Distribution,enrichment mechanism and risk assessment for fluoride in groundwater: a case study of Mihe-Weihe River Basin,China

● High fluorine is mainly HCO₃·Cl-Na and HCO₃-Na type. ● F⁻ decreases with the increase of depth to water table. ● High fluoride is mainly affected by fluorine-containing minerals and weak alkaline. ● Fluorine pollution is mainly in the north near Laizhou Bay (wet season > dry season). ● Groundwater samples have a high F⁻ health risk (children > adults). Due to the unclear distribution characteristics and causes of fluoride in groundwater of Mihe-Weihe River Basin (China), there is a higher risk for the future development and utilization of groundwater. Therefore, based on the systematic sampling and analysis, the distribution features and enrichment mechanism for fluoride in groundwater were studied by the graphic method, hydrogeochemical modeling, the proportionality factor between conventional ions and factor analysis. The results show that the fluorine content in groundwater is generally on the high side, with a large area of medium-fluorine water (0.5–1.0 mg/L), and high-fluorine water is chiefly in the interfluvial lowlands and alluvial-marine plain, which mainly contains HCO₃·Cl-Na- and HCO₃-Na-type water. The vertical zonation characteristics of the fluorine content decrease with increasing depth to the water table. The high flouride groundwater during the wet season is chiefly controlled by the weathering and dissolution of fluorine-containing minerals, as well as the influence of rock weathering, evaporation and concentration. The weak alkaline environment that is rich in sodium and poor in calcium during the dry season is the main reason for the enrichment of fluorine. Finally, an integrated assessment model is established using rough set theory and an improved matter element extension model, and the level of groundwater pollution caused by fluoride in the Mihe-Weihe River Basin during the wet and dry seasons in the Shandong Peninsula is defined to show the necessity for local management measures to reduce the potential risks caused by groundwater quality.     

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

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.     

新疆阿克苏地区平原区高砷地下水分布特征及富集因素分析

地下水砷污染是全球化环境问题.本文基于阿克苏地区平原区2017年75个地下水砷实测含量进行分析.结果表明,研究区地下水砷含量变化范围为ND—98.70μg·L^-1,平均值为9.42μg·L^-1,超标率达26.7%.水平方向上,高砷地下水主要集中在研究区的中部偏南一带;垂直方向上,山麓斜坡冲洪积砾质平原潜水区地下水砷含量平均值表现为深层潜水>浅层潜水,中下游河流冲积平原区承压水区地下水砷含量平均值表现为深层承压水>浅层承压水>潜水.采用绘制Piper三线图、Gibbs图、离子比例图等方法对研究区地下水砷的富集因素进行研究.结果表明,研究区地下水砷主要为自然来源;封闭的地质构造和造山带与河流等沉积环境相结合的水文地质条件有利于研究区地下水砷的富集;研究区高砷地下水水化学类型主要为HCO3·SO4-Na,还原性-弱碱性环境利于地下水砷富集;研究区地下水砷受强烈的蒸发浓缩作用进一步浓缩,同时地下水阴离子浓度增大加剧了地下水中阴离子与砷酸根、亚砷酸根之间的竞争吸附,利于地下水砷的富集.     

Isotopic and hydrogeochemical evaluation of groundwater at Qusier-Safaga area,eastern desert,Egypt

The groundwater resources of the El-Qusier-Safaga area on the Red Sea coastal zone have still to be utilised fully for social and economic development. In the present study, an inventory of recharge sources and quality of groundwater in different water bearing formations is made to assist in management of these vital resources. From a hydrochemical point of view, the origin of salinity in the five investigated aquifers are mainly dissolution of terrestrial minerals, leaching of soilsvia floods or ion exchanges processes. Stable isotope data clarify the interaction between different aquifers and indicate that the source of recharge is mainly meteoric water originating from palaeowater of the Pleistocene pluvial period, and from local precipitation as well as some marine water. Evaluation of the groundwater quality for domestic, irrigation and industrial purposes is discussed.     

