Hydrogeochemical characteristics, stable isotopes, positive matrix factorization, source apportionment, and health risk of high fluoride groundwater in semiarid region.

Chronic exposure to high fluoride (F-) levels in groundwater causes community fluorosis and non-carcinogenic health concerns in local people. This study described occurrence, dental fluorosis, and origin of high F-groundwater using δ2H and δ18O isotopes at semiarid Gilgit, Pakistan. Therefore, groundwater (n = 85) was collected and analyzed for F- concentrations using ion-chromatography. The lowest F- concentration was 0.4 mg/L and the highest 6.8 mg/L. F- enrichment is linked with higher pH, NaHCO3, NaCl, δ18O, Na+, HCO3-, and depleted Ca+2 aquifers. The depleted δ2H and δ18O values indicated precipitation and higher values represented the evaporation effect. Thermodynamic considerations of fluorite minerals showed undersaturation, revealing that other F-bearing minerals viz. biotite and muscovite were essential in F- enrichment in groundwater. Positive matrix factorization (PMF) and principal component analysis multilinear regression (PCAMLR) models were used to determine four-factor solutions for groundwater contamination. The PMF model results were accurate and reliable compared with those of the PCAMLR model, which compiled the overlapping results. Therefore, 28.3% exceeded the WHO permissible limit of 1.5 mg/L F-. Photomicrographs of granite rocks showed enriched F-bearing minerals that trigger F- in groundwater. The community fluorosis index values were recorded at > 0.6, revealing community fluorosis and unsuitability of groundwater for drinking.

Groundwater Quality, Health Risk Assessment, and Source Distribution of Heavy Metals Contamination around Chromite Mines: Application of GIS, Sustainable Groundwater Management, Geostatistics, PCAMLR, and PMF Receptor Model.

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.

Hydrochemical evaluation of groundwater for drinking and irrigation purposes using multivariate indices along Indus Suture Zone, North Pakistan.

The present study is aimed to investigate the hydrochemical characteristics, spatial distribution and suitability of groundwater for drinking and irrigation purposes along the Indus Suture Zone (ISZ), north Pakistan. Physicochemical parameters and hazardous trace elements (HTEs) like Cd, Co, Cu and Mn were determined following standard methods. The mean and median concentrations were found below the World Health Organization (WHO) drinking water guidelines values. Hydrochemical results indicate that groundwater sources were mainly attributed to rock-water interaction category. Piper diagram shows that most of the groundwater samples fall in Ca-HCO3─ class presenting weak-alkaline proportion type. The drinking water quality index (DWQI) ranking was categorized as good to excellent, indicating the overall quality of the groundwater may pose no health hazard concern. Based on irrigation WQI (SAR, Na%, MAR, KR), the groundwater was found fit for irrigation except SAR whereas 36% of the groundwater samples fall within the poor class. The total HI values through dermal contact exceeded the safe non-carcinogenic threshold of HI = 1. Therefore, there is required an effective groundwater monitoring and management facility in the study area to safeguard residents from various illnesses associated with varying HTEs concentrations in drinking water. The major response actions needed for groundwater bodies restoration are including the installation of a continuous groundwater monitoring network and control of agricultural fertilizers that seems to be the most effective and tangible for immediate action.

Natural Clay Minerals as Potential Arsenic Sorbents from Contaminated Groundwater: Equilibrium and Kinetic Studies.

Arsenic (As) contaminated groundwater is a worldwide concern due to its chronic effects on human health. The objectives of the study were to evaluate natural inexpensive raw laterite (RL) and kaolinite (RK) for their potential use as As sorbents and to understand the As sorption on laterite and kaolinite by employing sorption and kinetic models. Raw laterite and RK were tested for EC, pH, XRF and CEC as basic parameters. Batch sorption and kinetic experiments data were fitted in the sorption (Langmuir and Freundlich) model and kinetic (pseudo-first and pseudo-second order) reaction equations, respectively. Morphological and structural changes were observed in RL and RK samples before and after As saturation by employing FTIR and SEM. The major constituent in RL was Fe and Al oxides while in RK major oxides were silica and Al. The Freundlich sorption model well explained the experimental data, indicating a greater sorption capacity of RL on a hetero-layered surface compared to RK. The kinetic reaction equations showed that equilibrium was achieved after a contact time of 240 min and the adsorption was chemisorption in nature. The RL and RK were found to be effective sorbents for As removal, however, RL showed maximum As adsorption and thus superior in comparison with RK. Structural and morphological characterization reveals the role of Fe and Al oxides in the case of RL, and Al oxides in the case of RK, in the adsorption of As. Hence this study concludes that these naturally occurring inexpensive resources can be used as sorbent agents for As-contaminated drinking water treatment.

Geochemical Modeling Source Provenance, Public Health Exposure, and Evaluating Potentially Harmful Elements in Groundwater: Statistical and Human Health Risk Assessment (HHRA).

