World Applied Sciences Journal 26 (12): 1610-1616, 2013 ISSN 1818-4952 © IDOSI Publications, 2013 DOI: 10.5829/idosi.wasj.2013.26.12.1682

An Investigation of Fluoride Distribution in Block of District, Central

11M. Arif, J. Hussain, 2 I. Hussain and 3 S. Kumar

1Department of Chemistry, Banasthali University, Niwai, District-Tonk-304022, Rajasthan, 2National River Water Quality Laboratory, Central Water Commission, New -1107 016, India 3Public Health Engineering Department (PHED) Laboratory, Bhilwara-311 001, Rajasthan, India

Submitted: Oct 17, 2013; Accepted: Nov 22, 2013; Published: Dec 4, 2013 Abstract: Fluoride in groundwater is known to contaminate the water sources globally. Rajasthan, one of the states in the western part of India, is known to have excessive fluoride contenting groundwater sources. The present work involves assessment of water quality with special reference to fluoride in Ladnu block of in Rajasthan. Fluoride concentration of groundwater samples from forty villages of Ladnu Block was monitored and Thirty one villages were found to have a fluoride concentration above 1.5 mg/l. The maximum fluoride concentration (7.1 mg/l) was recorded in groundwater of the Roja, while minimum (0.5 mg/l) was recorded in Hudas. As per the desirable and maximum permissible limit for fluoride in drinking water, recommended by the WHO and BIS, the groundwater of thirty one villages is unfit for drinking purpose.

Key words: Fluoride Groundwater Drinking water Ladnu Block Rajasthan

INTRODUCTION states. It appears that high-well fluoride may exist in many more districts [7]. The prominent states, which are In most water resources, naturally occurring levels severely affected, are Andhra Pradesh, Rajasthan, of fluoride can be found. In surface waters, fluoride can , Uttar Pradesh and Tamilnadu [8-10]. Earlier occur naturally by the deposition of atmospheric derived reports in different parts of India indicate certain particles and /or by fluoride-containing soils and rocks instances of fluorosis [11-14]. weathering and in ground water resources by leaching of In India, fluoride was first detected in drinking water rocks and soils. Also, fluoride makes its way into the at Nellore district of Andhra Pradesh in 1937 [10]. Since public sources of water through diverse human activities, then, considerable work has been done in different parts such as chemical manufacturing plants and manufacturing of India to explore the fluoride-laden water sources. At of tile, brick, glass and so on [1,2]. present, it has been estimated that fluorosis is prevalent High fluoride concentrations in groundwater are also in 17 states of India, indicating that endemic fluorosis is found in the USA, Africa and Asia [3]. The most severe one of the most alarming public health problem of the problem associated with high fluoride waters occurs in country, especially in Rajasthan, Madhya Pradesh, China, India, Sri Lanka and Rift Valley countries in Africa Andhra Pradesh, Tamil Nadu, Gujarat and Uttar Pradesh. [4, 5]. High fluoride groundwater has been studied in The State wise fluoride concentration is shown in Table1. detail in Africa, in particular in Kenya and Tanzania [6]. In the early 1980s, it was estimated that 260 million people Geological Framework of Nagaur District: The worldwide (in 30 countries) were drinking water with >1 geological set up of the district is presented by different mg/L of fluoride. sedimentary, igneous and metamorphic rocks belonging In India, the excessive presence of fluorides in to Bhilwara super Group, Delhi super Group. Marwar groundwater is present in nearly 177 districts covering 19 super Group, Palana Formation and Quaternary alluvium.

