A mechanistic approach to arsenic adsorption and immobilization in aqueous solution, groundwater, and contaminated paddy soil using pine-cone magnetic biochar.

Arsenic (As) poisoning in groundwater and rice paddy soil has increased globally, impacting human health and food security. There is an urgent need to deal with As-contaminated groundwater and soil. Biochar can be a useful remedy for toxic contaminants. This study explains the synthesis of pinecone-magnetic biochar (PC-MBC) by engineering the pinecone-pristine biochar with iron salts (FeCl3.6H2O and FeSO4.7H2O) to investigate its effects on As(V) adsorption and immobilization in water and soil, respectively. The results indicated that PC-MBC can remediate As(V)-contaminated water, with an adsorption capacity of 12.14 mg g-1 in water. Isotherm and kinetic modeling showed that the adsorption mechanism involved multilayer, monolayer, and diffusional processes, with chemisorption operating as the primary interface between As(V) and biochar. Post-adsorption analysis of PC-MBC, using FTIR and XRD, further revealed chemical fixing and outer-sphere complexation between As(V) and Fe, O, NH, and OH as the main reasons for As(V) adsorption onto PC-MBC. Recycling of PC-MBC also had excellent adsorption even after several regeneration cycles. Similarly, PC-MBC successfully immobilized As in paddy soil. Single and sequential extraction results showed the transformation of mobile forms of As to a more stable form, confirmed by non-destructive analysis using SEM, EDX, and elemental dot mapping. Thus, Fe-modified pine-cone biochar could be a suitable and cheap adsorbent for As-contaminated water and soil.

Natural carbon mineralization and its control on the geochemical evolution of coal-based aquifers in the Salt Range, Punjab, Pakistan.

Hydrochemical analysis of the Salt Range was conducted to understand carbon weathering and its impact on groundwater evolution within the complex geological framework of Punjab. Our results showed that groundwater samples were alkaline with a pH range of 7.0-8.6 and 7.8-8.8 for the eastern Salt Range (ESR) and Trans-Indus Salt Range (TSR), respectively, while that of the Central Salt Range (CSR) was acidic to moderately alkaline ranging between 5.7 and 7.5. The water types of Ca-Mg-HCO3, Ca-Mg-Cl, and Ca-Cl2 were the dominant hydro-chemical facies in ESR and CSR sites. However, groundwater of the TSR site falls under Ca-Mg-Cl, Ca-Cl2, and mixed types of Ca-Mg-SO4. Our new findings suggest that groundwater chemistry is primarily controlled by rock dominance and reverse ion exchange reaction, followed by evapotranspiration processes. The wells of ESR, CSR, and TSR were reported with higher levels of Fe and Zn. Regarding the suitability for irrigation, sodium adsorption ratio (SAR), magnesium adsorption ratio (MAR), sodium percentage (Na%), Kelley's ratio (KR), and potential salinity (PS) at all three sites (ESR, TSR, and CSR) had the potential to become a salinity hazard. The conceptual model of geochemical evolution shows that both local and regional salinization is driven by local geology and intensive coal mining activities. The neutralization capacity of the parent geological formation buffers the acidity and lowers the overall trace element enrichment. The potential of natural weathering could be further explored as a solution to coal mining's impact on the environment.

Groundwater nitrate and fluoride profiles, sources and health risk assessment in the coal mining areas of Salt Range, Punjab Pakistan.