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.

Impacts of the linear flowing industrial wastewater on the groundwater quality and human health in Swabi, Pakistan.

The present study aimed to probe the extent and mobility of contamination in wastewater and its impact on groundwater and human health in the Swabi region in Pakistan. Representative samples (n = 86) were collected from both wastewater streams and groundwater in an analogous environmental setting. The result showed that pH, color, hardness, alkalinity, chemical oxygen demand, chloride, suspended solids, total dissolved solids, Cr, Cd, Pb, Cu, Fe, Mg, Na, Ca, and K in industrial wastewater were higher than the Pak-EPA (Pakistan Environmental Protection Agency) and the United State Environmental Protection Agency (US-EPA) devised standards. In groundwater, the concentration (µg L-1) of trace elements, namely, Cd (1.16), Pb (17.4), Fe (12426), Mn (320), Mg (129784), Na (33630), Ca (177944), and K (9558) was significantly higher than the WHO (World Health Organization) acceptable level, showing decreasing tendency with increasing distance from the industrial zone. The study perceived that wastewater caused permanent hardness, while groundwater hardness was decreased from permanent to temporary at a distance from industries. Integrated health risk assessment revealed that Cu, Zn, and Co may cause low risk, Na, Mn, Ni, Pb, and Cr cause medium risk, whereas Cd, Fe, Mg, Ca, and K may cause a high health risk. Moreover, the average daily intake of Fe, Mn, Mg, Na, Ca, and K was comparably higher than Cr, Cd, Pb, Ni, Cu, Zn, and Co in both adults and children. The mode of occurrence of contaminants in groundwater was due to the leaching of contaminated wastewater and the oxidation of metals. Furthermore, carbonates, chloride, and SAR (sodium adsorption ratio) precipitation have a key role in groundwater contamination and influencing the natural water quality. The study concluded that the health problems in the surrounding areas were due to the use of contaminated water for drinking and household purpose. The study suggests filtering the drinking water and treating the wastewater before releasing it into the environment.

Evaluation of the Swat River, Northern Pakistan, water quality using multivariate statistical techniques and water quality index (WQI) model.

This study evaluates the characteristics of water along the Swat River, Northern Pakistan. For this purpose, water samples (n = 30) were collected and analyzed for physicochemical parameters including heavy metals (HM). The mean concentrations of physicochemical parameters and HM were within the drinking water guideline values set by the World Health Organization (WHO 2011) except 34%, 60%, and 56% of copper (Cu), nickel (Ni), and lead (Pb), respectively. Pollution sources were identified by various multivariate statistical techniques including correlation analysis (CA) and principal component analysis (PCA) indicating different origins both naturally and anthropogenically. Results of the water quality index (WQI) ranged from 13.58 to 209 with an average value of 77 suggesting poor water quality for drinking and domestic purposes. The poor water quality was mainly related to high sodium (alkalinity) and salinity hazards showing > 27% and 20% water samples have poor alkalinity and salinity hazards, respectively. Hazard quotient (HQ) and hazard index (HI) were used to determine the health risk of HM in the study area. For water-related health risk, HQingestion, HQdermal, and HI values were > 1, indicating noncarcinogenic health risk (NCR) posed by these HM to the exposed population.

Human health risks by potentially toxic metals in drinking water along the Hattar Industrial Estate, Pakistan.

This study aimed to investigate the contamination of drinking water sources with potentially toxic metals (PTMs) together with some hydrochemical characteristics in the highly populated industrial zone of Pakistan. For this purpose, drinking (n = 40) and surface (n = 20) water samples were collected and analyzed for PTM using graphite furnace atomic absorption spectrophotometer (GFAAS, PerkinElmer-700, USA). The metals, including cadmium (Cd), chromium (Cr), nickel (Ni), lead (Pb), and zinc (Zn), showed significantly (p = 0.05) higher concentrations than their respective limits set by the World Health Organization (WHO 2011) in drinking water. The chronic daily intake (CDI) and human hazard quotient (HQ) were also evaluated. The highest daily intake through drinking water consumption was found for Ni (4.3 µg/kg/day), while lowest for Cd (0.25 µg/kg/day). The highest hazard quotient values were found for Cd (0.33) and Ni (0.29) that could be attributed to industrial wastewater discharge. Higher CDI and HQ values of Ni and Cd may cause chronic human health problems. According to the Chadha Piper diagram, the hydrochemical facies distribution indicated that water trend in the study area followed an order such as follows: Ca-Mg-Cl < Na-Cl < Ca-HCO3 < Na-HCO3. Statistical analysis using one-way ANOVA, correlation analysis, and principal component analysis (PCA) revealed that the elevated levels of PTM were attributed to industrial wastewater discharge. This study provides baseline information for policy makers and the effective management of water in populated industrialized zone.

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.