Corresponding Author: M. Arif, Department of Chemistry, Banasthali University, Niwai, District-Tonk-304022, Rajasthan, India. Tel: +919929784396. 1610 World Appl. Sci. J., 26 (12): 1610-1616, 2013

Table 1: District showing fluoride concentration > 1.5 mg/L in groundwater in India in 2010 State District Range Assam Goalpara, Kamrup, Karbi Anglong and Nagaon 1.45-7.8 Andhra Pradesh Adilabad, Anantpur, Chittoor, Guntur, Hyderabad, Karimnagar, Khammam, Krishna, Kurnool, Mahbubnagar, Medak and Nalgonda 1.8-8.4 Bihar Aurangabad, Banka, Buxar, Jamui, Kaimur(Bhabua), Munger, Nawada, Rohtas and Supaul 1.7-2.85 Chhattisgarh Bastar, Bilaspur, Dantewada, Janjgir-Champa, Jashpur, Kanker, Korba, Koriya, Mahasamund, Raipur, Rajnandgaon and Surguja 1.5-2.7 Delhi East Delhi, North West Delhi, South Delhi, South West Delhi, West Delhi, Kanjhwala, Najafgarh and Alipur 1.57-6.10 Gujarat Ahmadabad, Amreli, Anand, Banaskantha, Bharuch, Bhavnagar, Dohad, Junagadh, Kachchh, Mehsana, Narmada, Panchmahals, Patan, Rajkot, Sabarkantha, Surat, Surendranagar and Vadodara 1.6-6.8 Haryana Bhiwani, Faridabad, Gurgaon, Hissar, Jhajjar, Jind, Kaithal, Kurushetra, Mahendragarh, Panipat, Rewari, Rohtak, Sirsa and Sonepat 1.5-17 Jammu and Kashmir Doda, Rajauri and Udhampur 2.0-4.21 Karnataka Bagalkot, Bangalore, Belgaun, Bellary, Bidar, Bijapur, Chamarajanagar, Chikmagalur, Chitradurga, Davangere, Dharwad, Gadag, Gulburga, Haveri, Kolar, Koppal, Mandya, Mysore, Raichur and Tumkur 1.5-4.4 Kerala Palakkad, Palghat, Allepy, Vamanapuram and Alappuzha 2.5-5.7 Maharashtra Amravati, Chandrapur, Dhule, Gadchiroli, Gondia, Jalna, Nagpur and Nanded 1.51-4.01 Madhya Pradesh Bhind, Chhatarpur, Chhindwara, Datia, Dewas, Dhar, Guna, Gwalior, Harda, Jabalpur, Jhabua, Khargaon, Mandsaur, Rajgarh, Satna, Seoni, Shajapur, Sheopur and Sidhi 1.5-10.7 Orissa Angul, Balasore, Bargarh, Bhadrak, Bandh, Cuttack, Deogarh, Dhenkanal, Jajpur, Keonjhar and Sonapur 1.52-5.2 Punjab Amritsar, Bhatinda, Faridkot, Fatehgarh Sahib, Firozepur, Gurdaspur, Mansa, Moga, Muktsar, Patiala and Sangrur 0.44-6.0 Rajasthan , Alwar, Banaswara, Barmer, Bharatpur, Bhilwara, , Bundi, Chittaurgarh, Churu, Dausa, Dhaulpur, Dungarpur, Ganganagar, Hanuman-garh, , , Jalor, Jhunjhunun, , Karauli, Kota, Nagaur, Pali, Rajsamand, Sirohi, Sikar, SawaiMadhopur, Tonk and 1.54-11.3 Tamilnadu Coimbatore, Dharmapuri, Dindigul, Erode, Karur, Krishnagiri, Namakkal, Perambalur, Puddukotai, Ramanathapuram, Salem, Sivaganga, Theni, Thiruvannamalai, Tiruchirapally, Vellore and Virudhunagar 1.5-3.8 Uttar Pradesh Agra, Aligarh, Etah, Firozabad, Jaunpur, Kannauj, Mahamaya Nagar, Mainpuri, Mathura and Mau 1.5-3.11 West Bengal Bankura, Bardhaman, Birbhum, Dakshindinajpur, Malda, Nadia, Purulia and Uttardinajpur 1.5-9.1

