Indian Journal of Fundamental and Applied Life Sciences ISSN: 2231– 6345 (Online) An Open Access, Online International Journal Available at http://www.cibtech.org/jls.htm 2015 Vol. 5 (1) January-March, pp. 280-285/Anbuvel et al. Research Article FLUORIDE ACCUMULATION ON PADDY (ORYZA SATIVA) AND BLACK GRAM (PHASEOLUS MUNGO LINN.) IN CULTIVATED AREAS OF DISTRICT, TAMILNADU, Anbuvel D.1, Kumaresan S.2 and *Jothibai Margret R.3 1Department of Chemistry, Vivekananda College, Agasteeswaram, K.K. Dist, TN, India, 629701 2Department of Biotechnology, Manonmaniam Sundaranar University, TN, Tirunelveli - 627 012, TN, 3Department of Chemistry, Pope’s College, Sawyerpuram, Tuticorin, TN, India, 628251 *Author for Correspondence

ABSTRACT In order to evaluate the accumulation of fluoride in more consumable produce, samples of paddy (Oryza Sativa, main crop) and black gram (Phaseolus Mungo Linn., pulse crop) were randomly collected from 18 villages near the bank of Thovalai and Nanchilnadu Puthanar Channel in Kanyakumari District, Tamilnadu where fluoride concentration in the ground water was found beyond permissible limit (>1.5 ppm). The concentration of the fluoride in samples was determined using ion-selective electrode coupled to an ion analyzer. The result showed that the fluoride content of the paddy-I (Ambai-16) contains 0.74- 2.40 mg/kg during southwest monsoon. Paddy-II (TPS-3) contains 0.65-2.40 mg/kg during northeast monsoon. Black gram contains 0.228-0.780 mg/kg during summer. The highest concentrations of fluoride in paddy-I and paddy-II were found in Sankaranputhur village (2.40 mg/kg) and Azaganpuram village (2.40 mg/kg). Fluoride is more soluble in acid soils due to which its uptake by plants is enhanced. Phosphate fertilizers especially the superphosphates are most important sources of fluoride in agricultural lands. Many farmers are unaware of the hidden presence of this highly toxic substance.

Keywords: Fluoride; Paddy; Black Gram

INTRODUCTION Elevated concentration of fluoride in ground water is responsible for serious health problem in various parts of the world (Dissanayake et al., 2007). Drinking water and edible vegetation are often the sources of fluoride intake by human especially in areas where fluoride concentration in ground water or surface water, and air are high (Tekle-Haimanot et al., 2006). Fluorine, unlike nitrogen, sulphur, and even chlorine, is not an essential element for plants. Plants absorb fluorine, both from the soil and air, as well as from falling atmospheric dust (Davision et al.,). The use of fluoride enriched ground water for irrigating the crops is prevalent in many parts of world. The fluoride in the irrigated water not only affects the growth and productivity of the crops, but also gets accumulated in plant tissues (Anasuya et al., 1995). Most foods, whether derived from plant or animal life, contain fluoride ion at least in minute amounts. Some foods concentrate additional fluoride ion from boiling, processing or contamination. Fluorides levels vary widely even between samples of the same kind of food. Some foodstuffs such as vegetables and fruits normally contain fluoride though at low concentrations (0.1-0.4 mg/kg) and thus contribute to fluoride intake by human. Higher levels (up to 2 mg fluoride per kg of foodstuff) have been found in barley and rice (WHO, 1986; WHO, 2006). Rice is one of the commonly consumed cereals for more than half of the world’s population in many regions. It is eaten with every meal and it provides more calories than any other single food (Pishgar et al., 2011). It is estimated that more than half of the population of India subsists on rice and it is among the important cereal crops grown in different parts of India as food crop (Anasuya et al., 1996). The accumulation of fluoride in rice has been studied previously (Anasuya et al., 1995; Anasuya et al., 1996; Gupta et al., 2009). Black gram, also known as urdbean, mash, black maple etc., an important short-duration pulse crop is grown in many parts of India. Black gram has been distributed mainly in tropical to sub-tropical countries where it is grown mainly in summer seasons.

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Indian Journal of Fundamental and Applied Life Sciences ISSN: 2231– 6345 (Online) An Open Access, Online International Journal Available at http://www.cibtech.org/jls.htm 2015 Vol. 5 (1) January-March, pp. 280-285/Anbuvel et al. Research Article In continuation of our work in the study of accumulation of fluoride in soil (Anbuvel et al., 2014) and water (Kumaresan et al., 2013; Kumaresan et al., 2013) in villages near the bank of Thovalai and NP Channel in Kanyakumari District, Tamilnadu, we have extended our study to assess the accumulation of fluoride in paddy and black gram in the same study area.

MATERIALS AND METHODS Study Area The high rainfall zone of Tamilnadu includes Kanyakumari District (K.K. Dist), located in the southern tip of the peninsular India, between 77.05o and 77.36o longitude and 8.03o and 8.35oN latitude. It is bordered by Tirunelveli District of Tamilnadu in the north and northeast, and Kerala State in the northwest, and sea in the west and the south.

