Hydrogeochemical and hydrodynamic surface/groundwater interactions were investigated at the urban floodplain aquifer in Delhi, India. The heavily polluted Yamuna River is in hydraulic contact to the groundwater and river seepage results in a contamination plume. A conceptual redox zonation was developed based on the occurrence or absence of terminal electron acceptors. The redox zonation shows an inverted zonation from sulphate-reducing conditions close to the river over manganese- and iron-reducing conditions to a mixed oxic/suboxic zone. This study shows that the occurrence of problematic substances such as ammonium and arsenic in the groundwater is a consequence of the high load of untreated sewage in the river in combination with losing river conditions. Sequential extraction of aquifer material was performed to obtain information on geochemical availability of arsenic associated with different mineral phases and binding forms. Geogenic and anthropogenic arsenic sources contribute to overall arsenic concentration, and arsenic is found to be attributed mainly to amorphous iron oxide and sulphidic phases in the sediment. The contamination plume at the urban floodplain aquifer makes the groundwater unfit for drinking water purposes.