济南市地下水硝酸盐污染研究

调查了济南市东郊工业区浅层地下水、南部山区补给区地下水及市区饮用水中硝酸盐现状及发展趋势。结果表明,工业区浅层地下水硝酸盐含量超出国家饮用水卫生标准;补给区地下水及市区饮用水硝酸盐也受到人类活动的影响,污染呈逐年上升趋势。分析了造成地下水硝酸盐污染的原因,提出了相应的防治措施与对策。     

内蒙古河套地区水体中砷的地球化学特征

采样分析典型地砷病区域——内蒙古河套地区地下水、地表水和自来水中砷含量和形态,研究河套地区水体中砷分布状况,并采集山西山阴县大营村(地下水)和山东招远地区水样(地表水、地下水),以用于污染特性比较和源解析。结果发现,内蒙古河套地区和山西省山阴县大营村作为生活饮用水的地下水中砷含量超标率较高,其中内蒙古临河区狼山镇先锋七社和山西大营村地下水砷含量平均值分别为368.9和443.5μg.L-1,分别有75%和100%的水样超过GB 5749—2006《生活饮用水卫生标准》中农村小型集中和分散式供水砷含量限值。内蒙古五原县乃日乡的175个水样中,也有59%的地下水样砷含量高于50μg.L-1,且砷形态主要以无机砷为主。河套地区地表水水样砷含量大部分在50μg.L-1以下,部分自来水(水源为地下水)样砷含量超过生活饮用水标准。     

广花盆地地下水化学特征及其演化分析

粤港澳大湾区(简称大湾区)建设已经上升为中国国家重大发展战略,水资源保障能力提升是大湾区建设的重点内容。城市应急备用水源建设是解决区内供水风险、保障特殊时期供水安全的重要手段,查明水环境质量状况及其演化对于备用水源地的科学建设意义重大。以粤港澳大湾区应急备用水源地-广花盆地为研究对象,采集并测试了41口监测井水样的常规化学组分,利用主成分分析、元素比值和Gibbs模型等多种方法,探讨了地下水主要离子来源及控制因子,评估了水质状况。结果表明:地下水的TDS变化范围为51.42-1 293.36 mg·L-1,Cl-为1.81-858.65 mg·L-1,淡水样占比95.1%,微咸水占比4.9%,反映地下水化学具有较大的空间差异;地下水阳离子以Ca2+和Na+为主,阴离子以HCO3-和Cl-为主,为HCO3-Ca、HCO3-Na·Ca、HCO3·SO4-Na·Ca和HCO3·Cl-Na·Ca型水;地下水的ρ(Na+)/ρ(Na++Ca2+)值为0.02-0.59,ρ(Cl-)/(Cl-+HCO3-)值为0.03-0.88,Ca/Na值为0.69-52.66,HCO3/Na值为1.28-41.64,据Gibbs模型和元素化学计量分析表明,其化学组成主要受含水层碳酸盐岩和硅酸盐岩风化控制;Na/Cl系数为0.31-6.39,局部地下水盐化明显,在北部高Cl-质量浓度区,其主要受古咸水与现代淡水混合影响,并有Na+与Ca2+离子交换,在南部的高Cl-质量浓度区,可能是海水沿流溪河咸潮上溯和河流侧向补给地下水所致;氨氮为0.05-7.50mg·L-1,有75.6%的样品超过Ⅲ类水标准,其主要来源为农业施肥、人畜粪便。由此,氨氮污染威胁地下水安全,作为应急备用水源应引起高度重视。     

Assessment of groundwater contamination using geographic information systems

In this study two sites were selected in order to investigate groundwater contamination and spatial relationships among groundwater quality, topography, geology, landuse and pollution sources. One site is the Asan area, an agricultural district where pollution sources are scattered and which is mainly underlain by granite of Cretaceous age. The other site is the Gurogu area of Seoul city, an industrial district where an industrial complex and residential areas are located and which is mainly underlain by gneiss of Precambrian age. Groundwater samples collected from these districts were analysed for chemical constituents. An attribute value files of chemical constituents of groundwater and the spatial data layers were constructed and pollution properties were investigated to establish out spatial relationships between the groundwater constituents and pollution sources using geographic information systems (GIS).Relatively high contents of Si and HCO₃ ^– in the groundwater from the Asan area reflect the effect of water–rock interaction whereas high contents of Cl^–, NO₃ ^– and Ca²⁺ in the groundwater from the Gurogu area are due to the pollution of various sources. The significant seasonal variation of SiO₂, HCO₂ ^– and Ca²⁺ contents, and that of Ca²⁺ content were observed in the Asan and the Gurogu areas, respectively. Seasonal variation of pollutants such as Cl^–, NO₃ ^– and SO₄ ^2– was not observed in either area. Pollution over the critical level of the Korean drinking water standard has been investigated from 15 sampling sites out of 40 in the Asan area, and 33 sampling sites out of 51 in the Gurogu area. Pollution by NO₃ ^–, Cl^–, Fe²⁺, Mn²⁺, SO₄ ^2– and Zn²⁺ in the groundwater from the industrial district (Gurogu area) and that of NO₃ , SO₄ ^2– and Zn²⁺ in the groundwater from the agricultural district (Asan area) were observed. The principal pollutant in both areas is NO₃ ^–. Deep groundwater from the Asan area is not yet contaminated with NO₃ ^– except for one site, but most of the shallow groundwater site occurring near the potential point sources is seriously contaminated. From the result of buffering analysis, it seems clear that factories and stock farms are the principal pollution sources in the Asan area. The groundwater from the Gurogu area has already been seriously polluted considering the fact of NO₃ ^– contamination of deep groundwater. Chlorine pollution of shallow groundwater in the Gurogu area was also observed. Spatial relationship between pollution level and its source was clarified in this study by using GIS, which will be applicable to the effective management of groundwater quality.     