Figure 1: Maps representing location sites

Based on the agro-climatic and topographic conditions, the district can be divided into three regions, namely: The up-, middle-, and low lands, providing different climatic conditions of this district make it favorable for the cultivation of a number of crops. The uplands consist of hills and hill bases favourable for growing crops like cloves, pepper, rubber, nutmeg, pineapple etc. The middle regions possess valleys and plains fit for growing crops like tapioca, paddy, black gram, banana, coconut, etc. and the lowlands consist of the coastal belt which is suitable for the growth of cashew, coconut, etc. In the plains, two crops of vegetation the major rice is raised in a year. The first crop variety of Ambai-16 from May/June to August/September (Southwest monsoon) and the second crop variety of TPS-3 from September/October to February/March (Northeast monsoon) are cultivated. Occasionally a third crop such as black gram is grown during summer season. Sample Collection In order to evaluate the impact of the fluoride pollution, samples of paddy (main crop) and black gram (pulse crop) randomly collected from 18 villages of the study area where fluoride concentration in the ground water was found beyond permissible limit (> 1.5 ppm) prescribed 1.5 ppm (WHO, 2006). The samples were collected in the period of 2011-12. Paddy is the main crop of this district. First crop is collected in the month of September (Kannipoo) and second crop is collected in the month of February (Kumbapoo) under irrigation and a third crop of pulse (black gram) during summer. The crops were collected in plastic packets and carried to the laboratory within three days in dried form. Sample Analysis Oxygen-flask combustion has been used successfully for plant extracts, Oxygen-flask methods (Cooke et al., 1976) involve ignition of the samples in a closed condition. Fluoride concentrations were determined © Copyright 2014 | Centre for Info Bio Technology (CIBTech) 281

Indian Journal of Fundamental and Applied Life Sciences ISSN: 2231– 6345 (Online) An Open Access, Online International Journal Available at http://www.cibtech.org/jls.htm 2015 Vol. 5 (1) January-March, pp. 280-285/Anbuvel et al. Research Article in the 54 samples extracts by electrochemical means using ion-selective electrode coupled to an ion analyzer. The instrument was standardized using fluoride standards containing TISAB III. The electrode reading was standardized using 1ppm and 10ppm solutions (Geetika et al., 2014). Fluoride was determined using an optimum buffer system with fluoride ion-selective electrode

RESULTS AND DISCUSSION The results of fluoride analysis in crops (paddy and black gram) and water around eighteen villages in different seasons of Kanyakumari District are presented in Tables 1.

Table 1: Fluoride content in water and crops in study areas S. Villages Fluoride Concentration of Ground Water and Crops No Ground Paddy-I Ground Paddy- Ground Black water (Ambai-16) water II water gram (Southwest (mg/kg) (Northea (TPS-3) (Summe (mg/kg) monsoon) st (mg/kg) r) (mg/L) monsoon (mg/L) ) (mg/L) 1 Puthugramam 2.00 1.60 2.10 1.56 2.50 0.765 2 Ramapuram 1.68 1.80 1.72 1.25 1.80 0.650 3 Sankaranputhur 1.50 2.40 1.60 1.85 2.20 0.630 4 Andarkulam 1.50 0.74 1.60 0.80 1.70 0.295 5 Kottaivilai 2.65 0.83 2.77 1.52 2.91 0.780 6 Azaganapuram 1.75 0.85 1.83 2.40 1.90 0.251 7 Padmanapanputhur 1.00 0.76 1.00 0.82 1.20 0.272 8 1.35 0.91 1.50 1.30 1.60 0.296 9 Nalloor 0.90 1.60 1.00 0.95 1.12 0.560 10 Eraviputhur 1.56 0.80 1.60 0.65 3.90 0.385 11 Athalavilai 1.50 0.82 1.57 0.96 1.60 0.280 12 Thoopur- 1.69 2.06 1.77 1.85 1.80 0.286 Srikrishnapuram 13 Rajavoor 1.65 0.85 1.60 0.90 1.70 0.232 14 Ramanathchinputhoo 1.00 0.90 1.00 1.02 1.80 0.276 r 15 Amaravathivilai 1.65 0.96 1.70 0.92 1.65 0.265 16 Azagappapuram 1.78 1.50 1.89 1.56 2.10 0.230 17 Indiranagar 1.78 1.20 1.82 1.48 1.85 0.228 18 Anjugramam 1.05 0.82 1.18 0.95 1.19 0.235 19 Minimum 0.90 0.74 1.00 0.65 1.12 0.228 20 Maximum 2.65 2.40 2.77 2.40 3.90 0.780 21 Average 1.55 1.89 1.62 1.26 1.92 0.384 22 Standard deviation 0.42 0.51 0.43 0.46 0.66 0.19

