The origin of fluoride in the granitic aquifer of Porto Alegre, Southern Brazil

The Porto Alegre region, Southern Brazil, comprises a fractured aquifer system constituted by pre-Cambrian granitic and gneissic rocks, and a porous aquifer system formed by Cenozoic muddy–sandy to sandy sediments. A model is presented for the origin of the fluoride in the groundwater of the fractured aquifer system, based on ionic interrelations, a statistical analysis of physicochemical parameters and geochemical modeling. The fluoride is present at levels of up to 6.13 mg/L in groundwater and it arises due to the dissolution of secondary fluorite filling fractures in the granitic and gneissic rocks. The dissolution of fluorite occurs at the same time as calcite and dolomite solubilization. The statistical analysis identified three chemically distinct groups (named 1, 2 and 3) and two subgroups (1A and 1B) of groundwater in the fractured aquifer. The most significant differences between these groups are the different concentration ranges of fluoride, calcium, bicarbonate, magnesium, total dissolved solids and chloride and pH values, as well as the correlations between them. The compositional evolution of each groundwater group is governed mainly by how much high-salinity groundwater from the porous aquifer system is mixed with them and the different thermodynamic equilibrium conditions of calcite, dolomite and fluorite.     

辽宁萤石矿成矿条件和成矿规律探讨

辽宁是国内萤石重要产地之一,分布着阜新哈尔套-义县地藏寺、辽阳隆昌—金州杏树屯两个萤石成矿带,带内已发现大中型矿床7处、中小型矿床和矿(化)点60余处。通过对辽宁萤石成矿特征和地层、侵入岩、构造等控矿条件与成矿关系的分析,认为萤石成矿类型为中低温岩浆期后热液充填交代型,围岩类型主要为碳酸盐岩和硅酸盐岩;萤石成矿时期为燕山期、印支期和华力西期,且以燕山期为主;萤石矿体多赋存在花岗岩岩体内部断裂带或与围岩外接触带的断裂带位置。依据萤石矿床的地质特征和成矿规律,结合构造、岩石与围岩、地球物理与地球化学等找矿标志,圈定出6个成矿远景区。     

Fluoride contamination in Gharbar Village of Dhanbad District,Jharkhand, India: source identification and management

This paper reports occurrence of high fluoride concentration in groundwater of Gharbar Village, Dhanbad District, Jharkhand, India. The concentration of fluoride varied from 0.3 to 14.9 mg/L in 27 groundwater samples. The correlation studies demonstrate that fluoride has strong positive correlation with pH and sodium and negative correlation with calcium. It indicates dominance of ion exchange activity and rock water interaction. Thermodynamic consideration shows that all the samples were oversaturated with calcite and most of the samples were under saturated with fluorite. The results indicate that occurrence of high concentration of fluoride is leading by geochemical composition of rocks, alkaline environmental condition, weathering of rocks and ion exchange processes.     

Isotope hydrochemical approach to understand fluoride release into groundwaters of Ilkal area,Bagalkot District,Karnataka, India

Isotope and hydrochemical investigations have been carried out in the Ilkal area of Karnataka, India, in order to determine the source and mechanism of fluoride release into groundwaters and to understand groundwater hydrochemistry. Agriculture, granite quarrying and rock-polishing industries are the main occupations in this area. Closepet granite, Peninsular gneiss and Dharwar schists are the major geological formations. Results show that the fluoride concentration in groundwater is 0.3–6.5 mg/L and it is found to increase from recharge area to discharge area. Fluoride variability is found to be influenced by the geology of the area and depth wise correlation was not observed. Water samples are unsaturated with respect to fluorite, indicating the possibility of further increase in fluoride in groundwater. Positive correlations between fluoride with sodium and bicarbonate in groundwater show that high fluoride content and alkaline sodic characteristics are the result of dissolution of fluoride bearing minerals, possibly derived from weathered granite and gneiss. A positive correlation between fluoride and δ¹⁸O, and the presence of high tritium in fluoride-contaminated groundwater, point to contribution from surface waters, contaminated by anthropogenic activities. Dumping of rock wastes that are rich in fluoride into the streams by the rock-polishing industries plays a significant role in contaminating groundwater.     

