Groundwater contamination by heavy metals (HMs) released by weathering and mineral dissolution of granite, gneisses, ultramafic, and basaltic rock composition causes human health concerns worldwide. This paper evaluated the heavy metals (HMs) concentrations and physicochemical variables of groundwater around enriched chromite mines of Malakand, Pakistan, with particular emphasis on water quality, hydro-geochemistry, spatial distribution, geochemical speciation, and human health impacts. To better understand the groundwater hydrogeochemical profile and HMs enrichment, groundwater samples were collected from the mining region (n = 35), non-mining region (n = 20), and chromite mines water (n = 5) and then analyzed using ICPMS (Agilent 7500 ICPMS). The ranges of concentrations in the mining, non-mining, and chromite mines water were 0.02–4.5, 0.02–2.3, and 5.8–6.0 mg/L for CR, 0.4–3.8, 0.05–3.6, and 3.2–5.8 mg/L for Ni, and 0.05–0.8, 0.05–0.8, and 0.6–1.2 mg/L for Mn. Geochemical speciation of groundwater variables such as OH⁻, H⁺, Cr⁺², Cr⁺³, Cr⁺⁶, Ni⁺², Mn⁺², and Mn⁺³ was assessed by atomic fluorescence spectrometry (AFS). Geochemical speciation determined the mobilization, reactivity, and toxicity of HMs in complex groundwater systems. Groundwater facies showed 45% CaHCO₃, 30% NaHCO₃, 23.4% NaCl, and 1.6% Ca-Mg-Cl water types. The noncarcinogenic and carcinogenic risk of HMs outlined via hazard quotient (HQ) and total hazard indices (THI) showed the following order: Ni > Cr > Mn. Thus, the HHRA model suggested that children are more vulnerable to HMs toxicity than adults. Hierarchical agglomerative cluster analysis (HACA) showed three distinct clusters, namely the least, moderately, and severely polluted clusters, which determined the severity of HMs contamination to be 66.67% overall. The PCAMLR and PMF receptor model suggested geogenic (minerals prospects), anthropogenic (industrial waste and chromite mining practices), and mixed (geogenic and anthropogenic) sources for groundwater contamination. The mineral phases of groundwater suggested saturation and undersaturation. Nemerow’s pollution index (NPI) values determined the unsuitability of groundwater for domestic purposes. The EC, turbidity, PO₄⁻³, Na⁺, Mg⁺², Ca⁺², Cr, Ni, and Mn exceeded the guidelines suggested by the World Health Organization (WHO). The HMs contamination and carcinogenic and non-carcinogenic health impacts of HMs showed that the groundwater is extremely unfit for drinking, agriculture, and domestic demands. Therefore, groundwater wells around the mining region need remedial measures. Thus, to overcome the enrichment of HMs in groundwater sources, sustainable management plans are needed to reduce health risks and ensure health safety.

Groundwater contamination by potentially harmful elements (PHEs) originating from the weathering of granitic and gneissic rock dissolution poses a public health concern worldwide. This study investigated physicochemical variables and PHEs in the groundwater system and mine water of the Adenzai flood plain region, in Pakistan, emphasizing the fate distribution, source provenance, chemical speciation, and health hazard using the human health risk assessment HHRA-model. The average concentrations of the PHEs, viz., Ni, Mn, Cr, Cu, Cd, Pb, Co, Fe, and Zn 0.23, were 0.27, 0.07, 0.30, 0.07, 0.06, 0.08, 0.68, and 0.23 mg/L, respectively. The average values of chemical species in the groundwater system, viz., H⁺, OH⁻, Ni²⁺, Mn²⁺, Mn³⁺, Cr³⁺, Cr⁶⁺, Cu⁺, Cu²⁺, Cd²⁺, Pb²⁺, Pb⁴⁺, Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, and Zn²⁺, were 1.0 × 10⁻⁴ ± 1.0 × 10⁻⁶, 1.0 × 10⁻⁴ ± 9.0 × 10⁻⁷, 2.0 × 10⁻¹ ± 1.0 × 10⁻³, 3.0 × 10⁻¹ ± 1.0 × 10⁻³, 1.0 × 10⁻²² ± 1.0 × 10⁻²³, 4.0 × 10⁻⁶ ± 2.0 × 10⁻⁶, 4.0 × 10⁻¹¹ ± 2.0 × 10⁻¹¹, 9.0 × 10⁻³ ± 1.0 × 10⁻², 2.0 × 10⁻¹ ± 2.0 × 10⁻³, 7.0 × 10⁻² ± 6.0 × 10⁻², 5.0 × 10⁻² ± 5.0 × 10⁻², 2.0 × 10⁻² ± 1.5 × 10⁻², 6.0 × 10⁻² ± 4.0 × 10⁻², 8.0 × 10⁻³¹ ± 6.0 × 10⁻³¹, 3.0 × 10⁻¹ ± 2.0 × 10⁻⁴, 4.0 × 10⁻¹⁰ ± 3.0 × 10⁻¹⁰, and 2.0 × 10⁻¹ ± 1.0 × 10⁻¹. The