Geochemical modeling, source apportionment, health risk exposure and control of higher fluoride in groundwater of sub-district Dargai, Pakistan.

The present study examined the hydrogeochemical profile of higher fluoride (F─) in groundwater of mixed industrial and mining areas of Dargai, northern Pakistan. Groundwater samples (n = 75) were collected from three hydrogeochemical environments. The mean concentrations of pH, EC, TDS, Depth and Temperature were (7.6, 1081 µS/cm, 590 mg/L, 75 m, 28.03 °C), for chemical ions viz. NO3, PO4, SO4, Cl, HCO3, Na, K, Ca and Mg were (18.5, 2.7, 161, 107, 330, 150, 9.76, 33, 52) mg/L respectively. Whereas, the mean concentration of F─ was 2.0 mg/L. Therefore, 51% groundwater samples exceeded the WHO guideline of F─ 1.5 mg/L. Additionally, we measured the mean F─ concentration in rocks, coal and wastewater, which were (670, 98) mg/Kg and 2.3 mg/L respectively. The principal component analysis multilinear regression (PCA─MLR) extracted five significant factors which shows natural, mixed and anthropogenic pollution. Thus, fluorite is the primary source of F─ contamination in groundwater. While apatite, biotite and muscovite minerals are the secondary sources which occurs in association with quartzite, granite rocks. Under alkaline conditions, F─ contamination is supported by higher Na+, HCO3─ and lower Ca++ concentrations. The accuracy and reproducibility of the measurement of fluoride was assessed by adopting a standard method of water. The percentage recovery of F─ was 97% and reproducibility was within ±5% error limit. Lastly, a health risk community fluorosis index (CFI) was calculated through Dean's formula which shows unsuitability of groundwater sources conceiving community fluorosis in the entire study area.

Mapping human health risk from exposure to potential toxic metal contamination in groundwater of Lower Dir, Pakistan: Application of multivariate and geographical information system.

The study aimed to assess the physicochemical parameters (pH, electrical conductivity (EC), total dissolve solid (TDS), oxidation reduction potential (ORP), Temperature) and potential toxic metals (PTMs), including Ni, Mn, Cr, Cu, Cd, Pb, Co, Fe and Zn in the groundwater of Lower Dir, Pakistan. Furthermore, the pollution sources and spatial distribution pattern of PTMs were also investigated via principal component analysis (PCA) and geographic information system (GIS) application to understand the changing behaviors of PTMs in groundwater. The average concentrations of physicochemical parameters such as pH, EC, TDS, ORP and Temperature were 7.1, 418 µS/cm, 251 mg/L, 193 mV and 25.7 ○C, while the concentrations of PTMs; Ni, Mn, Cr, Cu, Cd, Pb, Co, Fe and Zn were 0.25, 0.34, 0.09, 0.29, 0.10, 0.08, 0.10, 0.83 and 0.25  mg/L, respectively. Among the selected metals, Mn, Cr, Cd, Pb, Co and Fe were exceeded the WHO guidelines and their percentage contribution were 43%, 57%, 45%, 70%, 70% and 62%, respectively. The increasing order of PTMs were; Pb > Co > Fe > Cr > Cd > Mn > Cu > Ni > Zn in the study area. PCA represented three significant factors, which explained 76% variability in the groundwater. Whereas, clustering analysis (CA) grouped groundwater into three distinct clusters less polluted (C1), moderate polluted (C2) and highly polluted (C3). Human health risk assessment was carried out to check the suitability of groundwater for drinking and domestic uses. The HQ and HRIs values of Cd were >1, suggested that the groundwater sources are unfit for drinking and domestic purposes and may be caused potential health risk after long term ingestion.

Fluoride prevalence in groundwater around a fluorite mining area in the flood plain of the River Swat, Pakistan.

This study investigated the fluoride (F-) concentrations and physicochemical parameters of the groundwater in a fluorite mining area of the flood plain region of the River Swat, with particular emphasis on the fate and distribution of F- and the hydrogeochemistry. To better understand the groundwater hydrochemical profile and F- enrichment, groundwater samples (n=53) were collected from shallow (24-40m), mid-depth (48-65m) and deep (85-120m) aquifers, and then analysed using an ion-selective electrode. The lowest F- concentration (0.7mg/L) was recorded in the deep-aquifer groundwater, while the highest (6.4mg/L) was recorded in shallow groundwater. Most groundwater samples (62.2%) exceeded the guideline (1.5mg/L) set by the World Health Organization (WHO); while for individual sources, 73% of shallow-groundwater samples (F- concentration up to 6.4mg/L), 42% of mid-depth-groundwater samples, and 17% of deep-groundwater samples had F- concentrations that exceeded this permissible limit. Assessment of the overall quality of the groundwater revealed influences of the weathering of granite and gneisses rocks, along with silicate minerals and ion exchange processes. Hydrogeochemical analysis of the groundwater showed that Na+ is the dominant cation and HCO3- the major anion. The anionic and cationic concentrations across the entire study area increased in the following order: HCO3>SO4>Cl>NO3>F>PO4 and Na>Ca>Mg>K, respectively. Relatively higher F- toxicity levels were associated with the NaHCO3 water type, and the chemical facies were found to change from the CaHCO3 to (NaHCO3) type in calcium-poor aquifers. Thermodynamic considerations of saturation indices indicated that fluorite minerals play a vital role in the prevalence of fluorosis, while under-saturation revealed that - besides fluorite minerals - other F- minerals that are also present in the region further increase the F- concentrations in the groundwater. Finally, a health risk assessment via Dean's classification method identified that the groundwater with relatively higher F- concentrations is unfit for drinking purposes.