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

Geothermal water, compared to cold groundwater, tends to carry a much higher fluoride content. When this high-fluoride geothermal water mixes with surface water or cold groundwater, it can lead to an increase in their fluoride concentrations, potentially restricting their usability for water supply. The concentration of fluoride in non-geothermal water depends on several factors: (1) the concentration and proportion of fluoride in the geothermal water; (2) the pH conditions of the mixed water…

Conclusions

This review focuses on the behavior of fluoride in geothermal water and its environmental impact. Through extensive analysis and synthesis of existing research, we have unveiled the diverse distribution patterns of fluoride across various geothermal systems and geothermal water types. Our investigation has disclosed that the most substantial fluorine concentrations within geothermal water are predominantly prevalent in volcanic systems, with the zenith observed in the acidic environs of crater…

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ABSTRACT ONLINE AT https://www.sciencedirect.com/science/article/abs/pii/S0375674224002565

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