Assessment of groundwater contamination caused by uncontrolled dumping in old gravel quarries in the Besòs aquifers (Barcelona,Spain)

The contamination of groundwater in the aquifer of the La Llagosta basin (Besòs river basin) due to waste disposal in quarries formerly used for the extraction of dry raw materials has led to the cessation of groundwater extraction for public water supply. The mobilization of pollutants was largely caused by fluctuations in piezometric levels, which led to the washing of buried waste. The hydrogeochemical processes associated with uncontrolled waste disposal in these landfilled areas of the La Llagosta basin aquifer were studied along a flow path that crosses the contaminated area. The PHREEQC code was used to establish the reactions associated with the different mineral phases through inverse modeling. This transport code, ionic exchange phenomena, surface reactions and balance (mineral phase) reactions were used to simulate the dilution phenomenon associated with the pollution after the potential removal of the sources of contamination. One-dimensional advective–dispersive modeling indicates a substantial reduction in Ca, Mg, Na and SO₄²⁻ within one year and stabilization within four years.     

Distribution and Risk Assessment of Fluoride in Drinking Water in the West Plain Region of Jilin Province, China

The west plain region of Jilin province of northeast China is one of the typical endemic fluorosis areas caused by drinking water for many years. Investigations of hydrogeological and ecoenvironmental conditions as well as endemic fluorosis were conducted in 1998. Results show that the ground water, especially, the water in the unconfined aquifer is the main source of drinking water for local residents. The fluoride concentration in groundwater in the unconfined aquifers is higher than that in the confined aquifer in the west plain of Jilin province. The fluoride concentration in the unconfined aquifer can be used to classify the plain into fluoride deficient area, optimum area and excess area, which trend from west to east. High fluoride (>1.0 mg L(-1)) in drinking water resulted in dental and skeletal fluorosis in local residents (children and pregnant women). There exists a positive correlation between fluoride concentration in the drinking water and the morbidities of endemic fluorosis disease (r1 = 0.781, r2 = 0.872). Health risks associated with fluoride concentration in drinking water are assessed. It has been determined that fluoride concentration in excess of 1.0 mg L(-1) exposes residents to high health risks based on risk identification. The study area is classified into five health risk classes as shown in Figure 4. The risk indexes of this area more than 1.0 are accounted for 68% of the total west plain region.     

Organic compounds in water extracts of coal: links to Balkan endemic nephropathy

The Pliocene lignite hypothesis is an environmental hypothesis that has been proposed to explain the etiology of Balkan endemic nephropathy (BEN). Aqueous leaching experiments were conducted on a variety of coal samples in order to simulate groundwater leaching of organic compounds, and to further test the role of the Pliocene lignite hypothesis in the etiology of BEN. Experiments were performed on lignite coal samples from endemic BEN areas in Romania and Serbia, and lignite and bituminous coals from nonendemic regions in Romania and the USA. Room temperature, hot water bath, and Soxhlet aqueous extraction experiments were conducted between 25 and 80 °C, and from 5 to 128 days in duration. A greater number of organic compounds and in higher concentrations were present in all three types of leaching experiments involving endemic area Pliocene lignite samples compared to all other coals examined. A BEN causing molecule or molecules may be among phenols, PAHs, benzenes, and/or lignin degradation compounds. The proposed transport pathway of the Pliocene lignite hypothesis for organic compound exposure from endemic area Pliocene lignite coals to well and spring drinking water, is likely. Aromatic compounds leached by groundwater from Pliocene lignite deposits in the vicinity of endemic BEN areas may play a role in the etiology of the disease. A better understanding of organic compounds leached by groundwater from Pliocene lignite deposits may potentially lead to the identification and implementation of effective strategies for the prevention of exposure to the causative agent(s) for BEN, and in turn, prevention of the disease.     