A few outcrops of gneisses belonging to the Mangalwar which is subdivided into Jodhpur, Bilara and Nagaur Complex of the Bhilwara Super group are exposed north- group representing arenaceous, Calcareous and areno- east of Nawa. The Delhi Super Group includes Alwar. argillaceous fancies respectively. These rocks are overlain Ajabgarh/ Kumbhalgarh and punagarh Group in by sandstone and bentonite of the Palana formation. descending order of antiquity. The rocks of Alwar Group The Marwar Super Group of rocks showing horizontal to are well exposed in the eastern part of the district and gently inclined disposition of different beds which are comprise arkose, grit, conglomerate and schist. The displaced by different faults. Palana and other Tertiary overlying Ajabgarh / Kumbhalgarh Group of rocks are formations are showing same altitude. exposed between kerkeri and Bijathal. The Ajabgarh At present, in India, endemic fluorosis is thought to Group mainly consists of Quartzite with schist and marble. affect 1 million people [15]. Rajasthan is known as a desert Kumbhalgarh comprises mica schist and marble. The state with acute water crisis. Since many pockets were overlying punagarh Group of rocks (quartzite, slate identified as fluoride affected belts [8, 16-23]. But Ladnu phyllite, marble etc.) occur as isolated outcrops. The rocks block of Nagaur district was not studied, so the main of Bhilwara Super Group and Delhi Super Group are objective of the study was to investigation of fluoride structurally isoclinal and recline fold which are exposed contamination in groundwater or Ladnu block of Nagaur along south eastern margin (trend NE-SW) of the district district, Central Rajasthan. adjacent to . The rocks of Delhi super Group have been intruded by the Erinpura granite and the Study Area: The district is located between Latitude Malani Igneous suite. All these rocks are overlain by the 26°25’ and 27°40’ and longitude 73°18 and 75°15 E, marine sedimentary sequence of the Marwar Super Group because of its central situation in Rajasthan, it shares its

1611 World Appl. Sci. J., 26 (12): 1610-1616, 2013 border with several other district of the state. On the north village Roja while the minimum 0.5 was in village Hudas it is bounded by Bikaner and Churu districts, on the east samples was found maximum desirable limit of Indian by Sikar and . The total geographical area of Drinking Water Standards IS: 10500, 1993 (i.e. 1.0 mg/l), the district is 17718 sq. km. The study area i.e. Ladnu while 31 samples were recorded beyond permissible limit located between Latitude 27°39’ and 27°65 N and as per decided by Indian Drinking Water Standards [27]. longitude 74°23’ and 74°38’ 33”E [24]. The fluoride concentration of various villages was shown in Table 2. MATERIAL AND METHOD All habitations were categorized in following five categories as proposed by Hussain et al. to demonstrate Water Sample Collection: Groundwater samples of the fluoride distribution [28]:- forty villages located in Ladnu Block of Nagaur district were collected in pre cleaned polythene bottles with Category I : Fluoride concentration below 1.0 mg/l necessary precautions [25]. The samples were collected, (Green) in year 2013, from manually operated public hand pumps Category II :Fluoride concentration between 1.0 mg/l and public walls in residential localities of studied and 1.5 mg/l (Yellow) habitations. Category III : Fluoride concentration between 1.5 mg/l and 3.0 mg/l (Red) Methodology: The fluoride concentration in water was Category IV : Fluoride concentration between 3.0 determined electrochemically; using fluoride in selective mg/l and 5.0 mg/l (Brown) electrode [26]. This method is applicable to the Category V : Fluoride concentration above 5.0 mg/l measurement of fluoride in drinking water in the (Black) concentration range of 0.01-1,000 mg/l. The electrode used was an Orion fluoride electrode, coupled to an Orion Ion Above categorization map is shown as figure 1. meter. Standards fluoride solutions (0.1-10 mg/l) were Higher content of fluoride in drinking water can prepared from a stock solution (100 mg/l) of sodium cause severe health problems, particularly in arid fluoride. As per experimental requirement, 1 ml of Total and semi-arid regions. This could be due to the Ionic strength Adjusting Buffer Grade III (TISAB III) was prevalent climatic conditions which necessitate people added in 10 ml of sample. The ion meter was calibrated for to drink water in quantities higher than what people a slop of-59.2 ±2 (APHA 2012). The composition of drink in temperate regions. In setting national TISAB solution was as 385.4 gm ammonium acetate, 17.3 standards or local guidelines for fluoride or in evaluating gm of cyclohexylenediaminetetraacetic acid and 234 ml of the possible health consequences of exposure to fluoride, concentrate hydrochloric acid per liter. All the experiments it is essential to consider the average daily intake of water were carried out in triplicate and the results were found by the population of interest and the intake of fluoride reproducible with ±2% error. from other sources (e.g. from food and air). Where the intakes are likely to approach, or be greater than, 6 RESULTS AND DISCUSSIONS mg/day, it would be appropriate to consider setting a standard or local guideline at a concentration lower than Randomly 40 villages were selected for sampling. 1.5 mg/L [29]. The samples were collected from public hand pumps and wells. The physical observations of the samples indicated Sources of Fluoride: The sources of fluoride in surface or that they are colorless and odorless in nature. The ground water are: concentration of fluoride in groundwater is not uniform in the area. This may be due to the differences in the The sea presence and accessibility of fluorine-bearing minerals to The atmosphere the circulating water and also due to the weathering and The earth’s crust leaching activities. Rock forming minerals The fluoride concentration varies from 0.5 to 7.1 mg/ Rocks L. The maximum concentration 7.1 mg/L was recorded in Commercial ores

