,54% and 67% respectively (Table 3) .This indicates with increase in adsorbent concentration there is a gradual decrease in the fluoride level. The percent removal efficiency of fluoride has gradually increased from 1 gm, 3gm, 5 gm and 10 gm respectively. The highest removal efficiency at 1 gm is observed in rice husk, at 3 gm it is in rice husk and mixture of molinga olifera, amla and garika. At 5 gm dosage, highest removal efficiency is found in rice husk (61%). Maximum removal efficiency at 10 gm dosage is found in rice husk (70%; Fig. 2).

Table 3 Defluoridation of adsorbents at different dosages Mixture Rice Husk Tulasi Powder Chalk Powder Dosage

(gm) 1 2 3 1 2 3 1 2 3 1 2 3 1 9.6 4.4 31 9.3 4.7 34 9.7 4.3 31 11.9 2.1 15 3 7.9 6.1 44 7.9 6.1 44 8.1 5.9 42 9.6 4.4 31 5 6.6 7.4 53 5.4 8.6 61 6.7 7.3 52 6.5 7.5 54 10 5.9 8.1 58 4.3 9.7 70 5.2 8.8 63 4.6 9.4 67 1, 2 and 3 indicates Final Fluoride (mg/L), Reduction fluoride (mg/L) and % removal fluoride respectively in Table 3

1 gm 3 gm

5 gm

10 gm

Figure 2 Fluoride removal efficiency at different dosages

6. CONCLUSIONS Contact time experimental analysis suggests that maximum defluoridation in water takes place at 24 hrs duration. It is observed maximum in rice husk (70%), tulasi powder (64%), mixture of molinga olifera, garika and amla (54%) followed by chalk powder (53 %). At 10 gm dosage the maximum removal efficiency is observed in rice husk (70%), chalk powder (67%), tulasi powder (63%) and mixture of molinga olifera, garika and amla (58%).

http://iaeme.com/Home/journal/IJCIET 998 [email protected] G. Babu Rao, A.V. Rama Raju and S. Kanakambara Rao

REFERENCES [1] Chidambaram. S, AL Ramanathan* and S Vasudevan (2003), Fluoride removal studies in water using natural materials. School of Environmental Sciences, J.N.U., New Delhi. Water SA 29 (3), 339-344. [2] Sanghratna S.Waghmare and Tanvir Arfin (2015), Fluoride Removal from Water by various techniques: Review, September, IJISET (ISSN2348 –7968). [3] World Health Organization (2014) ,Potable water – standards 2.Water – standards 3.Water quality – standards 4.Guidelines I.Title. ISBN 92 4 154638 7. [4] BIS 10500 (1991), Indian standard Drinking water specification, Bureau of India Standards, New Delhi. [5] Vivek Vardhan C.M. and Karthikeyan J. (2011). “Removal of Fluoride From Water Using Low-Cost Materials”, Fifteenth International Water Technology Conference, IWTC-15, pp. 1-14. [6] Susheela (1999), Fluorosis Management Programme in India Article, Current science 77(10):1250-1256 • [7] Eenadu (2013) Relief to fluoride-affected areas in budget 2013 (daily news paper in Telugu), p 6. [8] Short H.E., G.R.Mc Robert, T.W., Bernard and Mannad inayar A .S. (1937), Endemic fluorosis in the Madras Presidency. Indian Journal of Medical Research.,25, pp 553-561. [9] Jamode A.V., Sakpal V.S. and Jamode V.S (2004), Defluoridation of water using inexpensive adsorbents ,Journal of Indian Institute of Science, 84, pp163-171. [10] APHA, AWWA and WEF (1996), Standard methods for the examination of water and wastewater, 19th edition , Washington, D.C, pp.657. [11] Paudyal H., Pangeni B., Inoue K., Kawakita H., Ohto K., Ghimire K.N., and Alam S. (2013), Preparation of novel alginate based anion exchanger from Ulva japonica and its application for the removal of trace concentrations of fluoride from water, Bio resource Technol.,148:221–227. [12] Prasenjit Mondal, Abhishek Nandan, Dr.N.A.Siddiqui and B.P.Yadav (2014), “Removal of fluoride from water by suitable low cost environmental friendly methods”, Environmental Pollution Control Journal”: Vol 17, No 6: . ISSN 0972-1541 [13] Jed, W (2005), Moringa oleifera: A Review of the medical evidence for its nutritional, therapeutic and prophylactic properties, part I, Trees for life journal Vol.1, p.5. [14] Parlikar AS, Mokashi SS (2013), “Defluoridation of Water by Moringa Oleifera -A Natural Adsorbent”, International Journal of Engineering Science and Innovative Technology (IJESIT) Vol. 2, pp. 245-252. [15] Runping, H., Yuanfeng, W., Weihong, Y., Weihua, Z., Jie, S. & Hongmin,(2007), Biosorption of methylene blue from aqueous solution by rice husk in a fixed-bed column. Water Supply, 2(1), pp. 311–317. [16] Sudarshan V, Narsimha A, Geeta S (2014), et al. Efficacy of tulasi for removal of fluoride in ground water. International journal of Recent Scientific Research Research 5(7):1236. [17] Abhishek Nandan (2014), University of Petroleum & Energy Studies , Removal of fluoride from water by suitable low cost environmental friendly methods View project, Environmental Pollution Control journal 17 (6), 41-44. [18] Aleena R Haneef and Nithya Kurup (2016). Comparative Study of Fluoride Removal from Water by Using Muringa Oleifera and Thulsi (Ocimum Sanctum). International Journal of Scientific & Engineering Research, Volume 7, Issue 4, 222 ISSN 2229-5518. [19] Gandhi N., Sirisha D., Chandra Shekar K.B. and Smita Asthana (2012),Removal Of Fluoride From Water And Waste Water By Using Low Cost Adsorbents., International Journal of Chem Tech Research, CODEN( USA): IJCRGG ISSN : 0974-4290 Vol.4, No.4, pp 1646-1653. [20] Ranjit N. Patil, Dr. P. B. Nagarnaik and Dr. D. K. Agrawal, Removal of Fluoride from Ground Water by Using Treated Bark of Phyllant hus Emblica (Amla) Tree. International Journal of Civil Engineering and Technology, 7(6), 2016, pp.11 – 20.

http://iaeme.com/Home/journal/IJCIET 999 [email protected]