mineral compositions of PHEs, viz. Ni, were bunsenite, Ni(OH)₂, and trevorite; Mn viz., birnessite, bixbyite, hausmannite, manganite, manganosite, pyrolusite, and todorokite; Cr viz., chromite and eskolaite; Cu viz., CuCr₂O₄, cuprite, delafossite, ferrite-Cu, and tenorite; Cd viz., monteponite; Pb viz, crocoite, litharge, massicot, minium, plattnerite, Co viz., spinel-Co; Fe viz., goethite, hematite, magnetite, wustite, and ferrite-Zn; and Zn viz., zincite, and ZnCr₂O₄ demarcated undersaturation and supersaturation. However, EC, Ca²⁺, K⁺, Na⁺, HCO₃⁻, Cr, Cd, Pb, Co, and Fe had exceeded the WHO guideline. The Nemerow’s pollution index (NPI) showed that EC, Ca²⁺, K⁺, Na⁺, HCO₃⁻, Mn, Cd, Pb, Co, and Fe had worse water quality. Principal component analysis multilinear regression (PCAMLR) and cluster analysis (CA) revealed that 75% of the groundwater contamination originated from geogenic inputs and 18% mixed geogenic-anthropogenic and 7% anthropogenic sources. The HHRA-model suggested potential non-carcinogenic risks, except for Fe, and substantial carcinogenic risks for evaluated PHEs. The women and infants are extremely exposed to PHEs hazards. The non-carcinogenic and carcinogenic risks in children, males, and females had exceeded their desired level. The HHRA values of PHEs exhibited the following increasing pattern: Co > Cu > Mn > Zn > Fe, and Cd > Pb > Ni > Cr. The higher THI values of PHEs in children and adults suggested that the groundwater consumption in the entire region is unfit for drinking, domestic, and agricultural purposes. Thus, all groundwater sources need immediate remedial measures to secure health safety and public health concerns.

Fluoride (F⁻) contamination in drinking groundwater is a significant human health risk in Pakistan. Moreover, high fluoride pollution in drinking water causes a variety of disorders, including dental, neurological, and skeletal fluorosis. The aim of this research was to evaluate the health risk of elevated fluoride in groundwater and its suitability assessment for drinking purposes. The total of (n = 37) samples were collected from community tube wells of Quetta Valley, Balochistan, Pakistan. The results show a mean pH value of 7.7, TDS of 404.6 mg/L, EC of 500 µs/cm, depth of 96.8 feet, and turbidity of 1.7 nephelometric turbidity units. The mean values of HCO₃⁻, Ca²⁺, Mg²⁺, and Na⁺, were 289.5, 47.5, 30.6, and 283.3 mg/L, respectively. The mean values of SO₄²⁻, NO₃⁻, K⁺, Cl⁻, and Fe²⁺, were 34.9, 1.0, 1.6, 25.6, and 0.01 mg/L, respectively. The F⁻ concentration in the groundwater varied between 0.19 and 6.21, with a mean value of 1.8 mg/L, and 18 samples out of 37 were beyond the WHO recommended limit of 1.5 mg/L. The hydrochemical analysis results indicated that among the groundwater samples of the study area, 54% samples were Na-HCO₃ type and 46% were mixed CaNaHCO₃ type. The saturation indices of the mineral phases reveal that the groundwater sources of the study area were saturated with CaCO₃ and halide minerals due to their positive (SI) values. Such minerals include calcite, dolomite, gypsum, and fluorite. The principal component analysis results reveal that the groundwater sources of the study area are contaminated due to geological and anthropogenic actions. The health risk assessment results of the F⁻ concentrations show the ranges of ADD_ingestion for children, females, and males in the Quetta Valley, and their mean values were observed to be 0.093052, 0.068825, and 0.065071, respectively. The HQ_ingestion mean values were 1.55086, 1.147089, and 1.084521 for children, females, and males, respectively. It was noticed that children had the highest maximum and average values of ADD_ingestion and HQ_ingestion in the research area, indicating that groundwater fluoride intake poses the greatest health risk to children. The water quality index (WQI) analyses show that 44% of the samples belong to the poor-quality category, 49% were of good quality, and 8% of the samples of the study area belong to the excellent category.