• Evaluation of headspace equilibration methods for quantifying greenhouse gases in groundwater

      Jahangir, Mohammad M. R.; Johnston, Paul; Khalil, Mohammed I.; Grant, Jim; Somers, Cathal; Richards, Karl G.; Department of Agriculture, Food and the Marine, Ireland; Department of Civil, Structural and Environmental Engineering, Trinity College Dublin; RSF 06383 (Elsevier, 23/08/2012)
      The objective of the study was to evaluate the different headspace equilibration methods for the quantification of dissolved greenhouse gases in groundwater. Groundwater samples were collected from wells with contrasting hydrogeochemical properties and degassed using the headspace equilibration method. One hundred samples from each well were randomly selected, treatments were applied and headspace gases analysed by gas chromatography. Headspace equilibration treatments varied helium (He):water ratio, shaking time and standing time. Mean groundwater N2O, CO2 and CH4 concentrations were 0.024 mg N L−1, 13.71 mg C L−1 and 1.63 μg C L−1, respectively. All treatments were found to significantly influence dissolved gas concentrations. Considerable differences in the optimal He:water ratio and standing time were observed between the three gases. For N2O, CO2 and CH4 the optimum operating points for He:water ratio was 4.4:1, 3:1 and 3.4:1; shaking time was 13, 12 and 13 min; and standing time was 63, 17 and 108 min, respectively. The headspace equilibration method needs to be harmonised to ensure comparability between studies. The experiment reveals that He:water ratio 3:1 and shaking time 13 min give better estimation of dissolved gases than any lower or higher ratios and shaking times. The standing time 63, 17 and 108 min should be applied for N2O, CO2 and CH4, respectively.
    • Groundwater: A pathway for terrestrial C and N losses and indirect greenhouse gas emissions

      Jahangir, Mohammad M. R.; Johnston, Paul; Khalil, Mohammed I.; Hennessy, Deirdre; Humphreys, James; Fenton, Owen; Richards, Karl G.; Department of Agriculture, Food and the Marine, Ireland; Department of Civil, Structural and Environmental Engineering, Trinity College Dublin; RSF 06383 (Elsevier, 16/07/2012)
      Estimating losses of dissolved carbon (C) and nitrogen (N) via groundwater in an agricultural system provides insights into reducing uncertainties in the terrestrial C and N balances. In addition, quantification of dissolved nitrous oxide (N2O), carbon dioxide (CO2) and methane (CH4) in groundwaters beneath agricultural systems is important for global greenhouse gas (GHG) budgets. Dissolved C (DC: dissolved organic carbon (DOC) + CO2-C + CH4-C) and dissolved nitrogen (DN: NO3−-N + NH4+ + NO2−-N + N2O-N + N2) in groundwater were measured in two low permeability (<0.02 m d−1) and two high permeability (>0.05 m d−1) aquifers in Ireland. Groundwater in multilevel piezometers was sampled monthly over two years. Mean groundwater discharge to surface water was higher in 2009 (587–836 mm) than in 2010 (326–385 mm). Dissolved C and N delivery to surface water via groundwater caused substantial losses of terrestrial C and N. The extent of delivery was site specific and depended on N input, recharge and aquifer permeability. Mean dissolved N losses ranged from 8–12% of N input in low permeability to 27–38% in high permeability aquifers. The dominant fraction of DN was NO3−-N (84–90% of DN) in high permeability aquifers and N2 (46–77% of DN) in low permeability aquifers. Indirect N2O emissions via groundwater denitrification accounted for 0.03–0.12% of N input, which was equivalent to 3–11% of total N2O emissions. Dissolved C loss to surface waters via groundwater was not significant compared to total carbon (TC) content of the topsoil (0.06–0.18% of TC). Site characteristics contributed greatly to the distribution of N between NO3−-N and dissolved N gases, N2O and N2. Indirect GHG emissions from groundwater were an important part of farm nutrient budgets, which clearly has implications for national GHG inventories.
    • Linking hydrogeochemistry to nitrate abundance in groundwater in agricultural settings in Ireland

      Jahangir, Mohammad M. R.; Johnston, Paul; Khalil, Mohammed I.; Richards, Karl G.; Department of Agriculture, Food and the Marine, Ireland; Department of Civil, Structural and Environmental Engineering, Trinity College Dublin; RSF 06383 (Elsevier, 11/05/2012)
      Nitrate (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.