Mohammad M. R. Jahangir

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

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.

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

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 N(2)O, CO(2) and CH(4) 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 N(2)O, CO(2) and CH(4) 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 N(2)O, CO(2) and CH(4), respectively.

Groundwater nitrate reduction versus dissolved gas production: A tale of two catchments

At the catchment scale, a complex mosaic of environmental, hydrogeological and physicochemical characteristics combine to regulate the distribution of groundwater and stream nitrate (NO3-). The efficiency of NO3- removal (via denitrification) versus the ratio of accumulated reaction products, dinitrogen (excess N2) & nitrous oxide (N2O), remains poorly understood. Groundwater was investigated in two well drained agricultural catchments (10km2) in Ireland with contrasting subsurface lithologies (sandstone vs. slate) and landuse. Denitrification capacity was assessed by measuring concentration and distribution patterns of nitrogen (N) species, aquifer hydrogeochemistry, stable isotope signatures and aquifer hydraulic properties. A hierarchy of scale whereby physical factors including agronomy, water table elevation and permeability determined the hydrogeochemical signature of the aquifers was observed. This hydrogeochemical signature acted as the dominant control on denitrification reaction progress. High permeability, aerobic conditions and a lack of bacterial energy sources in the slate catchment resulted in low denitrification reaction progress (0-32%), high NO3- and comparatively low N2O emission factors (EF5g1). In the sandstone catchment denitrification progress ranged from 4 to 94% and was highly dependent on permeability, water table elevation, dissolved oxygen concentration solid phase bacterial energy sources. Denitrification of NO3- to N2 occurred in anaerobic conditions, while at intermediate dissolved oxygen; N2O was the dominant reaction product. EF5g1 (mean: 0.0018) in the denitrifying sandstone catchment was 32% less than the IPCC default. The denitrification observations across catchments were supported by stable isotope signatures. Stream NO3- occurrence was 32% lower in the sandstone catchment even though N loading was substantially higher than the slate catchment.

Permeable reactive interceptors: blocking diffuse nutrient and greenhouse gases losses in key areas of the farming landscape

Engineered remediation technologies such as denitrifying bioreactors target single contaminants along a nutrient transfer continuum. However, mixed contaminant discharges to a water body are more common from agricultural systems. Indeed, evidence presented herein indicates that pollution swapping within denitrifying bioreactor systems adds to such deleterious discharges. The present paper proposes a more holistic approach to contaminant remediation on farms, moving from the use of ‘denitrifying bioreactors’ to the concept of a ‘permeable reactive interceptor’ (PRI). Besides management changes, a PRI should contain additional remediation cells for specific contaminants in the form of solutes, particles or gases. Balance equations and case studies representing different geographic areas are presented and used to create weighting factors. Results showed that national legislation with respect to water and gaseous emissions will inform the eventual PRI design. As it will be expensive to monitor a system continuously in a holistic manner, it is suggested that developments in the field of molecular microbial ecology are essential to provide further insight in terms of element dynamics and the environmental controls on biotransformation and retention processes within PRIs. In turn, microbial and molecular fingerprinting could be used as an in-situ cost-effective tool to assess nutrient and gas balances during the operational phases of a PRI.

Mustard catch crop enhances denitrification in shallow groundwater beneath a spring barley field

Over-winter green cover crops have been reported to increase dissolved organic carbon (DOC) concentrations in groundwater, which can be used as an energy source for denitrifiers. This study investigates the impact of a mustard catch crop on in situ denitrification and nitrous oxide (N2O) emissions from an aquifer overlain by arable land. Denitrification rates and N2O-N/(N2O-N+N2-N) mole fractions were measured in situ with a push-pull method in shallow groundwater under a spring barley system in experimental plots with and without a mustard cover crop. The results suggest that a mustard cover crop could substantially enhance reduction of groundwater nitrate NO3--N via denitrification without significantly increasing N2O emissions. Mean total denitrification (TDN) rates below mustard cover crop and no cover crop were 7.61 and 0.002 μg kg(-1) d(-1), respectively. Estimated N2O-N/(N2O-N+N2-N) ratios, being 0.001 and 1.0 below mustard cover crop and no cover crop respectively, indicate that denitrification below mustard cover crop reduces N2O to N2, unlike the plot with no cover crop. The observed enhanced denitrification under the mustard cover crop may result from the higher groundwater DOC under mustard cover crop (1.53 mg L(-1)) than no cover crop (0.90 mg L(-1)) being added by the root exudates and root masses of mustard. This study gives insights into the missing piece in agricultural nitrogen (N) balance and groundwater derived N2O emissions under arable land and thus helps minimise the uncertainty in agricultural N and N2O-N balances.

An evaluation of urine patch simulation methods for nitrous oxide emission measurement

Global nitrous oxide (N 2 O) inventory estimates for pasture systems are refined based on measurements of N 2 O loss from simulated urine patches. A variety of methods are used for patch simulation but they frequently use a uniform wetted area (UWA), often smaller than a bovine urine patch. However, natural patches follow non-uniform infiltration patterns expanding naturally from a point of deposit with a non-wetted zone of influence. Using 2 litres of urine the UWA method was compared, using a 0·156 m 2 collar, with a naturally expanding effective area (NEEA) method, using a 0·462 m 2 collar under high (HL) and low (LL) N 2 O loss conditions. The method chosen affects urine nitrogen (N) loading to the soil. Under HL the UWA method induced a N 2 O-N loss of 280·6 mg/patch, significantly less than the 434·8 mg/patch loss for the NEEA method, for the same simulated urination. Under LL there was no method effect. Efforts should be made to employ patch simulation methods, which mimic natural deposits and can be achieved, at least in part, by: (a) Using a urine volume and N content similar to that of the animal of interest. (b) Allowing natural infiltration of the chosen urine volume to permit tapering towards the edges. (c) Measuring from the zone of influence in addition to the wetted area, i.e. the patch effective area.

The interactive effects of fertiliser nitrogen with dung and urine on nitrous oxide emissions in grassland

Abstract Nitrous oxide (N2O) is an important and potent greenhouse gas (GHG). Although application of nitrogen (N) fertiliser is a feature of many grazing systems, limited data is available on N2O emissions in grassland as a result of the interaction between urine, dung and fertiliser N. A small plot study was conducted to identify the individual and interactive effects of calcium ammonium nitrate (CAN) fertiliser, dung and urine. Application of CAN with dung and urine significantly increased the mass of N2O-N emission. Importantly, the sum of N2O-N emitted from dung and CAN applied individually approximated the emission from dung and CAN fertiliser applied together, that is, an additive effect. However, in the case of urine and CAN applied together, the emission was more than double the sum of the emission from urine and CAN fertiliser applied individually, that is, a multiplicative effect. Nitrous oxide emissions from dung, urine and fertiliser N are typically derived individually and these individual emission estimates are aggregated to produce estimates of N2O emission. The presented findings have important implications for how individual emission factors are aggregated; they suggest that the multiplicative effect of the addition of CAN fertiliser to urine patches needs to be taken into account to refine the estimation of N2O emissions from grazing grasslands.