Abstract

Groundwater fluoride contamination is a global concern, particularly in South Asia. Like other Asian countries, this problem has also been reported on a large spatial scale in Pakistan. The present study was designed to investigate the geochemical mechanisms responsible for fluoride mobilization in different geological settings of Punjab, Pakistan, and the human health risk to the local populations due to elevated fluoride (F) intake via groundwater. Groundwater samples (N = 134) were collected in diverse aquifer systems (Thal Desert, Upper and Lower Indus floodplain areas) of Punjab, Pakistan, and analyzed for F and other anions by using ion-chromatography (IC). Fluoride concentrations (mg/L) ranged from 0.1 to 6.2 (2 % samples >1.5 mg/L) in Lower Indus Areas (LIA), 0.3–10.3 (25 % samples >1.5 mg/L) in Upper Indus Areas (UIA), and 0.6–4.7 (71 % samples>1.5 mg/L) in Thal desert areas (TDA). The mineral saturation indices suggest that fluoride-bearing minerals (e.g. fluorite) are mainly responsible for fluoride mobilization in the study area. The extensive fluoride contamination in the Thal desert areas is associated with the dissolution of evaporites due to a rapid increase of aquifer levels in recent years and may result in elevated pH, HCO3, and Na along with Ca-deficient water (controlled by calcisols) and Na-HCO3 type facies, which finally triggers the F mobilization into groundwater via ion exchange process. On the other hand, alkaline aquifers in the upper Indus areas (Kasur, Okara) experience excessive pumping and fluoride leaching due to the evaporative dissolution process. A human health risk assessment model (HHRA) shows that children and male populations are at a higher risk of fluorosis particularly in Thal desert areas of Punjab, Pakistan. Furthermore, large numbers of people (approximately 100–200 people/km2 at TDA and 200–500 people/km2 at UIA) in the studied areas are at risk of fluorosis and other health risks due to ingestion of fluoride-contaminated drinking water.

Introduction

Groundwater is a primary drinking water source, particularly in developing countries, and its contamination with different anions and/or metal ions is a major concern on a global scale (Lapworth et al., 2022, Younas et al., 2019). Different natural (geogenic) processes such as mineral weathering and dissolution, volcanic activities and anthropogenic processes such as agricultural and mining activities, surface runoff etc. leads to the disturbance of the natural aquifer system, and may result in varying amounts of chemicals/contaminants into groundwater Qin et al., 2013; Rehman et al., 2022). Fluorine is an abundant trace element present in earth’s crust/soil which ranges from about 500–700 mg/kg and may leach into groundwater through different hydrological processes (Nordstrom and Smedley, 2022). Previous studies reported that natural groundwater fluoride enrichment is controlled by various hydrogeological factors including groundwater levels, the local geology and geochemical conditions (pH, HCO3?, Na+/Ca+, Cl). Other important factors that may affect the solubility of fluoride in groundwater includes residence time, cation and anion exchange processes and arid to semiarid climatic conditions (Farooqi et al., 2007a; De et al., 2023).

Fluoride is often a natural constituent of groundwater and is considered hazardous at high concentrations Viz; beyond the World Health Organization (WHO) guideline of 1.5 mg/L and may lead to dental and/or skeletal fluorosis (Wang et al., 2024). On the other hand, lower concentrations (e.g. <0.5 mg/L) into drinking water may cause dental caries. According to the WHO, about 65 % of waterborne human diseases are associated with F contaminated water sources (De et al., 2023). Therefore, this issue is a global problem that needs detailed insight into the fluoride dynamics of natural aquifer systems for water resource management purposes. Globally, 180 million people are potentially exposed to fluoride-contaminated groundwater and at risk of fluorosis due to natural/geogenic elevated groundwater fluoride concentrations, especially in Africa and Asia. In Asia, more than 90 million people are at risk of fluorosis with the largest affected populations living in India (49 million), China (22 million), and Pakistan (7.6 million) (Podgorski and Berg, 2022; Araya et al., 2022; Podgorski et al., 2018). Given that excessive chronic intake of fluoride poses serious health threats, it is considered an emerging environmental and public health issue in various countries, including Pakistan (Rahman et al., 2020; Bhattacharya et al., 2020).