浙江省萤石矿床区域成矿规律与找矿方向研究

萤石矿是浙江省的优势矿种之一,储量在中国名列前茅。根据矿床成因可分为火山-次火山热液充填型、岩浆期后热液充填型和岩浆热液交代型3种类型。火山-次火山热液充填型萤石矿床主要分布于浙东南火山岩分布区,成矿作用与中生代火山活动关系密切;岩浆期后热液充填型和岩浆热液交代型萤石矿床主要分布于浙西北燕山期花岗岩周围,成矿作用与燕山期岩浆侵入活动密切相关。文章根据浙江省萤石矿床的成因类型、成矿作用、构造环境、成矿时代等特征,可将其归纳为2个成矿系列:与中生代火山-次火山热液有关的萤石矿床成矿系列和与中生代岩浆侵入作用有关的萤石矿床成矿系列。其中,与中生代岩浆侵入作用有关的萤石矿床成矿系列又可分为与燕山期中酸性岩浆期后热液充填作用有关的萤石矿床成矿亚系列及与燕山期中酸性岩浆热液交代作用有关的萤石矿床成矿亚系列。在此基础上,提出了2大萤石矿床成矿系列的找矿方向分别为浙东南晚白垩世火山断陷盆地边缘断裂、火山口环形和放射状断裂及浙西北高氟岩体。     

Association of hydrogeological factors in temporal variations of fluoride concentration in a crystalline aquifer in India

The major part of groundwater in India is found in granitic aquifers. Fluoride in groundwater from a crystalline aquifer in a semi-arid region of granitic rocks in India, known as Maheshwaram watershed, was analyzed for spatial and temporal variability during 1999–2002 to assess the effect of hydrogeological factors on fluoride concentration. Samples were collected from 32 representative wells in the area for the pre- and post-monsoon seasons and analyzed for F content. The CHESS computer program was used to calculate ionic activities of aqueous species and the mineral saturation index (SI) for calcite and fluorite. The GARDENIA computer program was used to calculate the recharge values in the study area. The influences of dissolution kinetics of fluoride minerals and recharge from rainfall on fluoride concentration were of interest and results clearly indicate that fluoride content in groundwater depends on the interaction period of groundwater with host rock. Results could also be utilized for designing remedial measures particularly with dilution method in an optimal way.     

Hydrochemical characteristics of groundwater quality with special reference to fluoride concentration in parts of Mulugu-Venkatapur Mandals,Warangal district,Telangana

Hydrochemical studies were carried out in Mulugu-Venkatapur Mandals of Warangal district, Telangana state, India to find out the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The fluoride concentration in groundwater ranges from 0.28 to 5.48 mg/l with a mean of 1.26 mg/l in pre-monsoon and 0.21 to 4.43 mg/l with a mean 1.45 mg/l in post-monsoon. About 32% and 34% of samples in pre and post-monsoon containing fluoride concentrations that exceed the permissible limit. The Modified Piper diagram reflects that, water belong to Ca⁺²-Mg⁺²-HCO₃ - to Na⁺-HCO₃ - facies. Negative chloroalkali indices in both the seasons prove that ion exchange took place between Na⁺ & K⁺ with Ca⁺² and Mg⁺² in aquatic solution in host rock. Different plots for major ions and molar ratios suggest that weathering of silicate rocks and water-rock interaction is responsible for major ion chemistry of water. High fluoride content in groundwater attributed to continuous water-rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high content of sodium bicarbonate in soils and waters are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.     

