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Fluoride in geothermal water: Occurrence, origin, migration and environmental impact.Abstract
Highlights
- Distribution and occurrence of fluoride in volcanic geothermal system and non-volcanic geothermal system
- Geothermal fluoride mobilization mechanisms and naturally occurring control strategies
- Environmental impact and treatment strategy of geothermal fluoride
Geothermal water, a vital renewable energy source extensively harnessed for heating and power generation, is marred by a prevalent issue – high fluoride content. The environmental impact of geothermal fluoride has been recognized globally. The natural discharge of geothermal water, coupled with its widespread exploitation, instigates the translocation of geothermal fluoride toward shallow and surface water ecosystems, culminating in escalating fluoride concentrations, thereby posing potential threats to both ecosystems and human health. Nevertheless, despite the pivotal significance of fluoride in geothermal water, a comprehensive understanding of its origins, migratory dynamics, ecological consequences, and ameliorative methodologies remains to be studied. This review provides a comprehensive examination of fluoride’s global occurrence and distribution in geothermal waters, emphasizing the contrast between volcanic and non-volcanic geothermal systems. It analyzes the various sources of fluoride in these waters and elucidates the mechanisms driving its mobilization. In volcanic geothermal systems, fluoride primarily derives from magmatic volatiles, while in non-volcanic systems, it mainly results from the dissolution of minerals. Temperature is a key factor influencing fluoride concentration in geothermal waters, with alkaline conditions and low calcium levels contributing to higher fluoride enrichment. The review details how fluoride concentrations change as geothermal fluids migrate from deeper to shallower layers. Based on the enrichment characteristics of fluorides, this paper explores the potential applications of geothermal fluorides. It also examines the environmental impacts of geothermal fluoride, presents various treatment methods, and provides a summary of current research both domestically and internationally, while proposing directions for future studies. This study is instrumental in formulating judicious fluoride management policies and establishing sustainable strategies for the development of geothermal resources.
Introduction
Geothermal water, a naturally occurring resource, is garnering increasing attention due to its burgeoning potential in renewable energy generation and direct-use applications like heating and bathing (Fridleifsson, 2001). However, the geochemical composition of geothermal water, encompassing various ions and trace elements, has raised environmental and health concerns (Bundschuh and Maity, 2015; Mott et al., 2022). Among these constituents, fluoride, a common presence in geothermal water, is of particular interest due to its dual role as both a beneficial and potentially harmful element.
Fluoride, when present in drinking water in small quantities (<0.5 mg/L), is essential for human health as it contributes to bone mineralization and helps prevent dental caries. It actively contributes to bone mineralization and plays a crucial role in the prevention of dental caries. Nevertheless, excessive intake of fluoride (>1.5 mg/L), can lead to fluorosis, affecting teeth and bones, and potentially causing health issues like kidney stones, thyroid function impairment, and reduced cognitive development in children (Ozsvath, 2009).
High concentrations of fluoride in geothermal water are reported worldwide, e.g., Argentina (Chiodi et al., 2019; Hudson-Edwards and Archer, 2012; Peralta Arnold et al., 2017; Varekamp et al., 2009), America (Deng et al., 2011), China (Guo, 2012; Guo et al., 2009, Guo et al., 2014; Huang et al., 2023), Chile (Munoz-Saez et al., 2018, Munoz-Saez et al., 2020; Tassi et al., 2010), France (Sanjuan et al., 2010), Indonesia (Delmelle and Bernard, 1994; Rahayudin et al., 2020), Iceland (Arnórsson et al., 1983a, Arnórsson et al., 1983b; Björke et al., 2015; Gudmundsson and Arnórsson, 2005; Kaasalainen and Stefánsson, 2012), and New Zealand (Christenson, 2000). Fluoride in geothermal water ranges from 0.01 to ~6000 mg/L, varying widely due to hydrogeological conditions (Nordstrom, 2022). While geothermal water with high fluoride concentrations has potential medical applications (Mel’nichuk and Khodasevich, 2015), it is often unsuitable for drinking, frequently exceeding the World Health Organization’s recommended drinking water guideline value (1.5 mg/L, WHO, 2011). Fluoride levels in geothermal water typically exceed those in other groundwater and surface water sources (Nordstrom, 2022). The presence of fluoride in geothermal water carries environmental implications (Abiye et al., 2018; Guo, 2012; Guo et al., 2014; Huang et al., 2023; Wang et al., 2021), particularly in regions where geothermal water is discharged without treatment which will hinder the development and utilization of geothermal resources in the area. High fluoride levels can be toxic to aquatic life, accumulate in soils, potentially impact plant growth, and enter the food chain (Ozsvath, 2009). Given the extensive use of geothermal resources, intensive research into the source and distribution of fluorine in geothermal water is crucial for effective resource management, minimizing environmental impacts, and safeguarding public health. However, despite the global prevalence of high fluoride concentrations in groundwater influenced by geothermal activity, the underlying mechanisms remain incompletely understood (Wang et al., 2021).
