Fluoride contamination in water is a major problem across the globe, with health hazards such as dental and skeletal fluorosis. Most earlier studies are confined to local or regional scales. As the problem has serious socioeconomic implications, there is a need for a global perspective. Thus, here we review worldwide research for nearly a century on fluoride contamination in water. We investigated the distribution of fluoride contamination in water, its sources, mobilization and association. The major findings are: (1) Anomalous fluoride concentration in groundwater is mainly confined to arid and semiarid regions of Asia and North Africa. (2) The geogenic sources of fluoride in water are mainly fluorine-bearing minerals in rocks and sediments, whereas anthropogenic sources of fluoride in water are mainly pesticides and industrial waste. (3) Fluoride mobilization from geogenic sources is mainly controlled by alkalinity and temperature. (4) Fluoride occurrence in water is associated with ions such as sodium, arsenic chloride and bicarbonate. There are few associations of fluoride in water with calcium and magnesium.

Worldwide contamination of water by fluoride

Fluoride (F−) has significant impacts on human health. High fluoride groundwater (up to 1.90 mg/L) has been found in upper confined aquifer underlying the first terrace of Weihe River during a hydrogeological investigation for water supply in 2005. To reveal the occurrence and hydrogeochemistry of high F− groundwater, hydrogeochemical tools such as saturation index, ionic ratios and correlation analysis were used in this study. The study shows that the concentrations of most physiochemical parameters from phreatic water, influenced by intensive evaporation and anthropogenic activities such as unregulated sewage and excreta disposal and agricultural practices in the area, are higher than those of confined water. The F− concentration in phreatic water is within the acceptable limits set by China and the World Health Organization (WHO), while that of upper confined water shows a decreasing trend northwestward as the Weihe River approaches, with F− concentration in the first terrace beyond the national and the WHO standards. High F− groundwater is observed in alkaline environment associated with high Na+, pH, HCO3
 − and low Ca2+ and Mg2+. The enrichment of F− is controlled by geologic and hydrogeological conditions, fluorine-bearing minerals presented in alluvial formations and their dissolution/precipitation under the alkaline environment along groundwater flow. Ion exchange, human activities and the mixing of different recharge waters may influence the enrichment of F− as well.

Occurrence and hydrogeochemistry of fluoride in alluvial aquifer of Weihe River, China

Fluoride contamination in the groundwater has got great attention in last few decades due to their toxicity, persistent capacity and accumulation in human bodies. There are several sources of fluoride in the environment and different pathways to enter in the drinking water resources, which is responsible for potential effect on human health. Presence of high concentration of fluoride ion in groundwater is a major issue and it makes the water unsuitable for drinking purpose. Availability of fluoride in groundwater indicates various geochemical processes and subsurface contamination of a particular area. Fluoride-bearing aquifers, geological factors, rate of weathering, ion-exchange reaction, residence time and leaching of subsurface contaminants are major responsible factors for availability of fluoride in groundwater. In India, several studies have reported that the groundwater of several states are contaminated with high fluoride. The undesirable level of fluoride in groundwater is one of the most natural groundwater quality problem, which affects large portion of arid and semiarid regions of India. Rajasthan, Andhra Pradesh, Telangana, Tamil Nadu, Gujarat, and West Bengal are the relatively high-fluoride-contaminated states in India. Chronic ingestion of high doses of fluoride-rich water leads to fluorosis on human and animal. Over 66 million Indian populations are at risk due to excess fluoride-contaminated water. Therefore, groundwater contamination subject to undesirable level of fluoride needs urgent attention to understand the role of geochemistry, hydrogeology and climatic factors along with anthropogenic inputs in fluoride pollution.

Groundwater fluoride contamination, probable release, and containment mechanisms: a review on Indian context.

Climatic condition, geology, and geochemical processes in an area play a major role on groundwater quality. Impact of these on the fluoride content of groundwater was studied in three regions-part of Nalgonda district in Telangana, Pambar River basin, and Vaniyar River basin in Tamil Nadu, southern India, which experience semi-arid climate and are predominantly made of Precambrian rocks. High concentration of fluoride in groundwater above 4 mg/l was recorded. Human exposure dose for fluoride through groundwater was higher in Nalgonda than the other areas. With evaporation and rainfall being one of the major contributors for high fluoride apart from the weathering of fluoride rich minerals from rocks, the effect of increase in groundwater level on fluoride concentration was studied. This study reveals that groundwater in shallow environment of all three regions shows dilution effect due to rainfall recharge. Suitable managed aquifer recharge (MAR) methods can be adopted to dilute the fluoride rich groundwater in such regions which is explained with two case studies. However, in deep groundwater, increase in fluoride concentration with increase in groundwater level due to leaching of fluoride rich salts from the unsaturated zone was observed. Occurrence of fluoride above 1.5 mg/l was more in areas with deeper groundwater environment. Hence, practicing MAR in these regions will increase the fluoride content in groundwater and so physical or chemical treatment has to be adopted. This study brought out the fact that MAR cannot be practiced in all regions for dilution of ions in groundwater and that it is essential to analyze the fluctuation in groundwater level and the fluoride content before suggesting it as a suitable solution. Also, this study emphasizes that long-term monitoring of these factors is an important criterion for choosing the recharge areas.

Fluoride in weathered rock aquifers of southern India: Managed Aquifer Recharge for mitigation.

Human Health Risk Assessment: Study of a Population Exposed to Fluoride Through Groundwater of Agra City, India

Hydrogeochemical investigations with emphasis on groundwater fluoride concentrations were carried out in the Shivani watershed area, Karnataka, South India. This drought-prone watershed is characterised by poor groundwater potential and is composed of different lithounits like gneisses, migmatites, tonalites, mafics–ultramafics, conglomerates and quartzites. Analysis of spatial variation of groundwater fluoride concentration through the use of GIS technology software platforms like ArcView 3.2a and MapInfo Professional 8.5 has enabled the identification of low-fluoride and high-fluoride areas within the watershed. Geochemical data indicates that 38% of groundwater samples have excessive fluoride concentration which poses a health risk to the population of the area. Correlation studies indicate that higher groundwater alkalinity activates leaching of fluoride resulting in elevated concentrations of fluoride. No other significant geochemical interrelationship could be identified between fluoride and rest of the physico-chemical parameters owing to the lack of any significant correlation coefficients. This holds good in the case of both low-fluoride ( 1.5 mg/L) groundwaters of the watershed. However, differential or non-uniform type (positive or negative) of coefficient of correlation is observed between fluoride at different levels and other physico-chemical parameters. Among the different lithounits of the study area, gneisses house comparatively more number of high-fluoride groundwaters. Fluoride-bearing minerals biotite, hornblende and apatite are the probable natural sources of groundwater fluoride.

Spatial analysis of fluoride concentration in groundwaters of Shivani watershed area, Karnataka state, South India, through geospatial information system

T. K. Lakkundi

Papers

Spatial analysis of fluoride concentration in groundwaters of Shivani watershed area, Karnataka state, South India, through geospatial information system