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.

Characterization and role of derived dissolved organic matter on arsenic mobilization in alluvial aquifers of Punjab, Pakistan.

Biogeochemical mobilization of arsenic in groundwater depends on the presence of dissolved organic matter (DOM) that likely promotes the As release, i.e., reductive dissolution, complexation, competition, and electron shuttling. We investigated the role of DOM in As release, along with its complete characterization, in the Indus plain of Pakistan, one of the worst arsenic impacted zones in the South Asian region. In total, 60 groundwater and 15 soil samples, collected at six sites from north to south within the flood plain of the Ravi River, Lahore, Pakistan were investigated. Arsenic concentration ranged from 9.61 µg/L to 386 µg/L in the groundwater samples (high As observed in areas close to the river). Dissolved organic carbon (DOC) in 29 groundwater samples ranged between 0 and 10.1 mg-C/L. A moderately positive correlation of As with DOC and Fe in the northern part of the study area suggest the reductive dissolution of FeOOH associated with dissolved organic matter (DOM). The reductive dissolution plays an essential role for As enrichment in the area evidenced by the lower concentrations of SO42-, NO3-, and PO34-and a non-correlative pattern with As. In contrast, a positive correlation of As with PO34-, DOC, and HCO3- in the southern part indicate competitive desorption behind the As release. Fluorescence excitation-emission matrix intensity data of DOM indicate the maximum presence of humic-like substances in the northern part that gradually shifts to aromatic, fulvic and protein type towards the southern part. Specific ultraviolet absorbance and fluorescence index display aromatic and terrestrial (allochthonous) sources of DOM near the riverbank and mixed (both allochthonous and autochthonous) source away from the river. The positive correlations of As with DOC and fluorescence intensity also attest that DOM played a vital role in the As mobilization in groundwater of the study area.