To assess the loading profiles of groundwater nitrate (NO3-) and fluoride (F-), their spatial distributions, geochemistry and associated health risks were determined for 131 groundwater samples from eastern (ESR), central (CSR) and Trans-Indus Salt Ranges (TSR) in Pakistan. Groundwater NO3- concentrations were 0.2-308 mg/L (mean 59 mg/L) in ESR, 2.7-203 mg/L (mean 73 mg/L) in CSR and 1.1-259 mg/L (mean 69 mg/L) in the TSR. Forty-one %, 57% and 36% of the ESR, CSR and TSR samples, respectively, exceeded the WHO and Pak-NEQs permissible limit of 50 mg/L NO3-. Likewise, groundwater F- concentrations ranged from 0.1-1.8 mg/L (mean 0.6 mg/L), 0.1-2.7 mg/L (mean 0.9 mg/L) and 0.3-2.5 mg/L (mean 1.6 mg/L) mg/L in the ESR, CSR and TSR sites, respectively. In this case, 3%, 17% and 27% of the ESR, CSR and TSR samples, respectively, exceeded the WHO and Pak-NEQs permissible limit of 1.5 mg/L F. Oxidation of coal and coal waste resulted in the release of NO3- to groundwater. By contrast, enrichment of F- in groundwater was due to dissolution and cation exchange processes. Elevated values of the Higher Pollution Index (PI) and Health Risk Index (HRI) reflect a non-acceptable carcinogenic risk for drinking water NO3- and F- which should be addressed on a priority basis to protect human health.

Arsenic and fluoride co-exposure through drinking water and their impacts on intelligence and oxidative stress among rural school-aged children of Lahore and Kasur districts, Pakistan.

Arsenic (As), and fluoride (F-) are potent contaminants with established carcinogenic and non-carcinogenic impacts on the exposed populations globally. Despite elevated groundwater As and F- levels being reported from various regions of Pakistan no biomonitoring study has been reported yet to address the co-exposure impact of As and F- among school children. We aimed to investigate the effects of these two contaminants on dental fluorosis and intelligence quotient (IQ) along with the induction of oxidative stress in rural children under co-exposed conditions. A total of 148 children (5 to 16 years old) from the exposed and control group were recruited in the current study from endemic rural areas of Lahore and Kasur districts, Pakistan having elevated As and F- levels in drinking water than permissible limits. We monitored malondialdehyde and its probable association with antioxidants activity (SOD, CAT, and GR) as a biomarker of oxidative stress. GSTM1/T1 polymorphisms were measured to find the impact of As on health parameters. Mean urinary concentrations of As (2.70 vs. 0.016 µg/L, P < 0.000) and F- (3.27 vs. 0.24 mg/L, P < 0.000) as well as the frequency of dental fluorosis were found elevated among the exposed group. The cases of children with lower IQ were observed high in the exposed group. Additionally, lower concentrations of antioxidants (SOD, CAT, and GR) were found suggesting high susceptibility to F- toxicity. The findings suggest that F- accounted for high variations in health parameters of children under the co-exposure conditions with As.

WITHDRAWN: Co-exposure effects of arsenic and fluoride on intelligence and oxidative stress in school-aged children: A cohort study.

This article has been withdrawn at the request of the editor. The Publisher apologizes for any inconvenience this may cause.

Groundwater fluoride concentrations in the watershed sedimentary basin of Quetta Valley, Pakistan.

Litho-geochemical characteristics of low and high fluoride (F-) groundwater along with hydrological processes were investigated to delineate its genesis and enrichment mechanism in a watershed sedimentary basin. In this study, groundwater F- concentration ranged from 0 to 20 mg/L with a mean and standard deviation of 2.8 and ± 3.7 mg/L, respectively. Out of N = 87, 63% of samples exceeded the World Health Organization (WHO) limit of 1.5 mg/L. The order of cationic and anionic dominance in groundwater samples with mean was found in decreasing order as Na+ > Mg2+ > Ca2+ > K+ and HCO3- > SO42- > Cl- > PO43- > NO3- measured in milligrams per liter. Groundwater chemistry changed from Ca-HCO3 to Na-HCO3 type and low to high fluoride as we moved from mountain foot towards the synclinal basin. Low fluoride groundwater reflected weathering, recharge, and reverse ion exchange processes with Ca-HCO3- and Ca-Mg-Cl-type water while high fluoride groundwater revealed base ion exchange, mixing, and desorption as dominant hydrological processes with Na-HCO3 and Na-Cl types of water. Gibb's diagram showed rock weathering and mineral dissolution as the major geochemical processes controlling water chemistry with an insignificant role of evaporation in the semi-arid area. Fluoride was undersaturated with mineral fluorite, indicating fluoride in groundwater is released by secondary minerals. However, due to complex geological features, groundwater fluoride enrichment was affected by a broad-scale process across a wide area such as depth, residence time, and most important geomorphological units hosting the aquifer.

