Understanding subsurface denitrification potential will give greater insights into landscape nitrate (NO3−) delivery to groundwater and indirect nitrous oxide (N2O) emissions to the atmosphere. Potential denitrification rates and ratios of N2O/(N2O + N2) were investigated in intact soil cores collected from 0–0.10, 0.45–0.55 and 1.20–1.30 m depths representing A, B and C soil horizons, respectively from three randomly selected locations within a single intensively managed grazed grassland plot in south eastern Ireland. The soil was moderately well drained with textures ranging from loam to clay loam (gleysol) in the A to C horizon. An experiment was carried out by amending soils from each horizon with (i) 90 mg NO3−–N as KNO3, (ii) 90 mg NO3−–N + 150 mg glucose-C, (iii) 90 mg NO3−–N + 150 mg DOC (dissolved organic carbon, prepared using top soil of intensively managed grassland) kg−1 dry soil. An automated laboratory incubation system was used to measure simultaneously N2O and N2, at 15 ◦C, with the moisture content raised by 3% (by weight) above the moisture content at field capacity (FC), giving a water-filled pore space (WFPS) of 80, 85 and 88% in the A, B and C horizons, respectively. There was a significant effect (p < 0.01) of soil horizon and added carbon on cumulative N2O emissions. N2O emissions were higher from the A than the B and C horizons and were significantly lower from soils that received only nitrate than soils that received NO3 − + either of the C sources. The two C sources gave similar N2O emissions. The N2 fluxes differed significantly (p < 0.05) only between the A and C horizons. During a 17-day incubation, total denitrification losses of the added N decreased significantly (p < 0.01) with soil depth and were increased by the addition of either C source. The fraction of the added N lost from each horizon were A: 25, 61, 45%; B: 12, 29, 28.5% and C: 4, 20, 18% for nitrate, nitrate + glucose-C and nitrate + DOC, respectively. The ratios of N2O to N2O + N2 differed significantly (p < 0.05) only between soil horizons, being higher in the A (0.58–0.75) than in the deeper horizons (0.10–0.36 in B and 0.06–0.24 in C), clearly indicating the potential of subsoils for a more complete reduction of N2O to N2. Stepwise multiple regression analysis revealed that N2O flux increased with total organic C and total N but decreased with NO3 −–N which together explained 88% of the variance (p < 0.001). The N2 flux was best explained (R2 = 0.45, p < 0.01) by soluble organic nitrogen (SON) (positive) and with NO3−–N (negative). Stepwise multiple regression revealed a best fit for total denitrification rates which were positive for total C and negative for NO3 −–N with the determination coefficient of 0.76 (p < 0.001). The results suggest that without C addition, potential denitrification rate below the root zone was low. Therefore, the added C sources in subsoils can satisfactorily increase nitrate depletion via denitrification where the mole fraction of N2O would be further reduced to N2 during diffusional transport through the soil profile to the atmosphere and/or to groundwater. Subsoil denitrification can be accelerated either through introducing C directly into permeable reactive barriers and/or indirectly, by irrigating dirty water and manipulating agricultural plant composition and diversity.peer-reviewedDepartment of Agriculture, Fisheries and Food Ireland - Research Stimulus Fund Programme (Grant RSF 06 383)

Identification of specific landscape areas with high and low groundwater denitrification potential is critical for improved management of agricultural nitrogen (N) export to ground and surface waters and indirect nitrous oxide (N₂O) emissions. Denitrification products together with concurrent hydrogeochemical properties were analysed over two years at three depths at two low (L) and two high (H) permeability agricultural sites in Ireland. Mean N₂O-N at H sites were significantly higher than L sites, and decreased with depth. Conversely, excess N₂-N were significantly higher at L sites than H sites and did not vary with depth. Denitrification was a significant pathway of nitrate (NO₃⁻-N) reduction at L sites but not at H sites, reducing 46-77% and 4-8% of delivered N with resulting mean NO₃⁻-N concentrations of 1-4 and 12-15 mg N L⁻¹ at L and H sites, respectively. Mean N₂O-N emission factors (EF₅g) were higher than the most recent Intergovernmental Panel on Climate Change (IPCC, 2006) default value and more similar to the older IPCC (1997) values. Recharge during winter increased N₂O but decreased excess dinitrogen (excess N₂-N) at both sites, probably due to increased dissolved oxygen (DO) coupled with low groundwater temperatures. Denitrifier functional genes were similar at all sites and depths. Data showed that highly favourable conditions prevailed for denitrification to occur--multiple electron donors, low redox potential (Eh<100 mV), low DO (<2 mg L⁻¹), low permeability (k(s)<0.005 m·d⁻¹) and a shallow unsaturated zone (<2 m). Quantification of excess N₂-N in groundwater helps to close N balances at the local, regional and global scales.

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate-N (NO3-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO3-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (Ksat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO3-N L(-1) showed, when assessed individually in a step wise procedure, Ksat was significantly related to groundwater NO3-N concentration. Distance of the point dirty water pollution source becomes significant when included with Ksat in the model. The model relationships show areas with higher Ksat values have less time for denitrification to occur, whereas lower Ksat values allow denitrification to occur. Areas with higher permeability transport greater NO3-N fluxes to ground and surface waters. When the distribution of Cl- was examined by the model, Ksat and ground elevation had the most explanatory power but Ksat was not significant pointing to dilution having an effect. Areas with low NO3 concentration and unaffected Cl- concentration points to denitrification, low NO3 concentration and low Cl- chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO3-N was significantly (P<0.05) related to groundwater N2/Ar ratio, redox potential (Eh), dissolved O2 and N2 and was close to being significant with N2O (P=0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.