Nitrate distribution and potential attenuation mechanisms of a municipal water supply bedrock aquifer

• Nitrate contamination was found for overburden and fractured bedrock in an agricultural setting.
• The hydrogeological configuration and the dissolved oxygen content condition the spatial distribution of nitrate.
• Autotrophic denitrification in bedrock was found to be an effective nitrate attenuation mechanism.
• Nitrate contamination due to an identified long term diffuse source could potentially impact municipal wells.

The Silurian bedrock aquifer constitutes a major aquifer system for groundwater supply across the Ontario province in Canada. The application of natural and industrial fertilizers near urban centers has led to groundwater NO3−-N concentrations that sometimes have exceeded the drinking water limit, posing a threat to the usage of groundwater for the human consumption. Therefore, there is a growing interest and concern about how nitrate is being leached, transported and potentially attenuated in bedrock aquifers. This study assesses the local distribution of groundwater NO3− in the up-gradient area of two historically impacted municipal wells, called Carter Wells, in the City of Guelph, Canada, in order to evaluate the potential nitrate attenuation mechanisms, using both groundwater geochemical and isotopic analysis (3H, δ15N-NO3, δ18O-NO3, δ18O-SO4, δ34S-SO4) and a detailed vertical hydrogeological and geochemical bedrock characterization. The results indicate that probably the main source of nitrate to the Carter Wells is the up-gradient Arkell Research Station (ARS), an agricultural research facility where manure has been historically applied. The overburden and bedrock groundwater with high NO3 concentrations at the ARS exhibits a manure-related δ15N and δ18O signature, isotopically similar to the high nitrate in the down-gradient groundwater from domestic wells and from the Carter Wells. The nitrate spatial distribution appears to be influenced and controlled by the geology, in which more permeable rock is found in the Guelph Formation which in turn is related to most of the high NO3− groundwater. The presence of an underlying low permeability Eramosa Formation favors the development of oxygen-depleted conditions, a key factor for the occurrence of denitrification. Groundwater with low NO3−-N concentrations associated with more oxygen-limited conditions and coincident with high SO42− concentrations are related to more enriched δ15N and δ18O values in NO3− and to more depleted δ34S and δ18O values in SO42−, suggesting that denitrification coupled with pyrite oxidation is taking place. The presence of macro crystalized and disseminated pyrite especially in the Eramosa Formation, can support the occurrence of this attenuation process. Moreover, based on tritium analysis, some denitrification can occur in shallow bedrock and within relatively short residence times, associated with less permeable conditions in depth which facilitates oxygen consumption through sulfide oxidation. The role of denitrification mediated by organic carbon cannot be discarded at the study site. This study suggests that the geological configuration and particularly the presence of low permeability Eramosa Formation can play an important role on nitrate natural attenuation, which may serve as a decision factor on defining the bedrock water supply system for both domestic and municipal purposes.