Seasonal Redox Decoupling Controls Multi-Metal (As–Cr–V–Se) Mobility in Alluvial Aquifers of the Mid-Gangetic Plain

Groundwater contamination by redox-sensitive elements (RSEs) such as arsenic (As), chromium (Cr), vanadium (V), and selenium (Se) pose a critical challenge in alluvial aquifers, where seasonal hydrological forcing drives dynamic hydrogeochemical and redox conditions. This study investigates the seasonal evolution of groundwater hydrogeochemistry and multi-metal behavior in shallow aquifers of the Mid-Gangetic Plain, India, with particular emphasis on the role of seasonal redox decoupling. Monsoon conditions were dominated by strongly reducing environments (ORP: −150 to −70 mV), predominantly Ca–Mg–SO4 and Na–Cl type facies. Under these conditions, significant correlations among RSEs in particular (As–V, As–Se) indicated coupled mobilization governed by the reductive dissolution of Fe–Mn (oxyhydr)oxides. Monsoon groundwater also exhibited strong associations between RSEs and agronomic indicators (NO3−, SO42−), suggesting the influence of recharge-mediated agricultural inputs on redox-sensitive geochemical processes. In contrast, post-monsoon conditions showed a clear transition to sub-oxic states (ORP up to +121 mV) and were dominated by Ca–Mg–HCO3 facies, accompanied by substantial increases in bicarbonate (~372%), electrical conductivity (~62%), and total dissolved solids (~21%). Despite the partial oxidation of the aquifer system, redox-sensitive metals did not respond uniformly. Instead, inter-element correlations weakened or disappeared, indicating a transition from coupled to decoupled contaminant behavior. Arsenic concentrations increased up to 20.8 µgL−1, whereas Cr and V displayed variable enrichment controlled by alkali-induced desorption and carbonate-mediated surface interactions. This transition reflects seasonal redox decoupling, whereby seasonal redox shifts lead to metal-specific rather than coordinated multi-metal behavior. We propose a Seasonal Redox Decoupling Framework (SRDF) to explain the shift from coupled reductive release during monsoon conditions to selective mobilization pathways in the post-monsoon period. These findings demonstrate that seasonal redox shifts control not only metal concentrations but also inter-element relationships, leading to metal-specific risk profiles. This underscores the need for seasonally adaptive monitoring and management strategies in hydrologically dynamic alluvial aquifers.