Hydrogeochemical Characterization and Determination of Arsenic Sources in the Groundwater of the Alluvial Plain of the Lower Sakarya River Basin, Turkey

Arsenic (As) contamination in groundwater represents a major global public health threat, particularly in alluvial aquifer systems where redox-sensitive geochemical processes facilitate the mobilization of naturally occurring trace elements. This study investigates groundwater quality, particularly focusing on the origin of arsenic contamination in shallow and deep alluvial aquifers of the Lower Sakarya River Basin, which are crucial for drinking, domestic, and agricultural uses. Groundwater samples were collected from 34 wells—7 tapping the shallow aquifer (<60 m) and 27 tapping the deep aquifer (>60 m)—during wet and dry seasons for the hydrogeochemical characterization of groundwater. Environmental isotope analysis (δ18O, δ2H, 3H) was conducted to characterize origin and groundwater residence times, and the possible hydraulic connection between shallow and deep alluvial aquifers. Mineralogical and geochemical characterization of the sediment core samples were carried out using X-ray diffraction and acid digestion analyses to identify mineralogical sources of As and other metals. Pearson correlation coefficient analyses were also applied to the results of the chemical analyses to determine the origin of metal enrichments observed in the groundwater, as well as related geochemical processes. The results reveal that 33–41% of deep groundwater samples contain arsenic concentrations exceeding the WHO and Turkish drinking water standard of 10 µg/L, with maximum values reaching 373 µg/L. Manganese concentrations exceeded the 50 µg/L limit in up to 44% of deep aquifer samples, reaching 1230 µg/L. On the other hand, iron concentrations were consistently low, remaining below the detection limit in nearly all samples. The co-occurrence of As and Mn above their maximum contaminant levels was observed in 30–33% of the wells, exhibiting extremely low sulfate concentrations (0.2–2 mg/L), notably low dissolved oxygen concentration (1.45–3.3 mg/L) alongside high bicarbonate concentrations (450–1429 mg/L), indicating localized varying reducing conditions in the deep alluvial aquifer. The correlations between molybdenum and As (rdry = 0.46, rwet = 0.64) also indicate reducing conditions, where Mo typically mobilizes with As. Arsenic concentrations also showed significant correlations with bicarbonate (HCO3−) (rdry = 0.66, rwet = 0.80), indicating that alkaline or reducing conditions are promoting arsenic mobilization from aquifer materials. All these correlations between elements indicate that coexistence of As with Mn above their MCLs in deep alluvial aquifer groundwater result from reductive dissolution of Mn/Fe(?) oxides, which are primary arsenic hosts, thereby releasing arsenic into groundwater under reducing conditions. In contrast, the shallow aquifer system—although affected by elevated nitrate, sulfate, and chloride levels from agricultural and domestic sources—exhibited consistently low arsenic concentrations below the maximum contaminant level. Seasonal redox fluctuations in the shallow zone influence manganese concentrations, but the aquifer’s more dynamic recharge regime and oxic conditions suppress widespread As mobilization. Mineralogical analysis identified that serpentinite, schist, and other ophiolitic/metamorphic detritus transported by river processes into basin sediments were identified as the main natural sources of arsenic and manganese in groundwater of deep alluvium aquifer.