Geochemistry of fluoride rich groundwater in Kolar and Tumkur Districts of Karnataka

Groundwater is a significant water resource in India for domestic, irrigation, and industrial needs. By far the most serious natural groundwater-quality problem in India, in terms of public health, derives from high fluoride, arsenic, and iron concentrations. Hydrogeochemical investigation of fluoride contaminated groundwater samples from Kolar and Tumkur Districts in Karnataka are undertaken to understand the quality and potability of groundwater from the study area, the level of fluoride contamination, the origin and geochemical mechanisms driving the fluoride enrichment. Majority of the groundwater samples did not meet the potable water criteria as they contained excess (>1.5 mg/L) fluoride, dissolved salts (>500 mg/L) and total hardness (75–924 mg/L). Hydrogeochemical facies of the groundwater samples suggest that rock weathering and evaporation–crystallization control the groundwater composition in the study area with 50–67% of samples belonging to the Ca–HCO₃ type and the remaining falling into the mixed Ca–Na–HCO₃ or Ca–Mg–Cl type. The saturation index values indicated that the groundwater in the study area is oversaturated with respect to calcite and under-saturated with respect to fluorite. The deficiency of calcium ion concentration in the groundwater from calcite precipitation favors fluorite dissolution leading to excess fluoride concentration.     

河南省萤石矿床地质特征、成矿规律及找矿方向

萤石是我国战略性矿种之一,提高其资源储备对国民经济发展具有重要意义。本研究对河南省萤石矿床的地质特征、时空分布、成矿物质来源等进行分析,系统总结萤石矿床的成矿规律,并提出河南省萤石找矿方向。结果表明：（1）河南省萤石矿床类型以热液充填型为主,全省可划分为三个萤石成矿带;（2）河南省萤石矿床主要分布于中生代花岗质侵入岩体的内部或其周边地层的北西向、北东向断裂构造带中,方城地区萤石矿床主要赋存于岩体附近的地层中;（3）萤石矿床的成矿年龄在120 Ma左右,方城地区萤石矿床可能形成于新元古代;（4）中生代花岗质岩浆作用或其期后热液活动为萤石成矿提供重要的物质和驱动热;地层岩石为萤石成矿提供重要的氟,其丰富钙源很可能是巨量萤石富集的关键;（5）萤石主成矿阶段的成矿流体应属低温、低盐度、低密度的流体系统,大气降水对萤石成矿具有重要作用;（6）河南省萤石找矿重点地区应在太华群地层岩石和中生代花岗质侵入岩体广泛发育的北带和中带,特别是合峪、太山庙、天目山、铜山等岩体的内部或其周围。     

Fluoride and arsenic hydrogeochemistry of groundwater at Yuncheng basin,Northern China

High fluoride and arsenic concentrations in groundwater have led to serious health problems to local inhabitants at Yuncheng basin, Northern China. In this study, groundwater with high fluoride and arsenic concentration at Yuncheng basin was investigated. A majority of the samples (over 60%) belong to HCO₃ type water. The predominant water type for the shallow groundwater collected from southern and eastern mountain areas was Ca/Mg-Ca-HCO₃ types. For the shallow groundwater from flow through and discharge area it is Na-HCO₃/SO₄-Cl/SO₄/Cl type. The predominant water type for the intermediate and deep groundwater is of Na/Ca/Mg-Ca-HCO₃ type. According to our field investigation, fluoride concentration in groundwater ranges between 0.31 and 14.2 mg/L, and arsenic concentration ranges between 0.243 and 153.7 μg/L. Out of seventy collected groundwater samples, there are 31 samples that exceed the World Health Organization (WHO) standard of 1.5 mg/L for fluoride, and 15 samples exceeds the WHO standard of 10 μg/L for arsenic. Over 40% of high fluoride and arsenic groundwater are related to the Na-HCO₃ type water, and the other fifty percent associated with Na-SO₄-Cl/HCO₃-SO₄-Cl type water; little relation was found in calcium bicarbonate type water. A moderate positive correlation between fluoride and arsenic with pH were found in this study. It is due to the pH-dependent adsorption characteristics of F and As onto the oxide surfaces in the sediments. The observed negative correlation between fluoride and calcium could stem from the dissolution equilibrium of fluorite. The high concentration of bicarbonate in groundwater can serve as a powerful competitor and lead to the enrichment of fluoride and arsenic in groundwater. Most of the groundwater with high fluoride or arsenic content has nitrate content about or over 10 mg/L which, together with the observed positive correlations between nitrate and fluoride/arsenic, are indicative of common source of manmade pollution and of prevailing condition of leaching in the study area.     