Health risk assessment of arsenic and other potentially toxic elements in drinking water from an industrial zone of Gujrat, Pakistan: a case study.

Present study aimed to provide a baseline data on arsenic (As) and other potentially toxic element (PTEs; Cd, Cr, Cu, Ni, and Pb) contamination in groundwater and soils (surface and sub-surface) from an industrial area of district Gujrat, Pakistan. Statistical parameters, principal component analysis-multiple linear regression (PCA-MLR), and health risk assessment model were used to elaborate the interrelations, source contributor, and associated health risks. This study revealed that the concentrations of Cd, Cr, Cu, and Pb in drinking water were within the permissible limits of the World Health Organization (WHO). However, As and Ni concentrations exceeded the WHO limits of 10 µg/L for As and 0.07 mg/L for Ni. In soils, the concentration of Cr was within permissible limits, whereas As, Cd, Cu, Ni, and Pb exceeded the prescribed values. Solid waste and industrial effluents from the area also contained high levels of As, Cd, Cr, Cu, Ni, and Pb. Calculated health index of As and other PTEs for industrial site and control area was less than 1 which indicated that the groundwater was assumed to be safe for drinking. High contamination of As (15 mg/kg) and other PTEs (Pb was 978, Cr 51, Cu 111, Cd 68, and Ni was 90 mg/kg, respectively) in upper soil could be due to the discharge of industrial effluent prior to the treatment, which signifies the industrial contribution towards As and heavy metal contamination. It can be concluded that critical examination of soil profile affinity to the respective, industrial waste pollutants can reduce the health risks to the local community. This trend not only reveals the geochemistry of the area but also useful for developing a link to access health risk and associated remediation processes.

A review of global outlook on fluoride contamination in groundwater with prominence on the Pakistan current situation.

Several million people are exposed to fluoride (F-) via drinking water in the world. Current review emphasized the elevated level of fluoride concentrations in the groundwater and associated potential health risk globally with a special focus on Pakistan. Millions of people are deeply dependent on groundwater from different countries of the world encompassing with an elevated level of fluoride. The latest estimates suggest that around 200 million people, from among 25 nations the world over, are under the dreadful fate of fluorosis. India and China, the two most populous countries of the world, are the worst affected. In Pakistan, fluoride data of 29 major cities are reviewed and 34% of the cities show fluoride levels with a mean value greater than 1.5 mg/L where Lahore, Quetta and Tehsil Mailsi are having the maximum values of 23.60, 24.48, > 5.5 mg/L, respectively. In recent years, however, other countries have minimized, even eliminated its use due to health issues. High concentration of fluoride for extended time period causes adverse effects of health such as skin lesions, discoloration, cardiovascular disorders, dental fluorosis and crippling skeletal fluorosis. This review deliberates comprehensive strategy of drinking water quality in the global scenario of fluoride contamination, especially in Pakistan with prominence on major pollutants, mitigation technologies, sources of pollution and ensuing health problems. Considering these verities, health authorities urgently need to establish alternative means of water decontamination in order to prevent associated health problems.

Legacy and emerging flame retardants (FRs) in the freshwater ecosystem: A review.

In this review article, we have compiled and reviewed the previously published available literature on environmental distribution, behaviour, fate and regional trends of legacy and emerging flame retardants (FRs) including brominated (BFRs), organo-phosphate (OPFRs), novel brominated flame retardants (NBFRs) and dechlorane plus (DP) in the freshwater ecosystem. Transport and fate is discussed briefly with the evidences of de-bromination, sedimentation and accumulation in biota. De-bromination of BDE-209 is considered of concern because the lower brominated congeners are more toxic and mobile thus posing increased risk to the freshwater ecosystem. The available data on temporal and spatial trends as yet, is too few to show any consistent trends, enabling only general conclusions to be drawn. There is a lack of temporal studies in Asia, while, overall the trends are mixed, with both increasing and decreasing concentrations of BFRs and OPFRs. OPFRs and NBFRs have replaced classical BFRs (polybrominated diphenyl ethers (PBDEs)) in some countries but the amount of PBDEs in the environment is still considerable. Knowledge gaps and recommendations for future research are discussed emphasizing on further monitoring, advanced analytical methodologies, and risk assessment studies to completely understand the science of flame retardants in the freshwater ecosystem.

