Nitrate (NO3) contamination in agricultural watersheds is a widespread problem that threatens local drinking supplies and downstream ecology. Dual isotopes of NO3- (d15N and d18O) have been successfully used to identify sources of NO3 contamination and nitrogen (N)-cycle processes in agricultural settings. From 1998 to 2000, tile drainage and stream waters at the Strawberry Creek Catchment were sampled for NO3- concentration and isotopes. The results suggest that tile NO3 were mainly derived from soil organic matter and manure fertilizers, and that they were not extensively altered by denitrification. NO3- concentrations and isotopes in the stream oscillated between the influence of tile inputs, during periods of higher basin discharge, and groundwater inputs, during low basin discharge. The affect of denitrification was evident in stream NO3- samples. Sources and processes of dissolved NO3- and N2O were explored using concentrations and stable isotopes during the 2007 Springmelt and 2008 mid-winter thaw events. Tiles are a source of NO3- to the stream during both events and concentrations at the outflow are above the 10 mg N/L drinking water limit during the 2008 mid-winter thaw. The stream was a source of N2O to the atmosphere during both events. d15N and d18O of N2O reveal that N2O is produced from denitrification during both events. d18O:d15N slopes measured in N2O were due to the influence of substrate consumption (tiles) and gas exchange (stream). The stable isotopes of dissolved NO3- and N2O were also characterized during non-melt conditions (October 2006 to June 2007 and Fall 2007) at the Strawberry Creek catchment. Again, the purpose was to determine the sources and processes responsible for the measured concentrations and isotopic signatures. The isotope data suggests that N2O was produced by denitrification. Furthermore, NO3- consumption and gas exchange altered the original N2O signature. Isotopic distinction between soil gas N2O and dissolved N2O is suggestive of different production mechanisms between the unsaturated and saturated zones. Since the range of dissolved N2O isotopes from the Strawberry Creek catchment are relatively constraned, definition of the local isotopic signature of secondary, agricultural N2O sources was possible.

Riparian zones (RZ) are known to act as buffers, reducing the transfer of potentially harmful nutrients from agricultural fields to surface water bodies. However, many of the same processes in the subsurface that help to reduce this nutrient loading, may also be leading to greenhouse gas (GHG) production and emissions from these areas. Agricultural riparian zones in Southern Ontario are often characterized by a sloped topography, with the highest topographic position being closest to the field edge, decreasing towards an adjacent stream or other surface water body. This topographic variability, combined with lateral chemical inputs from both upland areas and the stream, is expected to cause variable hydrochemical environments throughout the RZ, which may therefore lead to variable N2O dynamics between upland, mid-riparian and lowland areas. The objectives of this study were to examine these spatial trends in N2O production and resulting emissions, as related to the hydrochemical environment in these three distinct zones. Objectives were achieved by instrumenting 6 sites across two transects running perpendicular from the agricultural field edge, towards the stream edge, analyzing for subsurface N2O, moisture and temperature, groundwater NO3, NH4, dissolved organic carbon (DOC), dissolved oxygen, and surface fluxes of N2O. Subsurface N2O concentrations and ground water nutrient concentrations displayed distinct spatial and temporal/seasonal trends in the three positions across the RZ, however N2O fluxes across the soil-atmosphere interface did not display strong or consistent spatial trends. There was a disconnect between the subsurface variables and the fluxes at the surface, in that N2O emissions did not reflect the N2O concentrations produced in the shallow soil profile (150 cm deep), nor were they significantly related to the geochemical environment at each position. The lack of visible spatial trends in N2O fluxes may have been due to an “oxic blanket” effect which may divide the surface from the subsurface soil profile. As N2O fluxes in this study (-0.28 to 1.3 nmol m-2 s-1) were within the range observed at other, similar study sites, the oxic blanket doesn’t appear to impede concentrations of N2O reaching the soil-atmosphere interface. This may suggest that the N2O released as a flux was being produced in the very shallow soil profile (0 – 5 cm), above the soil gas profile arrays installed at this site. Subsurface concentrations of N2O were fairly high at certain depths and times, which was not reflected in the fluxes. This may have resulted from nitrifier denitrification reducing N2O to N2 before it reached the surface, in aerobic zones above the water table. Another potential reason for the lack of connection between subsurface processes and surface emissions was the high heterogeneity observed across the RZ, which may have overshadowed potential differences between positions. Physical soil properties like porosity and bulk density across the RZ also potentially impacted the N2O movement through the soil profile, resulting in similar fluxes among positions, and over time. The missing connection between subsurface N2O concentrations, ground water nutrients, and the surface fluxes was not a hypothesized result, and requires further research and analysis for a better understanding of the production and consequent movement of N2O.