Maximum fluoride concentration in ground water samples of 18 villages was found to vary from a minimum of 0.90 mg/lit of Nalloor village (southwest monsoon) to a maximum of 3.9 mg/lit Eraviputhur village (summer season) respectively during the study year of 2011-12 (Table 1). This may lead to the weathering of rocks containing fluoride minerals viz. amphiboles, hornblende, topaz, rock phosphates etc. which ultimately leads to the leaching of fluoride in the groundwater (Salve et al., 2008; Chanderkar et al., 2010; Reshma et al., 2003). The study revealed low fluoride concentrations during monsoon seasons compared to summer season; this may be due to the dilution with rain water. Most of the ground water

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Indian Journal of Fundamental and Applied Life Sciences ISSN: 2231– 6345 (Online) An Open Access, Online International Journal Available at http://www.cibtech.org/jls.htm 2015 Vol. 5 (1) January-March, pp. 280-285/Anbuvel et al. Research Article samples were found to be well above the permissible limit prescribed by Indian standard (B.I.S 1991)18 and WHO (WHO 2006)6 standard. The problem of high fluoride in groundwater has been reported by several researchers (Desbarats et al., 2009; Keshavarzi et al., 2010; Brindha et al., 2011). The present study (study year 2011-2012) revealed that fluoride concentration in paddy-I (Ambai-16) crop during southwest monsoon was found between 0.74 mg/kg in Andarkulam village and 2.40 mg/kg in Sankaranputhur village (Table 1). The fluoride concentration of another variety, paddy-II (TPS-3) crop, during northeast monsoon was observed from 0.80 mg/kg (Andarkulam village) to 2.40 mg/kg (Azaganapuram village). Similarly Bisratewongel et al., studied the fluoride levels ranged from 0.1-5.5 mg/kg in raw rice samples in Ethiopia. The difference might be due to difference in their genetic makeup, the variety of rice plant, fertilizer used, soil type, and quality of water used for plantation (Renato et al., 2007). In these study areas, the fluoride concentration in black gram was estimated to be 0.230 mg/kg in Azagappapuram village and 0.780 mg/kg in Kottavilai village during summer. High fluoride levels in water are associated with the high concentrations of paddy because of greater consumption of fluoride in water by paddy crop. After evaluating the data of the present study, it was observed that the fluoride content of soil (Anbuvel et al., 2014) and ground water (Kumaresan et al., 2013) samples of irrigated areas exceeded the permissible limit. From the evidence, fluoride enters through the ground water, soil, and usage of phosphate fertilizer (Gautam et al., 2010) into crops especially, rice. The results indicated that the fluoride concentration of all the rice samples are higher than the black gram samples, this is due to water stagnation in rice crop only. The fluoride contents of all the black gram samples are within permissible limit, which is because the black gram is basically a hot season crop exhibiting tolerance to higher temperature and susceptibility. Correlation and Regression of Fluoride Content between Water and Crops

(a) Fluoride content of water and fluoride (b) Fluoride content of water and fluoride content of paddy-I content of paddy-II

(c) Fluoride content of water and fluoride content of black gram

Figure 2: Fluoride content of water and fluoride content of paddy-I/paddy-II/black gram © Copyright 2014 | Centre for Info Bio Technology (CIBTech) 283

Indian Journal of Fundamental and Applied Life Sciences ISSN: 2231– 6345 (Online) An Open Access, Online International Journal Available at http://www.cibtech.org/jls.htm 2015 Vol. 5 (1) January-March, pp. 280-285/Anbuvel et al. Research Article A significant positive correlation between fluoride concentration in ground water and fluoride content of paddy-I (r = 0.0792), paddy-II (r = 0.4874), and black gram (r = 0.3895) were observed (Figure 2a-c). Results revealed that fluoride content of crops were increased linearly with elevation in water fluoride concentration. The regression coefficients (R2) were 0.006, 0.237, and 0.151 respectively. Linear regression fitting equations were obtained through statistical regression analysis of data presented in Table 1. The pairs are: (a) fluoride content of water and fluoride content of paddy-I (Figure 2a); (b) fluoride content of water and fluoride content of paddy-II (Figure 2b); (c) fluoride content of water and fluoride content of black gram (Figure 2c) Conclusion Keeping in view, the ground water quality that is the source of drinking water, the residents of this locality of these study areas are in an alarming position. In order to reduce the risk of human exposure to fluoride, the use of fluoride contaminated water, especially for crops that tend to accumulate fluoride, should be reduced as much as possible. It can be concluded that the fluoride is consumed by grazing animals and human beings through the plants from the water. Prolonged excessive intake of fluoride will result in fluorosis. It is recommended that organic manures have to be used for improvement in fertility of soil instead of chemical fertilizers and water analysis should be carried out from time to time to monitor the rate and kind of contamination. It is the need of awareness among the farmers to maintain the cleanliness of water at their highest quality and purity levels to achieve a healthy life.

ACKNOWLEDGEMENT One of the authors D. Anbuvel thanks the management of Vivekananda College, Agasteeswaram for laboratory facilities.

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