Arsenic and fluoride co-contamination in shallow aquifers from agricultural suburbs and an industrial area of Punjab, Pakistan: Spatial trends, sources and human health implications.

Release of arsenic (As) and fluoride (F-) species into groundwater is a serious health concern around the world. The present study was the first systematic baseline study conducted in Rahim Yar Khan district, Punjab, focusing on As and F- contamination in groundwater. A total of 51 representative groundwater samples comprising of 44 samples from agricultural suburbs and 7 from an industrial base were analysed. Statistical parameters, principal component analysis-multiple linear regression (PCA-MLR) and health risk assessment model were used to investigate the hydro geochemistry, spatial patterns, interrelation, source contribution and associated health risks of high As and F- in groundwater of the study area. Results showed high risk of F- exposure to people of the study area, with all samples exceeding the WHO standard of 1.5 mg/L, and for As, 32.5% of the studied groundwater samples exceeded the WHO standard (10 µg/L). The maximum As (107.23 µg/L) and F- (26.4 mg/L) levels were observed in samples close to the agricultural and smelting areas, implicating the frequent use of fertilizers and influence of industrial effluents in the study area. The PCA-MLR receptor model quantitatively illustrates that the majority of As and F- comes from natural sources, while, among anthropogenic sources, industrial and agricultural activities contributed the most. Health risk assessment revealed a high risk of As and F- contamination to the exposed population; therefore, detailed control strategies and policies are required in order to mitigate the health risks.

Arsenic and fluoride removal by potato peel and rice husk (PPRH) ash in aqueous environments.

Finding appropriate adsorbent may improve the quality of drinking water in those regions where arsenic (As) and fluoride (F-) are present in geological formations. In this study, we evaluated the efficiency of potato peel and rice husk ash (PPRH-ash)-derived adsorbent for the removal of As and F from contaminated water. Evaluation was done in batch adsorption experiments, and the effect of pH, initial adsorbate concentration, contact time, and adsorbent dose were studied. Characteristics of adsorbents were analyzed using scanning electron micropcope (SEM) and Fourier transform infrared (FTIR) spectroscopy. Both the Langmuir and Freundlich isotherm models fitted well for F- and As sorption process. The maximum adsorption capacity of adsorbent for As and F- was 2.17 µg g-1 and 2.91 mg g-1, respectively. The As and Fi removal was observed between pH 7 and 9. The sorption process was well explained with pseudo-second order kinetic model. Arsenic adsorption was not decreased in the presence of carbonate and sulfate. Results from this study demonstrated potential utility of this agricultural biowaste, which could be developed into a viable filtration technology for As and F- removal in As- and F-contaminated water streams.

Quality of tube well water intended for irrigation and human consumption with special emphasis on arsenic contamination at the area of Punjab, Pakistan.

In the present study, the tube well water quality and the associated health risks, emphasizing on arsenic contamination, were investigated in rural and urban samples from Tehsil Mailsi located in Punjab, Pakistan. Arsenic concentrations (µg/L) were ranged from 12 to 448.5 and which exceeded the WHO recommended limit (10 µg/L) in all cases. The calculated average daily dose (3.3 × 10-0.4 to 1.2 × 10-0.2 mg/kg day) and hazard quotient (1.1-40) reflected the potential health risk to local population due to tube well water consumption as drinking purpose. Sodium percent (Na%), sodium absorption ratio, residual sodium carbonate, Kelly's index and magnesium absorption ratio were also determined to assess the suitability of tube well water for irrigation purpose. The resulting piper plot revealed the Na-Ca-HCO3 type water chemistry of the area and generally alkaline environment. The spatial distribution of arsenic in the tube well waters pinpoints the significant contribution of anthropogenic activities to arsenic pollution. Nevertheless, different statistical tools, including principal component analysis, hierarchical cluster analysis and correlation matrices, revealed the contribution of both natural and anthropogenic activities and alkaline type of aquifers toward the high level of arsenic contamination.