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Table 2: Fluoride concentration in villages of Ladnu block S. No. Name of habitation Census Code no. (2001) Population (2001) Fluoride 1 Manu 01757700 1421 0.6 2 Hudas 01757800 3141 0.5 3 Nimbijodhan 01758200 9686 1.4 4 Odeet 01758500 3171 1.2 5 Hirawati 01758700 1718 1.5 6 01758800 3108 2.3 7 Vishwanathpura 01759000 810 2.2 8 Dujar 01759600 2819 0.6 9 Bankaliya 01759700 2423 2.3 10 01760500 8890 3.6 11 KasumbiAlipur 01760600 3563 5.0 12 KasumbiUpadara 01760700 730 2.6 13 Lodsar 01761000 1486 2.1 14 Tanwara 01761100 3114 4.1 15 Bhamas 01761200 710 1.7 16 Udrasar 01761800 919 6.1 17 Reengan 01762300 2882 3.1 18 Rodoo 01762400 5613 3.5 19 Bhidasari 01762700 1633 1.7 20 Sardi 01762800 2242 4.1 21 Dholiya 01762900 2912 5.1 22 Chhapara 01763300 1890 2.3 23 Khokhari 01763900 1455 5.5 24 Malgaon 01764100 1262 2.8 25 Sandas 01764200 1478 1.4 26 Sikarali 01764300 1096 1.6 27 Dheengsari 01764500 1989 2.8 28 Roja 01764600 1621 7.1 29 Silanwad 01764700 3672 6.2 30 Titri 01764900 952 2.2 31 Khamiyad 01765100 1156 2.3 32 Dhurila 01765200 2228 1.7 33 Seenwa 01765300 2501 2.5 34 Ratau 01765400 5898 2.6 35 01765500 4268 2.5 36 Simla 01765600 877 1.2 37 Sanwrad 01765800 1248 2.2 38 GheerdodaKhara 01766200 1340 4.3 39 Dhyawa 01766500 3470 5.5 40 Phirwasi 01767300 2472 1.7

Soils: The fluoride content of surface and Routes of Fluoride Intake: Although fluoride can be underground waters depends on a wide variety of ingested through drinking water, some food items and factors. The major availability and solubility of the parent beverages as well as cosmetics, may contain high fluoride minerals with which the waters are in contact [30]. concentration of fluorosis. However, the most important It is also found that around mica mines, groundwater is route of intake of fluoride has been identified to be the rich is fluorides and Rajasthan is a rich source of mica drinking water. It is estimated that 60% of the total [31]. fluoride intake is through drinking water [32].

