Exposure Time Distributions reveal Denitrification Rates along Groundwater Flow Path of an Agricultural Unconfined Aquifer

Groundwater contamination by nitrate is nearly ubiquitous in agricultural regions. Nitrate is highly mobile in groundwater and though it can be denitrified in the aquifer (reduced to inert N2 gas), this process requires the simultaneous occurrence of anoxia, an electron donor (e.g. organic carbon, pyrite), nitrate, and microorganisms capable of denitrification. In addition to this the ratio of the time groundwater spent in a denitrifying environment (exposure time) to the characteristic denitrification reaction time plays an important role, because denitrification can only occur if the exposure time is longer than the characteristic reaction time. Despite a long history of field studies and numerical models, it remains exceedingly difficult to measure or model exposure times in the subsurface at the catchment scale. To approach this problem, we developed a unified modelling approach combining measured environmental proxies with an exposure time based reactive transport model. We measured groundwater age, nitrogen and sulfur isotopes, and water chemistry from agricultural wells in an unconfined aquifer in Brittany, France, to quantify changes in nitrate concentration due to dilution and denitrification. Field data showed large differences in nitrate concentrations among wells, associated with differences in the exposure time distributions. By constraining a catchment-scale characteristic reaction time for denitrification with water chemistry proxies and exposure times, we were able to assess rates of denitrification along groundwater flow paths. This unified modeling approach is transferable to other catchments and could be further used to investigate how catchment structure and flow dynamics interact with biogeochemical processes such as denitrification.