Linking hydrogeochemistry to nitrate abundance in groundwater in agricultural settings in Ireland

peer-reviewedNitrate (NO3-–N) contamination of groundwater and associated surface waters is an increasingly important global issue with multiple impacts on terrestrial, aquatic and atmospheric environments. Investigation of the distribution of hydrogeochemical variables and their connection with the occurrence of NO3-–N provides better insights into the prediction of the environmental risk associated with nitrogen use within agricultural systems. The research objective was to evaluate the effect of hydrogeological setting on agriculturally derived groundwater NO3-–N occurrence. Piezometers (n = 36) were installed at three depths across four contrasting agricultural research sites. Groundwater was sampled monthly for chemistry and dissolved gases, between February 2009 and January 2011. Mean groundwater NO3-–N ranged 0.7–14.6 mg L−1, with site and groundwater depth being statistically significant (p < 0.001). Unsaturated zone thickness and saturated hydraulic conductivity (Ksat) were significantly correlated with dissolved oxygen (DO) and redox potential (Eh) across sites. Groundwater NO3-–N occurrence was significantly negatively related to DOC and methane and positively related with Eh and Ksat. Reduction of NO3-–N started at Eh potentials <150 mV while significant nitrate reduction occurred <100 mV. Indications of heterotrophic and autotrophic denitrification were observed through elevated dissolved organic carbon (DOC) and oxidation of metal bound sulphur, as indicated by sulphate (SO42-). Land application of waste water created denitrification hot spots due to high DOC losses. Hydrogeological settings significantly influenced groundwater nitrate occurrence and suggested denitrification as the main control.Department of Agriculture, Food and the Marine Ireland - Research Stimulus Fund Programme (Grant RSF 06383); Department of Civil, Structural and Environmental Engineering, Trinity College Dublin

Denitrification and indirect N2O emissions in groundwater: Hydrologic and biogeochemical influences

peer-reviewedIdentification 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 (ks < 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.Department of Agriculture, Food and Marine, Ireland - Research Stimulus Fund Programme (Grant RSF 06383); The University of Dublin, Trinity College Dublin

Denitrification potential in subsoils: A mechanism to reduce nitrate leaching to groundwater

peer-reviewedUnderstanding 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.Department of Agriculture, Fisheries and Food Ireland - Research Stimulus Fund Programme (Grant RSF 06 383)