Denitrification and dilution along fracture flowpaths influence the recovery of a bedrock aquifer from nitrate contamination

Abstract

In 2000, elevated nitrate concentrations ranging from 12 to 34mg/L NO3N were discovered in groundwater from numerous domestic bedrock wells adjacent to a large dairy farm in central Vermont. Long-term plots and contours of nitrate vs. time for bedrock wells showed "little/no", "moderate", and "large" change patterns that were spatially separable. The metasedimentary bedrock aquifer is strongly anisotropic and groundwater flow is controlled by fractures, bedding/foliation, and basins and ridges in the bedrock surface. Integration of the nitrate concentration vs. time data and the physical and chemical aquifer characterization suggest two nitrate sources: a point source emanating from a waste ravine and a non-point source that encompasses the surrounding fields. Once removed, the point source of NO3 (manure deposited in a ravine) was exhausted and NO3 dropped from 34mg/L to <10mg/L after ~10years; however, persistence of NO3 in the 3 to 8mg/L range (background) reflects the long term flux of nitrates from nutrients applied to the farm fields surrounding the ravine over the years predating and including this study. Inferred groundwater flow rates from the waste ravine to either moderate change wells in basin 2 or to the shallow bedrock zone beneath the large change wells are 0.05m/day, well within published bedrock aquifer flow rates. Enrichment of (15)N and (18)O in nitrate is consistent with lithotrophic denitrification of NO3 in the presence of dissolved Mn and Fe. Once the ravine point-source was removed, denitrification and dilution collectively were responsible for the down-gradient decrease of nitrate in this bedrock aquifer. Denitrification was most influential when NO3N was >10mg/L. Our multidisciplinary methods of aquifer characterization are applicable to groundwater contamination in any complexly-deformed and metamorphosed bedrock aquifer.

Nitrate reduction potential of a fractured Middle Triassic carbonate aquifer in Southwest Germany

“…While natural organic matter (NOM) is the most common electron donor for (heterotrophic) denitrification in shallow alluvial aquifers (Smith and Duff 1988;Zarnetske et al 2011), ferrous iron [Fe(II)] and reduced sulfur [S(-I)] bearing minerals such as pyrite were found to dominate (autotrophic) denitrification in aquifers with low amounts and limited bioavailability of NOM. This includes fractured aquifers in carbonate rocks (Baker et al 2012;Kim et al 2016;Opazo et al 2016), and crystalline bedrock (Pauwels et al 2000;Orr et al 2016), but also porous aquifers (e.g., Schwientek et al 2008;Zhang et al 2013). The presence of denitrifying microorganisms within fractured carbonate aquifers was confirmed by studies investigating microbial communities in the major conduit and fracture network (Farnleitner et al 2005;Jakus et al 2021) or attached to the limestone rock matrix (Herrmann et al 2017;Starke et al 2017).…”