Hydrochemistry of groundwater (GW) and surface water (SW) for assessment of fluoride in Chinnaeru river basin,Nalgonda district, (AP) India

Hydrochemical studies were conducted in Chinnaeru river basin of Nalgonda district, Andhra Pradesh, India, to explore the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The concentration of fluoride in groundwater ranges from 0.4 to 2.9 and 0.6 to 3.6 mg/l, stream water ranges from 0.9 to 3.5 and 1.4 to 3.2 mg/l, tank water ranges from 0.4 to 2.8 and 0.9 to 2.3 mg/l, for pre- and post-monsoon periods, respectively. The modified Piper diagram reflects that the water belongs to Ca²⁺–Mg²⁺–HCO₃ ^? to Na⁺–HCO₃ ^? facies. Negative chloroalkali indices in both the seasons prove that ion exchange between Na⁺ and K⁺ in aquatic solution took place with Ca²⁺ and Mg²⁺ of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water–rock interaction is responsible for major ion chemistry of groundwater/surface water. High fluoride content in groundwater was attributed to continuous water–rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high levels of sodium bicarbonate are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.     

The origin of fluoride-rich groundwater in Mizunami area, Japan — Mineralogy and geochemistry implications

The aim of this paper was to explore new factors that might be reasons for the occurrence of fluoride-rich groundwater in the area around a construction site. During the construction of two deep shafts of the Mizunami Underground Research Laboratory (MIU) in Mizunami city, central Japan, a large quantity of groundwater with high fluoride concentration was charged into the shafts. Chemical investigation carried out during the excavation revealed that fluoride concentrations in the area around the MIU site greatly exceeded those prescribed by Japanese standards. Therefore, the origin of fluoride ion was experimentally investigated. Samples were collected from the core of a deep borehole drilled in the study area. The weathering - and alteration levels of the collected granites varied greatly. Granitic powders were used to measure fluoride content in the granitic rock mass. The fluoride content ranged between 200 and 1300 mg/kg. The powders were reacted with purified water for 80 days. The results of water–rock interaction showed granitic rock to be one of the main sources of fluoride-rich groundwater in Mizunami area. Fluoride concentrations in these solutions that were shaken for 80 days varied between 2 and 7 mg/l. This change may have occurred as a result of the spatial distribution of fluoride ions in the granite mass as evidenced by mineralogical analysis of fluoride content in several specimens. X-ray powder diffraction analysis of the rock before- and after the water–rock interaction tests manifested that the presence of fluorite mineral was relatively small compared to other minerals. The degree of weathering and alteration might be an additional factor causing dissolution of fluoride-rich minerals. However, it was difficult to interpret the change in fluorite composition by X-ray diffraction analysis.     

Hydrogeochemical genesis of groundwaters with abnormal fluoride concentrations from Zhongxiang City,Hubei Province,central China

The groundwaters from Zhongxiang City, Hubei Province of central China, have high fluoride concentration up to 3.67 mg/L, and cases of dental fluorosis have been found in this region. To delineate the nature and extent of high fluoride groundwaters and to assess the major geochemical factors controlling the fluoride enrichment in groundwater, 14 groundwater samples and 5 Quaternary sediment samples were collected and their chemistry were determined in this study. Some water samples from fissured hard rock aquifers and Quaternary aquifers have high fluoride concentrations, whereas all karst water samples contain fluoride less than 1.5 mg/L due to their high Ca/Na ratios. For the high fluoride groundwaters in the fissured hard rocks, high HCO₃ ⁻ concentration and alkaline condition favor dissolution of fluorite and anion exchange between OH⁻ in groundwater and exchangeable F⁻ in some fluoride-bearing minerals. For fluoride enrichment in groundwaters of Quaternary aquifers, high contents of fluoride in the aquifer sediments and evapotranspiration are important controls.     

