Hydrochemical profiles in urban groundwater systems: new insights into contaminant sources and pathways in the subsurface from legacy and emerging contaminants

It has long been known that groundwaters beneath urban areas carry a fingerprint from urban activities but finding a consistent tracer for anthropogenic influence has proved elusive. The varied sources of urban contaminants means that a single consistent and inexpensive means of tracing the fate of urban contaminants is not generally possible and multiple tracers are often required to understand the contaminant sources and pathways in these complex systems. This study has utilized a combination of micro‐organic (MO) contaminants and inorganic hydrochemistry to trace recharge pathways and quantify the variability of groundwater quality in multi‐level piezometers in the city of Doncaster, UK. A total of 23 MO’s were detected during this study, with more compounds consistently detected during higher groundwater table conditions highlighting the importance of sampling under different hydrological conditions. Four of the compounds detected are EU Water Framework Directive priority substances; atrazine, simazine, naphthalene and DEHP, with a maximum concentration of 0.18, 0.03, 0.2, 16 μg/l respectively. Our study shows that the burden of the banned pesticide atrazine persisting in the Sherwood sandstone is detected at two of the three study sites. Emerging contaminants’ are seen throughout the borehole profiles and provide insights into transient pathways for contaminant migration in the sub‐surface. Long term changes in inorganic hydrochemistry show possible changes in contaminant input or the dissolution of minerals. Nitrate was detected above 50 mg/L but on the whole nitrate concentrations have declined in the intervening years either due to a reduction of nitrate application at the surface or a migration of peak nitrate concentrations laterally or to greater depth. This study shows that multiple tracers together with multi‐level piezometers can give a better resolution of contaminant pathways and variable flow regimes within the relatively uncomplicated aquifer of the Sherwood Sandstone compared with single long screened wells.