This review is dedicated to providing a comprehensive overview of the current state of knowledge regarding fluoride in geothermal water. Based on extensive fluoride data, the distribution of fluorine in different types of geothermal systems and different types of geothermal water is described. We summarized the sources, mobilization, environmental impacts, and treatment of the geothermal fluoride. Additionally, combining insufficient current research, we identified current challenges and introduced the future perspective on managing fluoride in geothermal water. This work contributes to a better understanding of the chemical behavior of fluorine in geothermal water and the fate of fluorine after geothermal water discharge, providing valuable insights for the sustainable and safe utilization of geothermal resources.
Section snippets
Occurrence and distribution of geothermal fluoride
High fluoride levels with a large range of concentrations are frequently found in geothermal water, exhibiting concentrations that span from a few milligrams to several thousand milligrams per liter. A comprehensive overview of fluoride concentrations in hot water across global geothermal systems is presented in Table S1.
Geothermal systems can be categorized into volcanic geothermal systems (VGS) and non-volcanic geothermal systems (NVGS) distinct groups based on their geological settings …
Sources
Studies on stable isotopes (?D and ?18O) of water show that geothermal water originates from atmospheric or seawater sources, occasionally encompassing a fraction of magmatic water–fluid derived from magma (Giggenbach, 1992). The chemical composition of geothermal water is contingent upon its provenance and the geological nature of the surrounding rock it flows.
Fluoride content in atmospheric precipitation is typically low, except in cases where it intermingles with volcanic ash containing…
Variations of fluoride during geothermal water ascent
In the ascent of reservoir fluid within a geothermal system, driven by thermodynamic forces, a complex interplay of transformations occurs. These changes encompass processes such as depressurization-induced boiling, the liberation of gas components like carbon dioxide due to reduced pressure, and adiabatic or conduction-driven cooling (Arnórsson et al., 2007). These dynamics collectively induce significant shifts in both the physical and chemical attributes of the fluid, consequently impacting…
Location and evaluation of geothermal resources
Fluoride is stably present in hydrothermal systems, and its concentration can reflect the temperature and extent of water-rock interaction in these systems. This characteristic allows fluoride concentration to be used in determining the distribution of geothermal anomalies and heat sources, thereby aiding in the localization and evaluation of geothermal resources.
In tectonically active areas, low-temperature groundwater (<30 °C) can help identify blind geothermal systems and blind fault…
Environmental impacts
Conclusions
References (97)
- et al.Fluoride concentrations in the arid Namaqualand and the Waterberg groundwater, South Africa: understanding the controls of mobilization through hydrogeochemical and environmental isotopic approaches
Groundw. Sustain. Dev.
(2018)
- et al.Trace elements in the thermal groundwaters of Vulcano Island (Sicily)
J. Volcanol. Geotherm. Res.
(2000)
- Co-occurrence of arsenic and fluoride in groundwater of semi-arid regions in Latin America: genesis, mobility and remediation
J. Hazard. Mater.
(2013)
- et al.The chemistry of geothermal waters in Iceland. II. Mineral equilibria and independent variables controlling water compositions
Geochim. Cosmochim. Acta
(1983)
- et al.The chemistry of geothermal waters in Iceland. III. Chemical geothermometry in geothermal investigations
Geochim. Cosmochim. Acta
(1983)
- et al.Fluoride removal from water by adsorption—a review
Chem. Eng. J.
(2011)
- et al.Surface water chemistry at Torfajökull, Iceland—quantification of boiling, mixing, oxidation and water–rock interaction and reconstruction of reservoir fluid composition
Geothermics
(2015)
- Mechanisms of fluoride release in sediments of Argentina’s central region
Sci. Total Environ.
(2013)
- et al.Geothermal arsenic: occurrence, mobility and environmental implications
Renew. Sustain. Energy Rev.
(2015)
- et al.Predicting geogenic groundwater fluoride contamination throughout China
J. Environ. Sci.
(2022)
- et al.Hydrogeochemistry of sodium-bicarbonate type bedrock groundwater in the Pocheon spa area, South Korea: water–rock interaction and hydrologic mixing
J. Hydrol.
(2006)
- Fluorine geochemistry in bedrock groundwater of South Korea
Sci. Total Environ.
(2007)
- A critical review on geochemical and geological aspects of fluoride belts, fluorosis and natural materials and other sources for alternatives to fluoride exposure
J. Hydrol.
(2019)
- Geochemistry of fluids associated with the 1995–1996 eruption of Mt. Ruapehu, New Zealand: signatures and processes in the magmatic-hydrothermal system
J. Volcanol. Geotherm. Res.
(2000)
- Fluoride: a naturally-occurring health hazard in drinking-water resources of Northern Thailand
Sci. Total Environ.