大同盆地高氟地下水水化学特征及其成因

为查明控制大同盆地高氟地下水形成的主要地球化学过程,对大同盆地地下水高氟区31个水样进行了水化学特征及因子分析研究.结果表明,研究区浅层和深层地下水中均检测出氟,且氟含量高,最大ρ(F)达10.37 mg/L.该区高氟地下水以Na-HCO3型水为主,具有典型的富Na特征.PHREEQC饱和指数计算结果表明,地下水中萤石为不饱和状态,地下水中ρ(F)主要受到萤石溶解影响.因子分析研究表明,水一岩相互作用、碳酸盐矿物溶解沉淀及Na- Ca离子交换作用是控制大同盆地地下水氟富集的主要水化学过程.     

Analysis of fluoride in rocks and an application to exploration

The fluoride^* content of rocks can be measured using a selective ion electrode. Analyses were made using a sodium hydroxide fusion and ammonium citrate buffer and measurements can be compared to standard or can be made by standard addition using the Gran's Plot method. The Gran's Plot method yields fluoride values in agreement with known values for standard rocks. Values obtained by these two methods vary sympathetically. Furthermore, whole rock fluoride values vary sympathetically with water-leachable fluoride values, which permits use of simpler, less expensive methods for field exploration purposes. Application of these procedures to an area of tin mineralization indicates that easily distinguishable anomalous fluoride values for water leach and total fluoride in rocks are associated with areas of tin mineralization.     

Geochemical Modelling of Fluoride Concentration in Hard Rock Terrain of Madhya Pradesh, India

The aim of the present study is to locate and decipher the groundwater quality,types,and hydrogeochemical reactions,which are responsible for elevated concentration of fluoride in the Chhindwara district in Madhya Pradesh,India.Groundwater samples,quality data and other ancillary information were collected for 26 villages in the Chhindwara District,M.P.India during May 2006.The saturation index was computed for the selected samples in the region,which suggest that generally most of the minerals are saturated with respect to water.The concentration of fluoride in the region varies from 0.6 to 4.74 mg/l,which is much higher as per the national and international water quality standards.The study also reveals that the fluoride bearing rock formations are the main source of the higher concentration of fluoride in groundwater along with the conjuncture of land use change.Moreover,the area is a hard rock terrain and consists of fractured granites and amygdaloidal and highly jointed compact basalt acting as good aquifer,which is probably enriching the high content of fluoride in groundwater.High concentration of fluoride is found in deeper level of groundwater and it is possible due to rock-water interaction,which requires further detailed investigation.The highly alkaline conditions indicate fluorite dissolution,which works as a major process for higher concentration of fluoride in the study area.The results of this study will ultimately help in the identification of risk areas and taking measures to mitigate negative impacts related to fluoride pollution and toxicity.     

Geochemical processes regulating groundwater chemistry with special reference to nitrate and fluoride enrichment in Chhatarpur area, Madhya Pradesh, India

The present study focuses on the hydrogeochemical composition of groundwater in Chhatarpur area with special focus on nitrate and fluoride contamination, considering the fact that groundwater is the only major source of drinking water here. Carbonate and silicate mineral weathering followed by ground water–surface water interactions, ion exchange and anthropogenic activities are mainly responsible for high concentrations of cations and anions in the groundwater in the region. The average concentration of nitrate and fluoride found in 27 samples is 1.08 and 61.4 mg/L, respectively. Nitrate enrichment mainly occurs in areas occupied with intense fertilizer practice in agricultural fields. Since the area is not dominated by industrialization, the possibility of anthropogenic input of fluoride is almost negligible, thus the enrichment of fluoride in groundwater is only possible due to rock–water interaction. The highly alkaline conditions, which favor the fluorite dissolution, are the main process responsible for high concentration of fluoride.     