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Fig. 1: Study Area and Fluoride Distribution Map of Ladnu Block

Table 3: Relation between concentration of fluorides and biological effects [34] Concentration of fluoride in mg/l Medium Effect 0.002 Air Injury to vegetation 1 Water Dental carries reduce 2 or more Water Mottled enamel 8 Water 100% osteosclerosis 50 Foods and water Thyroid changes 100 Foods and water Growth retardation 120 Foods and water Kidney changes

Fluoride when consumed or inhaled in excess has adversely affected the socio-economic status of the (more than 1 ppm) can cause several health problems. state. Therefore, for combating this problem, following It affects young and old alike. An individual may suffer mitigating measures are suggested. from Inculcation of awareness amongst rural and urban Skeletal fluorosis, or population regarding harmful effects of quality Dental fluorides, or parameters. Non-skeletal fluorosis, Popularizing simple and handy defluoridation All or a combination of the above. techniques at domestic and community level in endemic areas. Fluoride is also known to induce aging [33]. Smith Avoid the habit of open air defecation. and Hedge have related the concentration of fluorosis to Avoid the sewage disposal directly to ground the biological effects as given in Table 3 [34]. water. Installation of reverse osmosis, Ion-exchange and Mitigation of Problem for Sustainable Future: Indeed electrodialysis plants in affected areas. high nitrate and high fluoride contents in drinking water Avoid indiscriminate use of nitrogenous fertilizers has created not only dealt problem but it has become a and promotion of use of bio-fertilizers and bio- serious livelihood problem for the consumers which inturn pesticides.

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Construction of wells/tube wells in low nitrate and 10. Ayoob, S. and A.K. Gupta, 2006. Fluoride in fluoride areas. drinking water: a. review on the status and Prohibition on use of fluoride rich edibles, cosmetics stress effects. Critical Rev. Environ. Sci. Technol., and luxury items. 36: 433-487. Supplementation of ascorbic acid, methionine and 11. Ramamohana Rao, N.V., K. Suryaprakasa Rao and methylene blue has been found to be effective in R.D. Schulling, 1993. Fluorine distribution in waters overcoming the problem of nitrate toxicity. of Nalgonda District, Andhra Pradesh, India. Promotion of breast feeding at least up to the age of Environmental Geology, 21: 84-89. 6 months of the infant. 12. Sharma, D.P.R. and S.L.N. Rao, 1997. Promulgation of Aquifer Protection Policy (APP) to Fluoride concentration in groundwater of avoid over-exploitation of ground water to alleviate Vishakapatnam, India. Bulletin of Environmental ingress of fluoride. Contamination and Toxicology, 58: 241-247. Mandatory provision of construction of Rain water 13. Babulal, D., T. Jitu, S. Surashree, B. Gohain, harvesting structures at domestic, official and R.K. Dutta and B.D. Himangshu, 2003. Fluoride and community levels. other inorganic constituents in groundwater of Guwahati, Assam, India. Current Science, REFERENCES 85(5): 657-661. 14. SubbaRao, N. and D. John Devadas, 2003. 1. Mohapatra, M., S. Anand and B.K. Mishra, 2009. Fluoride incidence in groundwater in an area of Review of fluoride removal from drinking water. peninsular India.Environmental Geology, 45: 243-251. J. Environ Manage, 91: 67-77. 15. Sneha, J., M.K. Yenkie, N. Labhsetwar and S. Rayalu, 2. Barbier, O., L. Arreola-Mendoza and L.M. Del Razo, 2012. Fluoride in drinking water and defluoridation of 2010. Molecular mechanisms of fluoride toxicity. water. Chem. Rev., 112: 2454-2466 doi.org/10. Chem-Biol Interact, 188: 319-333. 1021/cr2002855. 3. Azbar, N. and A. Turkman, 2000. Defluoridation 16. Arif, M., J. Hussain, I. Hussain and S. Neyol, 2011. in drinking waters. Water Sci. Technol., 42(1-2): 403- Fluoride Contamination of Ground Water of Merta 407. Block in Nagaur District, Rajasthan, India. In the 4. Wang, W., R. Li, J. Tan, K. Luo, L. Yang, H. Li and conference of advance in Environmental chemistry Y. Li, 2002. Adsorption and leaching of fluoride in (AEC), Aizwal, Mizoram, pp: 146-148. China. Fluoride, 35: 122-129. 17. Arif, M., I. Hussain, J. Hussain, S. Sharma and 5. Agarwal, M., K. Rai, R. Shrivastav and S. Dass, 2003. S. Kumar, 2012. Fluoride in the Drinking Water of Defluoridation of water using amended clay. J. Nagaur Tehsil of Nagaur District, Rajasthan, India. Cleaner Produc., 11: 439-444. Bull Environ Contam Toxicol DOI 10.1007/s00128-012- 6. Moturi, W.K.N., M.P. Tole and T.C. Davies, 2002. 0572-4. The contribution of drinking water towards dental 18. Arif, M., S. Joshi and S. Kumar, 2012. A Study of fluorosis: a case study of Njoro Division, Nakuru Fluoride Contaminated Ground Water in Uniara District, Kenya. Environ Geochem Health, 24: 123-130. Tehsil, District-Tonk, Rajasthan, India. In India Water 7. Muralidharan, D., A.P. Nair and U. Sathyanarayana, Week. 2002. Fluoride in shallow aquifers in Rajgarh tehsil of 19. Arif, M., J. Hussain, I. Hussain and S. Kumar, 2013. Rajasthan-An arid environment. An Assessment of Fluoride Concentration in Current Science, 83: 699-702. Groundwater and Risk on Health of North Part of 8. Arif, M., I. Husain, J. Hussain and S. Kumar, 2013. Nagaur District, Rajasthan, India World Applied Assessment of fluoride level in groundwater and Sciences Journal, 24(2): 146-153. prevalence of dental fluorosis in block of 20. Hussain, J., K.C. Sharma, M. Arif and I. Hussain, Nagaur district, central Rajasthan, India. Int J. Occup 2007. Fluoride distribution and modelling using best Environ Med., 4: 178-184. subset procedure in Nagour District of Central 9. Susheela, A.K., 2001. A treatise on fluorosis (pp: 15). Rajasthan, India. In The XXVIIth conference of the Delhi: Fluorosis Research and Rural Development international society for fluoride research Foundation. (ISFR XXVII), Beijing, China.