(2016)
- et al.Heated column experiments: a proxy for investigating the effects of in situ thermal recovery operations on groundwater geochemistry
J. Contam. Hydrol.
(2021)
- et al.Environmental hazards of fluoride in volcanic ash: a case study from Ruapehu volcano, New Zealand
J. Volcanol. Geotherm. Res.
(2003)
- et al.Recharge history and controls on groundwater quality in the Yuncheng Basin, north China
J. Hydrol.
(2010)
- et al.Geochemistry, mineralogy, and chemical modeling of the acid crater lake of Kawah Ijen Volcano, Indonesia
Geochim. Cosmochim. Acta
(1994)
- et al.Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation
Geochim. Cosmochim. Acta
(2011)
- Fluorine chemistry at the millennium
J. Fluor. Chem.
(2005)
- Geothermal energy for the benefit of the people
Renew. Sustain. Energy Rev.
(2001)
- Geothermal solute equilibria. Derivation of Na-K-Mg-Ca geoindicators
Geochim. Cosmochim. Acta
(1988)
- Isotopic shifts in waters from geothermal and volcanic systems along convergent plate boundaries and their origin
Earth Planet. Sci. Lett.
(1992)
- et al.Secondary mineral–fluid equilibria in the Krafla and Námafjall geothermal systems, Iceland
Appl. Geochem.
(2005)
- Hydrogeochemistry of high-temperature geothermal systems in China: a review
Appl. Geochem.
(2012)
- et al.Hydrogeochemistry and environmental impact of geothermal waters from Yangyi of Tibet, China
J. Volcanol. Geotherm. Res.
(2009)
- The impact of the hyperacid Ijen Crater Lake: risks of excess fluoride to human health
Sci. Total Environ.
(2005)
- Fluorine in formation waters, Alberta Basin, Canada
Appl. Geochem.
(1995)
- Fluoride occurrence in geothermal water of fault zone area, Southeast China
Chemosphere
(2023)
- et al.Geochemistry of As-, F- and B-bearing waters in and around San Antonio de los Cobres, Argentina, and implications for drinking and irrigation water quality
J. Geochem. Explor.
(2012)
- et al.The chemistry of trace elements in surface geothermal waters and steam, Iceland
Chem. Geol.
(2012)
- et al.Leakage of Active Crater lake brine through the north flank at Rincón de la Vieja volcano, northwest Costa Rica, and implications for crater collapse
J. Volcanol. Geotherm. Res.
(2000)
- et al.Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV acid–sulfate waters
Appl. Geochem.
(2009)
- Fluoride and iodine enrichment in groundwater of North China Plain: evidences from speciation analysis and geochemical modeling
Sci. Total Environ.
(2017)
- Monitoring and prediction of high fluoride concentrations in groundwater in Pakistan
Sci. Total Environ.
(2022)
- et al.Temperature influence on mobilisation and (re)fixation of trace elements and heavy metals in column tests with aquifer sediments from 10 to 70 °C
Water Res.
(2020)
- et al.New geothermometers for carbonate—evaporite geothermal reservoirs
Geothermics
(1986)
- et al.The bimodal pH distribution of volcanic lake waters
J. Volcanol. Geotherm. Res.
(2003)
- et al.Use of reaction path modeling to identify the processes governing the generation of neutral Na–Cl and acidic Na–Cl–SO4 deep geothermal liquids at Miravalles geothermal system, Costa Rica
J. Volcanol. Geotherm. Res.
(2003)
- et al.The composition of the Earth
Chem. Geol.
(1995)
- et al.Fluoride in drinking water and its removal
J. Hazard. Mater.
(2006)
- Behaviour of major elements and some trace elements (Li, Rb, Cs, Sr, Fe, Mn, W, F) in deep hot waters from granitic areas
Chem. Geol.
(1990)
- Catalog of geothermal play types based on geologic controls
Renew. Sustain. Energy Rev.
(2014)
- et al.Review of fluoride removal from drinking water
J. Environ. Manage.
(2009)
- Boron in geothermal energy: sources, environmental impacts, and management in geothermal fluid
Renew. Sustain. Energy Rev.
(2022)
- et al.Hydrothermal discharge from the El Tatio basin, Atacama, Chile
J. Volcanol. Geotherm. Res.
(2018)
- Fluoride in thermal and non-thermal groundwater: insights from geochemical modeling
Sci. Total Environ.
(2022)
There are more references available in the full text version of this article
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ABSTRACT ONLINE AT https://www.sciencedirect.com/science/article/abs/pii/S0375674224002565
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