Arsenic(V) biosorption by charred orange peel in aqueous environments.

Biosorption efficiency of natural orange peel (NOP) and charred orange peel (COP) was examined for the immobilization of arsenate (As(V)) in aqueous environments using batch sorption experiments. Sorption experiments were carried out as a function of pH, time, initial As(V) concentration and biosorbent dose, using NOP and COP (pretreated with sulfuric acid). Arsenate sorption was found to be maximum at pH 6.5, with higher As(V) removal percentage (98%) by COP than NOP (68%) at 4 g L(-1) optimum biosorbent dose. Sorption isotherm data exhibited a higher As(V) sorption (60.9 mg g(-1)) for COP than NOP (32.7 mg g(-1)). Langmuir model provided the best fit to describe As(V) sorption. Fourier transform infrared spectroscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy analyses revealed that the -OH, -COOH, and -N-H surface functional groups were involved in As(V) biosorption and the meso- to micro-porous structure of COP sequestered significantly (2-times) higher As(V) than NOP, respectively. Arsenate desorption from COP was found to be lower (10%) than NOP (26%) up to the third regeneration cycle. The results highlight that this method has a great potential to produce unique 'charred' materials from the widely available biowastes, with enhanced As(V) sorption properties.

Distribution, enrichment, and source identification of selected heavy metals in surface sediments of the Siran River, Mansehra, Pakistan.

To assess the trace metal pollution in the Siran River, sediments were collected from 12 sites, from the left and right banks of the river in 2013. The concentrations, accumulation, distribution pattern, and pollution status of heavy metals in sediments were investigated using geoaccumulation index (I geo) and enrichment factor (EF). The toxic risk of heavy metals was assessed using interim sediment quality guidelines (ISQGs), portable effect level (PEL), threshold effect level (TEL), and toxic effect threshold (TET). I geo and EF values showed that sediments were loaded with Ni, Cd, Pb, and Co and no obvious variations were found among the left and right banks of the river. The EF and I geo values were found in order of Co > Pb > Ni > As > Cd > Cu > Zn > Fe and Cd > Co > Pb > Ni > As > Fe > Zn > Cu > Mn, respectively. Furthermore, multivariate statistical analysis like inter-metal correlation, cluster analysis (CA), and principal component analysis (PCA) results revealed that geogenic and anthropogenic activities were major sources of sediment contamination in the study area. These results indicated that more attention should be paid to the inner loads of sediment in order to achieve improvements in reservoir water quality after the control of external pollution.

Arsenic concentration variability, health risk assessment, and source identification using multivariate analysis in selected villages of public water system, Lahore, Pakistan.

This paper reports high levels and variability in arsenic (As) levels at locations identified as one of the highest As-contaminated locations in Pakistan. Groundwater pollution related to arsenic has been reported since many years in the areas lying in outskirts of District Lahore, Pakistan. A comparative study is done to determine temporal variations of As from three villages, i.e., Kalalanwala (KLW), Manga Mandi (MM), and Shamki Bhattian (SKB). Seventy-three percent of the 30 investigated samples ranging in depth from 20 to 200 m, show an increasing trend in variations of As concentration over a time span of 4 years and 87% of samples exceeded the WHO standard of 10 µg/L for As while 77% of samples have As concentration >50 µg/L (national standard). Further results indicate that high levels of As is accompanied with increase pH (r = 0.8) favoring desorption of As from minerals at higher pH under oxidizing conditions. For health risk assessment of arsenic, the average daily dose, hazard quotient (HQ), and cancer risk were calculated. The residents of the studied areas had toxic risk index in the order of SKB>KLW>MM, with 87% of samples exceeding the typical toxic risk index 1.00 (ranging from 2.3-48.6) which was 83% (ranging from 0.3-41) 4 years before. The results of the present study therefore indicate that arsenic concentrations are increasing in the area, which needs an immediate attention to provide alternate sources of water to save people at risk.

Metabolomics profiling reveals the detoxification and tolerance behavior of two bread wheat (Triticum aestivum L.) varieties under arsenate stress.