1615 World Appl. Sci. J., 26 (12): 1610-1616, 2013

21. Husain, I., M. Arif and J. Husain, 2012. 28. Husain, J., I. Husain and K.C. Sharma, 2010. Fluoride contamination in drinking water in rural Fluoride and health hazards: community perception in habitations of central Rajasthan, India. Environmental a fluorotic area of Central Rajasthan (India), an arid Monitoring and Assessment 184(8), 5151-5158; environment. Environmental Monitoring and doi: 10.1007/s10661-011-2329-7. Assessment, 162: 1-14. 22. Hussain, J., I. Hussain and M. Arif, 2013. 29. World Health Organization, 2011. Revision of the Fluoride occurrence in Groundwater of Central WHO guidelines for drinking water quality. World Rajasthan, India and its Toxicity in Rural Habitants. Health Organization, Geneva. Toxicological and Environmental Chemistry. DOI: 30. World Health Organization, 1970. Fluoride and human 10.1080/02772248.2013.832545. health. WHO monograph series no., pp: 59. 23. Choubisa, S.L., L. Choubisa and D.K. Choubisa, 2001. 31. Shiv Chandra, 1993. Endemic fluorosis in Rajasthan, Endemic fluorosis in Rajasthan. Indian Journal of Ind. Association of preventive and social medicine, Environmental Health, 43: 177-189. Raj. Chapter, Conference, S.P. Medical College, 24. Census, 2001. District Nagaur, Rajasthan, Bikaner. Government of Rajasthan. 32. Gupta, S.K., 1997. A process for defluoridation of 25. Brown E., M.W. Skougstad and M.J. Fishman, 1974. water by a filter bed using indigenous material. Indian Method for collection and analysis of water sample J. of Env. Sci., 1(2): 149-156. for dissolved minerals for dissolved minerals and 33. Susheela, A.K., 1991. Prevention and control of gases (Book No. 5). Washington, DC: US Department fluorosis, Technical information for traiing cum of Interior. awareness camp for doctors, Public health engineers 26. APHA, 2012. Standard methods for the examination and other officers, Published by National of water and wastewater. (22nd Ed.), Washington, Technology Mission of drinking water, New Delhi. DC: American Public Health Association. 34. Smith, F.A. and H.C. Hedge, 1959. Fluoride toxicity, 27. BIS, 2012. Drinking Water Standard 10500. Bureau of Indiana University press, Bloomington. Indian Standard, India.

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