Fluoride concentrations in a crystalline bedrock aquifer Marathon County, Wisconsin

Water samples from 2,789 private water-supply wells in Marathon County, Wisconsin reveal that fluoride concentrations in the crystalline bedrock range from <0.01 to 7.60 mg/L, with 0.6% of the values exceeding the Environmental Protection Agency’s (EPA’s) maximum contaminant level of 4 mg/L, and 8.6% exceeding the EPA’s secondary maximum contaminant level of 2.0 mg/L. Roughly a quarter of the wells contain dissolve fluoride within the range considered optimal for human health (between 0.5 and 1.5 mg/L), whereas 63.3% fall below 0.5 mg/L. Consistent with studies conducted in other regions, felsic rocks have significantly higher fluoride concentrations than mafic and metasedimentary rocks. Syenites yield the most fluoriferous groundwaters, but the highest median concentration occurs in a sodium-plagioclase granite. A relationship between plagioclase composition and fluoride concentrations suggests that dissolved fluoride levels are controlled by fluorite solubility and that higher fluoride concentrations are found in soft, sodium-rich groundwater.     

The origin of fluoride in groundwater supply to Hermosillo City, Sonora, México

Anomalous high fluoride concentration up to 7.59 mg/dm³ is found in groundwater from “La Victoria” area. This water is used to supply drinking water to Hermosillo City, Sonora. Geochemistry of groundwater, relationship between physicochemical parameters, hydrogeology and geologic setting were correlated to define the origin and the geochemical mechanisms of groundwater fluorine enrichment. High fluoride concentration is associated with high bicarbonates, pH and temperature, and it decreases toward the west and south of the area. Fluoride is in negative correlation to calcium concentration. Sodium sulphate facies of regional deep water flow are related to high fluoride concentration. High electric resistivity rocks associated with granites from the Sierra Bachoco basement might be the deep source of fluoride. Outcropping of Sierra Bachoco in the west causes upward regional flow. Groundwater of longer residence time can be pumped there. The anomalous area is restricted to “La Victoria” because calcareous paleozoic rocks outcrop to the south.     

Chemical,isotopic and mineralogical characteristics of volcanogenic epithermal fluorite deposits on the Permo-Mesozoic foreland of the Andean volcanic arc in Patagonia (Argentina)

Epithermal deposits mined for fluorite in Patagonia, Argentina, are closely related to late Triassic through Jurassic magmatic activity which brought about felsic to intermediate magmatic rocks. The fluorite mineralization in the Patagonian epithermal system resulted from gaseous F-and CO₂-enriched magmas which lead to an explosive phreatomagmatic volcanism, when getting in contact with groundwater near the surface. As a result of these hydrothermal processes, rapid cooling took place in the epithermal mineralization. Changes in the viscosity along with the cooling down of mineralizing fluids caused mottled mineral colors blurring the boundaries between the stages and ore textures.The fluids accountable for the main constituents fluorite, quartz, barite and silica were operative over a vertical extension of roughly 600 m. Their temperature of formation dropped from 379 °C through 64 °C, while the pH decreased from the heat center towards the paleosurface under oxidizing conditions. This steep temperature gradient conducive to the telescoping of mineral associations into each other was accompanied by a rapid loss in CO₂, and a mixing of meteoric and magmatic fluids. Even the boundary between the hypogene and supergene alteration cannot be drawn precisely within the assemblage of Mn oxides, which bridge the gap between hypogene and supergen mineralization. The physical-chemical parameters of the fluids, particularly, the redox conditions did not allow sulfides to be preserved. A classification of the epithermal system as to its degree of sulfidation is based on K-feldspar and kaolinite which are present in significant amounts, whereas APS (aluminum-phosphate-sulfate) minerals are absent. Therefore a categorization as an epithermal fluorite deposit of low- to intermediate sulfidation is justified, because the only mineral of economic interest in the system is fluorite.The data obtained during this joint study render the Patagonian fluorite district a reference type of fluorite in an epithermal system of low- to intermediate sulfidation which are widespread in Argentina, e.g., Sierras Pampeanas, and evolved on part of the stable craton, called Gondwana and which grade into epithermal Au, Ag, In, Pb and Zn deposits.