Arsenic and fluoride in the groundwater of Mexico

Concentrations of arsenic and fluoride above Mexican drinking water standards have been detected in aquifers of various areas of Mexico. This contamination has been found to be mainly caused by natural sources. However, the specific processes releasing these toxic elements into groundwater have been determined in a few zones only. Many studies, focused on arsenic-related health effects, have been performed at Comarca Lagunera in northern México. High concentrations of fluoride in water were also found in this area. The origin of the arsenic there is still controversial. Groundwater in active mining areas has been polluted by both natural and anthropogenic sources. Arsenic-rich minerals contaminate the fractured limestone aquifer at Zimapán, Central México. Tailings and deposits smelter-rich fumes polluted the shallow granular aquifer. Arsenic contamination has also been reported in the San Antonio-El Triunfo mining zone, southern Baja California, and Santa María de la Paz, in San Luis Potosí state. Even in the absence of mining activities, hydrogeochemistry and statistical techniques showed that arsenopyrite oxidation may also contaminate water, as in the case of the Independencia aquifer in the Mexican Altiplano. High concentrations of arsenic have also been detected in geothermal areas like Los Azufres, Los Humeros, and Acoculco. Prevalence of dental fluorosis was revealed by epidemiological studies in Aguascalientes and San Luis Potosí states. Presence of fluoride in water results from dissolution of acid-volcanic rocks. In Mexico, groundwater supplies most drinking water. Current knowledge and the geology of Mexico indicate the need to include arsenic and fluoride determinations in groundwater on a routine basis, and to develop interdisciplinary studies to assess the contaminant's sources in all enriched areas.     

Origin and assessment of groundwater pollution and associated health risk: a case study in an industrial park,northwest China

Groundwater quality which relates closely to human health has become as important as its quantity due to the demand for safe water. In the present study, an entropy-weighted fuzzy water quality index (WQI) has been proposed for performing groundwater quality assessment in and around an industrial park, northwest China, where domestic water requirements are solely met by groundwater. The human health risk was assessed with the model recommended by the United States Environmental Protection Agency. In addition, the sources of major ions and main contaminants were also analyzed. The study shows that groundwater in the study area has been contaminated conjunctively by natural processes and industrial and agricultural activities. Nitrate, manganese (Mn), fluoride, total dissolved solids, total hardness and sulfate are major contaminants influencing groundwater quality. Nitrate and heavy metals such as Mn are mainly affected by human agricultural activities and industrial production, while other contaminants are mainly originated from mineral weathering and water–rock interactions. The results of water quality assessment suggest that half of the groundwater samples collected are of medium quality thus require pretreatment before human consumption. The mean health risk caused by the consumption of contaminated groundwater in the area is 8.42 × 10^?5 per year which surpasses the maximum acceptable level (5 × 10^?5 per year) recommended by the International Commission on Radiologic Protection. The entropy-weighted fuzzy WQI proposed in this study can not only assign proper weights to parameters but also treat uncertainties associated with water quality classification. This study will be of interest to international environmentalists and hydrogeologists. It will also be useful in regional groundwater management and protection.     

Elemental Analysis of Water and Sediments by External Beam PIXE Part 2. Industrial Zone of Ptolemais, Greece

In the industrial zone of Ptolemais, Greece there are two coal-fired power plants, one nitrogen-fertilizer producing plant and a factory making coal-bricks. The industrial and the municipal waste effluents of this area are discharged into the lake Vegoritis via a small stream named Solou. Water and core or grab sediment samples taken from the Solou stream and Vegoritis Lake were analyzed for metallic elements by the proton induced X-ray emission (PIXE) method and the different pollution sources of the area under study, as far as metal pollution is concerned, were tentatively identified. The communities contribute to the pollution with loads of Pb and Ni; Ca, Cr, and Mo are contributed mainly by industries, while Fe, Zn, Mn, Sr, and Br have their origin to both sources. Also the sediment enrichment factors (SEF) are calculated and discussed.     