The present study conducted metabolomics profiling (targeted and untargeted) in the roots of two wheat varieties (BARANI-70 and NARC-09) under arsenate stress in a hydroponic experiment. The findings indicated a better growth response of BARANI-70 compared to the NARC-09. From amino acid profiling, a total of 26 amino acids (AAs) were quantified in roots. BARANI-70 showed higher induction of stress-responsive AAs compared to the NARC-09. From untargeted metabolomics, a total of 136 metabolites were identified: AAs, fatty acids, purines, carnitines, LysoPCs, and others. The KEGG pathway identified pathways such as linoleic acid metabolism, TCA cycle, glutathione metabolism, and aminoacyl-tRNA biosynthesis that were regulated to improve the defense of tolerant variety. BARANI-70 emerged as a tolerant variety based on the psychological response, As accumulation, and behavior of stress-responsive metabolites. This study should facilitate the breeding of low-As accumulating wheat varieties for future application to ensure sustainable production and food safety.

Elevated arsenic concentrations in groundwater of the Upper Indus Plain of Pakistan across a range of redox conditions.

Groundwater of the Ravi River floodplain is particularly elevated in arsenic (As) on both sides of the Pakistan-India border. To understand this pattern, 14 sites were drilled to 12-30 m depth across floodplains and doabs of Pakistan after testing over 20,000 wells. Drill cuttings were collected at 1.5 m intervals, 132 of which were sand overlain by 77 intervals of clay and/or silt. Radiocarbon dating of clay indicates deposition of the aquifer sands tapped by wells 20-30 kyr ago. Most (85 %) of the sand samples were gray in color, indicating partial reduction to Fe(II) oxides, whereas most (92 %) of the clay and/or silt samples were orange. Associations between groundwater electrical conductivity, dissolved Fe, sulfate, and nitrate suggest that wells can be elevated (>10 µg/L) in As in the region due to either reductive dissolution of Fe oxides, evaporative concentration, or alkali desorption. In the Ravi floodplain, 47 % of 6445 wells tested contain >10 µg/L As compared to only 9 % of 14,165 tested wells in other floodplains and doabs. The As content of aquifer sands in the Ravi floodplain of Pakistan averages 4 ± 4 mg/kg (n = 66) and is higher than the average of 2 ± 2 mg/kg (n = 51) for aquifer sands outside the Ravi. Synchrotron spectroscopy and column-based speciation indicate predominance of As(V) over As(III) in both aquifer sands and groundwater. Whereas multiple processes may be responsible for elevated levels of As in groundwater across the region, spatial heterogeneity in groundwater As concentrations in the Ravi floodplain seems linked to variations in As concentrations in aquifer sands. Regulation by the solid phase may limit variations in groundwater As over time in response to natural and human-induced changes in hydrology. This means spatial heterogeneity could be taken advantage of to lower the exposure across the region with more testing and targeted drilling.

Machine learning-based assessment and simulation of land use modification effects on seasonal and annual land surface temperature variations.

Rapid urban sprawl adversely impacts the local climate and the ecosystem components. Islamabad, one of South Asia's green and environment-friendly capitals, has experienced major Land Use Land Cover (LULC) changes over the past three decades consequently, elevating the seasonal and annual Land Surface Temperature (LST) in planned and unplanned urban areas. The focus of this study was to quantify the fluctuations in LULC and LST in planned and unplanned urban areas using Landsat data and Machine Learning algorithms involving the Support Vector Machine (SVM) over the 1990-2020 data period. Moreover, hybrid Cellular Automata-Markov (CA-Markov) and Artificial Neural Network (ANN) models were employed to project the future changes in LULC and annual LST, respectively, for the years 2035 and 2050. The findings of the study reveal a distinct difference in seasonal and annual LST in planned and unplanned areas. Results showed an increase of ∼22 % in the built-up area but vegetation and bare soil decreased by ∼10 % and ∼12 %, respectively. Built-up land showed a maximum annual mean LST followed by bare-soil and vegetative surfaces. Seasonal analysis showed that summer months experience the highest LST, followed by spring, autumn and winter. Future projections revealed that the built-up areas (∼27 % in 2020) are likely to increase to ∼37 % and ∼50 %, and the areas under the highest annual mean LST class i.e., ≥28 °C are likely to increase to ∼19 % and ∼21 % in planned, and ∼38 % and ∼42 % in unplanned urban areas for the years 2035 and 2050, respectively. Planned areas have better temperature control with urban green spaces, and controlled infrastructure. The Capital Development Authority of Islamabad may be advised to control the expansion of built-up areas, grow urban forests, and thus mitigate the possible Urban Heat Island (UHI) effect.

