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.

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.

Salinity enrichment, sources and its contribution to elevated groundwater arsenic and fluoride levels in Rachna Doab, Punjab Pakistan: Stable isotope (δ2H and δ18O) approach as an evidence.

The present study aimed at exploring the sources of salinity and the link it shares with the enrichment of As (arsenic) and F- (fluoride) in the groundwater of Rachna Doab. Total Dissolved Solids (TDS) were used as the measure of salinity to classify samples into three groups: TDS <1000 mg/L (freshwater), 1000-3000 mg/L (slightly saline) and 3000-10,000 mg/L (moderately saline). The stable isotope analysis (δ2H and δ18O relative to VSMOW) were used to explore the sources of salinity and a conceptual model, based on secondary data was used for comparing the current and past scenarios of groundwater salinization sources. Groundwater ion chemistry and geochemical modeling (PHREEQC) were used to develop a link between the occurrence of salinity and enrichment patterns of As and F- in the groundwater of study area. TDS, As and F- concentrations in groundwater ranged from 234 to 4557 mg/L, below detection limit to 240 µg/L and below detection limit to 3.9 mg/L, respectively. Mineral dissolution, ion exchange processes, and partial input of evaporation were identified as the factors affecting groundwater salinity in the region in accordance with the conceptual model developed based on secondary data. Groundwater salinity accounts as one of the factors that positively influence the enrichment of F- in groundwater, whereas As shows no clear relationship with saline groundwaters.

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.

High levels of fluoride contamination in groundwater of the semi-arid alluvial aquifers, Pakistan: evaluating the recharge sources and geochemical identification via stable isotopes and other major elemental data.

Hydrogeochemical methods were integrated to delineate the geochemical factors controlling fluoride (F-) contamination in groundwater at four sites in the districts of Lahore (Samada) and Kasur (Sari Chimba, Kot Maiga, and Chah Fatehwala) in Panjab province of Pakistan. Hydrochemical data and stoichiometric ratios indicate Na-Cl and Na-HCO3 as the dominant water types with silicate weathering influencing overall hydrogeochemistry of the study area. The groundwater F- concentrations ranged between 0.54 mg/L and 17.5 mg/L, with more than 70% samples having F- concentrations above the World Health Organization (WHO) provisional drinking water guideline (1.5 mg/L). Saturation indices determined that 100% samples were saturated with respect to calcite and 96% samples were undersaturated with respect to fluorite, indicating the influence of calcite precipitation on fluoride enrichment. A positive correlation was observed between fluoride with pH, Na+, and HCO3-, confirming that high fluoride concentrations were the result of weathering of silicate minerals and the exchange of OH- on clay surface under the alkaline pH conditions. The isotopic values of δ18O and δ2H in groundwater ranged from 9.14 to - 5.51‰ and 56.57 to - 39.5‰, respectively. The stable isotope data indicated the meteoric origin of groundwater with some evaporative effect, which is partly influencing groundwater quality such as high pH and salinity, as a result facilitating anion exchange (OH- for F-) on clays surface. The research indicates that the groundwater quality of the study area is not recommendable for drinking due to its high total dissolved solids (TDS) and elevated fluoride concentrations.

Field testing of over 30,000 wells for arsenic across 400 villages of the Punjab plains of Pakistan and India: Implications for prioritizing mitigation.

Most of the rural population of 90 million in Punjab province in Pakistan and Punjab state in India drinks, and cooks with, untreated water drawn from shallow wells. Limited laboratory testing has shown that groundwater in the region can contain toxic levels of arsenic. To refine this assessment, a total of 30,567 wells from 383 villages were tested with a field kit in northern Punjab province of Pakistan and western Punjab state of India. A subset of 431 samples also tested in the laboratory show that 85% of wells were correctly classified by the kit relative to the World Health Organization guideline of 10 µg/L for arsenic in drinking water. The kit data show that 23% of the tested wells did not meet the WHO guideline for arsenic but also that 87% of households with a well high in arsenic live within 100 m of a well that meets the WHO guideline. The implication is that many households could rapidly lower their exposure if the subset of safe wells could be shared. In a follow-up conducted one year later in five villages where 59% of wells were elevated in arsenic, two-thirds of households indicated that they had switched to a neighboring well in response to the testing. The blanket testing of millions of wells for arsenic in the region should therefore be prioritized over much costlier water treatment and piped water supply projects that will take much longer to have a comparable impact.