Pakistan is among the countries with widespread groundwater fluoride contamination due to its natural sedimentary setting and a semi-arid/arid climate (Ling et al., 2022). To date, several studies have reported fluoride contamination on a small spatial scale (Rasool et al., 2015; Rasheed et al., 2022; Rehman et al., 2022). Furthermore, a recent study utilizing over 5000 fluoride data points highlighted extensive fluoride contamination at different hotspot areas, suggesting detailed insights of underlying mechanisms at these locations, including the Thal desert and Indus floodplain (Ling et al., 2022). This study focuses on three areas of the Punjab province: Lower Indus Areas (LIA), Upper Indus Areas (UIA), and Thal Desert Areas (TDA). By comparing groundwater chemistry in these spatially distinct areas within the same basin, more attention can be devoted to the influence of hydrogeochemical conditions. The specific objectives of this study are I). To assess the spatial distribution of fluoride and other water quality parameters, II). To understand the key hydrogeochemical controlling factors involved in fluoride enrichment. III). To assess the human health risk due to fluoride contaminated drinking water at different areas of Punjab, Pakistan.

Section snippets

Study area

The Punjab Province is the most populous region of Pakistan with more than 125 million inhabitants and is located between 35.91° N to 75.34° E and 27.42° N to 69.82° E with an area of 205,344 km2 (Fig. 1). The province hosts the five tributaries of the Indus River (Indus, Jhelum, Chenab, Ravi, and Sutlej Rivers) along with the world’s 2nd largest canal system. Climatic conditions range from sub-humid in the north to semi-arid in the south with monthly mean temperatures ranging from 23 to 45 °C.

Hydrochemistry and fluoride distributional patterns

A summary of the water quality parameters representing an overview of the overall hydrochemistry of the area is given as (Table 1). The WQI was calculated using the EPA relationship (Equation i) and factors such as weight assigned (wi), relative weightage (Wi), average values of the selected water variables (Ci), and the WHO guidelines (Si) (Table S4). The WQI index assigned one of four classes to groundwater quality: Excellent, Good, Poor, or Unfit. The calculated WQI classifies the…

Human health risk assessment (HHRA)

Drinking water is the main pathway of fluoride ingestion in humans, and prolonged consumption of fluoride-contaminated water may increase the risk of fluorosis among the residents of these areas (Rehman et al., 2022). The human health effects due to fluoride intake via drinking water at different levels in the Indus Basin are categorized into five classes (Fig. S6) (Ahada and Suthar, 2019). About 44 % of samples fall under Class-I, indicating that groundwater fluoride values are below the…

Conclusion

The present study was conducted to assess the spatial distribution of fluoride, risk factors associated with fluoride mobilization, and non-carcinogenic human health hazards in a diverse aquifer system of the Indus Basin in Punjab, Pakistan. The relative degree of fluoride contamination in the studied areas was found to be Thal Desert Area (TDA) > Upper Indus Area (UIA) > Lower Indus Area (LIA). The WHO guideline of 1.5 mg/L of F in drinking water was exceeded in 71 % of the groundwater samples…

CRediT authorship contribution statement

Muhammad Sadiq: Writing – original draft, Methodology, Investigation, Formal analysis. Syed Ali Musstjab Akber Shah Eqani: Writing – original draft, Supervision, Resources, Project administration, Investigation, Funding acquisition, Conceptualization. Ismat Nawaz: Writing – review & editing, Resources, Project administration, Methodology, Investigation. Nazneen Bangash: Writing – review & editing, Resources, Investigation. Shazia Ilyas: Writing – review & editing, Validation, Investigation,

Funding

This work is funded by the Higher Education Commission (HEC) of Pakistan under the International Research Support Initiative Program (IRSIP) (Project No. I-8/HRD/2021/10887) and HEC Funded project/NRPU-14825.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References (48)

There are more references available in the full text version of this article.

ABSRTRACT ONLINE AT
https://www.sciencedirect.com/science/article/abs/pii/S004896972502090X?via%3Dihub