Spatial distribution of drinking and irrigation water quality in different climatic zones of Baluchistan, Pakistan.

Baluchistan's water profile was developed by dividing it into seven zones (Northern Highlands-NH, Southern Highlands-SH, Quetta Valley-QV, Desert-D, Sibbi Plains-SP, Coastal Lasbella-CL, Coastal Gwadar-CG) based on geography, water availability, and climate of the area. A total of 106 water samples were collected from karaiz, spring water, and tube wells. Spatial distribution of EC, TDS, TH, SO42-, Cl-, Na+, and K+ showed an increasing trend in concentration from the highlands towards the desert and coastal zones. For anion, HCO3- is predominant in NH, SH, and QV, Cl- in D, CL, and CG and only SO42- in SP, whereas the cationic trend in overall zones is Na+>Ca2+>Mg2+>K+. In the NH, SH, QV, and SP zones, the physicochemical parameters met the drinking water quality guidelines; however, D, CL, and CG exceeded in almost all quality parameters. Furthermore, the drinking water quality index (WQI) shows excellent to good water quality in NH, SH, QV, and D zones, while CL and CG fall in poor to unsuitable water classes. In terms of hydrogeochemical facies, maximum water samples from NH fall in Ca-Mg-HCO3, and SH, QV, and SP in Ca-Mg-Cl type, where major ion chemistry is controlled by rock-weathering, while D, CL, and CG fall in the NaCl type, where evaporation is dominant. Similarly, irrigation water quality parameters (EC, SAR, RSC, Na%, MH%, PI, SSP, and KR) reveal that NH, SH, QV, and SP have suitable water for irrigation, and D, CL, and CG require proper treatment. Additionally, USSL and Wilcox's diagrams indicated that NH, SH, QV, and SP have "excellent to permissible"; however, D, CL, and CG have "permissible to unsuitable" class water, requiring special management practices. Consequently, appropriate control measures and targeted water purification programmes should be implemented to protect the public health and sustainability of water resources in Baluchistan.

Groundwater fluoride across the Punjab plains of Pakistan and India: Distribution and underlying mechanisms.

Chronic exposure from drinking well-water with naturally high concentrations of fluoride (F-) has serious health consequences in several regions across the world including South Asia, where the rural population is particularly dependent on untreated groundwater pumped from private wells. An extensive campaign to test 28,648 wells was conducted across the Punjab plains of Pakistan and India by relying primarily on field kits to document the scale of the problem and shed light on the underlying mechanisms. Groundwater samples were collected from a subset of 712 wells for laboratory analysis of F- and other constituents. A handful of sites showing contrasting levels of F- in groundwater were also drilled to determine if the composition of aquifer sediment differed between these sites. The laboratory data show that the field kits correctly classified 91% of the samples relative to the World Health Organization guideline for drinking water of 1.5 mg/L F-. The kit data indicate that 9% of wells across a region extending from the Indus to the Sutlej rivers were elevated in F- relative to this guideline. Field data indicate an association between the proportion of well-water samples with F- > 1.5 mg/L and electric conductivity (EC) > 1.5 mS/cm across six floodplains and six intervening doabs. Low Ca2+ concentrations and elevated bicarbonate (HCO3- > 500 mg/L) and sodium (Na+ > 200 mg/L) in high F- groundwater suggest regulation by fluorite. This could be through either the lack of precipitation or the dissolution of fluorite regulated by the loss of Ca2+ from groundwater due to precipitation of calcite and/or ion exchange with clay minerals. Widespread salinization of Punjab aquifers attributed to irrigation may have contributed to higher F- levels in groundwater of the region. Historical conductivity data suggest salinization has yet to be reversed in spite of changes in water resources management.