Hydrogeochemistry and statistical analysis applied to understand fluoride provenance in the Guarani Aquifer System, Southern Brazil

High fluoride concentrations (up to 11 mg/L) have been reported in the groundwater of the Guarani Aquifer System (Santa Maria Formation) in the central region of the state of Rio Grande do Sul, Southern Brazil. In this area, dental fluorosis is an endemic disease. This paper presents the geochemical data and the combination of statistical analysis (Principal components and cluster analyses) and geochemical modeling to achieve the hydrogeochemistry of the groundwater and discusses the possible fluoride origin. The groundwater from the Santa Maria Formation is comprised of four different geochemical groups. The first group corresponds to a sodium chloride groundwater which evolves to sodium bicarbonate, the second one, both containing fluoride anomalies. The third group is represented by calcium bicarbonate groundwater, and in the fourth, magnesium is the distinctive parameter. The statistical and geochemical analyses supported by isotopic measurements indicated that groundwater may have originated from mixtures of deeper aquifers and the fluoride concentrations could be derived from rock/water interactions (e.g., desorption from clay minerals).     

Worldwide contamination of water by fluoride

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.     

Groundwater quality assessment in different land-use areas of Faridabad and Rohtak cities of Haryana using deviation index

Physico-chemical parameters were analysed to evaluate the groundwater quality of the two important cities of Haryana, Faridabad and Rohtak, and the pollution status of groundwater was compared using deviation index (DI). Groundwater of both the cities had high alkalinity, hardness, total dissolved solids (TDS) and electrical conductivity. The groundwater of Faridabad showed low fluoride concentration whereas in 74% of groundwater samples of Rohtak the fluoride levels were high. Land use and waste disposal practices were found to have an important effect on groundwater pollution.     

Groundwater fluoride and dental fluorosis in southwestern Nigeria

This study was carried out to assess the fluoride levels of groundwater from open wells, consumed by the residents of three communities located in two distinct geological terrains of southwestern Nigeria. Fluoride concentration was determined using spectrophotometric technique, while analysis of other parameters like temperature, pH and total dissolve solids followed standard methods. Results of the analysis indicated that groundwater samples from Abeokuta Metropolis (i.e., basement complex terrain) had fluoride content in the range of 0.65?±?0.21 and 1.20?±?0.14. These values were found to be lower than the fluoride contents in the groundwater samples from Ewekoro peri-urban and Lagos metropolis where the values ranged between 1.10?±?0.14-1.45?±?0.07 and 0.15?±?0.07-2.20?±?1.41?mg/l, respectively. The fluoride contents in almost all locations were generally higher than the WHO recommended 0.6?mg/l. Analysis of Duncan multiple range test indicated that there is similarity in the level of significance of fluoride contents between different locations of same geological terrain at p?≤?0.05. It was also observed that fluoride distribution of groundwater samples from the different geological terrain was more dependent on factors like pH and TDS than on temperature. The result of the analyzed social demographic characteristics of the residents indicated that the adults (between the age of 20 and >40?years) showed dental decay than the adolescent (<20?years). This signifies incidence of dental fluorosis by the high fluoride content in the drinking water of the populace. Further investigation on all sources of drinking water and other causes of tooth decay in the area is suggested.     

Survey of chemical constituents of Tehran's groundwater

One hundred and forty wells throughout the City of Tehran and its environs were sampled to determine the chemical quality of the groundwater. Total alkalinity, pH, conductivity, total dissolved solids, hardness and detergent concentrations were determined as well as levels of bicarbonate, calcium, magnesium, sulphate, chloride, sodium, potassium, fluoride, iodide and nitrate. Generally, chemical pollution of the water supplies was low. There were, however, regional elevations in nitrate, chloride and fluoride. Elevated fluoride levels were primarily in the northern regions of the city while high nitrates and chlorides were found primariiy in industrial areas. The health implications of chemical constituents in drinking water are discussed.     

新疆阿拉尔市苦咸水水化学特征、分布及成因分析

准确查明苦咸水分布、水化学特征及成因对此类非常规水资源的开发利用及当地水安全保障能力的提高具有重要意义.通过对新疆阿拉尔市地下水进行采样分析,利用水化学图解、描述性统计分析、离子比值法、饱和指数法等方法分析苦咸水的水化学特征及形成机制.结果表明,研究区苦咸水水化学类型以HCO₃·SO₄·Cl-Na·Ca·Mg、SO₄·Cl-Na·Mg和SO₄·Cl-Na型为主,苦咸水分布面积2163.45 km²,占总面积的77.26%,主要分布在平原水库下游及塔里木河在该市范围内的后段,苦咸水的形成主要受蒸发-浓缩作用的影响,其次是岩石风化作用,同时,人类活动对研究区苦咸水的空间分布也施加了一定的积极影响.