Environmental tracers and groundwater residence time indicators reveal controls of arsenic accumulation rates beneath a rapidly developing urban area in Patna, India

Groundwater security is a pressing environmental and societal issue, particularly due to significantly increasing stressors on water resources, including rapid urbanization and climate change. Groundwater arsenic is a major water security and public health challenge impacting millions of people in the Gangetic Basin of India and elsewhere globally. In the rapidly developing city of Patna (Bihar) in northern India, we have studied the evolution of groundwater chemistry under the city following a three-dimensional sampling framework of multi-depth wells spanning the central urban zone in close proximity to the River Ganges (Ganga) and transition into peri-urban and rural areas outside city boundaries and further away from the river. Using inorganic geochemical tracers (including arsenic, iron, manganese, nitrate, nitrite, ammonium, sulfate, sulfide and others) and residence time indicators (CFCs and SF6), we have evaluated the dominant hydrogeochemical processes occurring and spatial patterns in redox conditions across the study area. The distribution of arsenic and other redox-sensitive parameters is spatially heterogenous, and elevated arsenic in some locations is consistent with arsenic mobilization via reductive dissolution of iron hydroxides. Residence time indicators evidence modern (<~60-70 years) groundwater and suggest important vertical and lateral flow controls across the study area, including an apparent seasonal reversal in flow regimes near the urban center. An overall arsenic accumulation rate is estimated to be ~0.003 ± 0.003 μM.yr-1 (equivalent to ~0.3 ± 0.2 μg.yr-1), based on an average of CFC-11, CFC-12 and SF6-derived models, with the highest rates of arsenic accumulation observed in shallow, near-river groundwaters also exhibiting elevated concentrations of nutrients including ammonium. Our findings have implications on groundwater management in Patna and other rapidly developing cities, including potential future increased groundwater vulnerability associated with surface-derived ingress from large-scale urban abstraction or in higher permeability zones of river-groundwater connectivity.