Nitrate (NO3) contamination in agricultural watersheds is a widespread problem that threatens local drinking supplies and downstream ecology. Dual isotopes of NO3- (d15N and d18O) have been successfully used to identify sources of NO3 contamination and nitrogen (N)-cycle processes in agricultural settings. From 1998 to 2000, tile drainage and stream waters at the Strawberry Creek Catchment were sampled for NO3- concentration and isotopes. The results suggest that tile NO3 were mainly derived from soil organic matter and manure fertilizers, and that they were not extensively altered by denitrification. NO3- concentrations and isotopes in the stream oscillated between the influence of tile inputs, during periods of higher basin discharge, and groundwater inputs, during low basin discharge. The affect of denitrification was evident in stream NO3- samples. Sources and processes of dissolved NO3- and N2O were explored using concentrations and stable isotopes during the 2007 Springmelt and 2008 mid-winter thaw events. Tiles are a source of NO3- to the stream during both events and concentrations at the outflow are above the 10 mg N/L drinking water limit during the 2008 mid-winter thaw. The stream was a source of N2O to the atmosphere during both events. d15N and d18O of N2O reveal that N2O is produced from denitrification during both events. d18O:d15N slopes measured in N2O were due to the influence of substrate consumption (tiles) and gas exchange (stream). The stable isotopes of dissolved NO3- and N2O were also characterized during non-melt conditions (October 2006 to June 2007 and Fall 2007) at the Strawberry Creek catchment. Again, the purpose was to determine the sources and processes responsible for the measured concentrations and isotopic signatures. The isotope data suggests that N2O was produced by denitrification. Furthermore, NO3- consumption and gas exchange altered the original N2O signature. Isotopic distinction between soil gas N2O and dissolved N2O is suggestive of different production mechanisms between the unsaturated and saturated zones. Since the range of dissolved N2O isotopes from the Strawberry Creek catchment are relatively constraned, definition of the local isotopic signature of secondary, agricultural N2O sources was possible.

Riparian zones (RZ) are known to act as buffers, reducing the transfer of potentially harmful nutrients from agricultural fields to surface water bodies. However, many of the same processes in the subsurface that help to reduce this nutrient loading, may also be leading to greenhouse gas (GHG) production and emissions from these areas. Agricultural riparian zones in Southern Ontario are often characterized by a sloped topography, with the highest topographic position being closest to the field edge, decreasing towards an adjacent stream or other surface water body. This topographic variability, combined with lateral chemical inputs from both upland areas and the stream, is expected to cause variable hydrochemical environments throughout the RZ, which may therefore lead to variable N2O dynamics between upland, mid-riparian and lowland areas. The objectives of this study were to examine these spatial trends in N2O production and resulting emissions, as related to the hydrochemical environment in these three distinct zones. Objectives were achieved by instrumenting 6 sites across two transects running perpendicular from the agricultural field edge, towards the stream edge, analyzing for subsurface N2O, moisture and temperature, groundwater NO3, NH4, dissolved organic carbon (DOC), dissolved oxygen, and surface fluxes of N2O. Subsurface N2O concentrations and ground water nutrient concentrations displayed distinct spatial and temporal/seasonal trends in the three positions across the RZ, however N2O fluxes across the soil-atmosphere interface did not display strong or consistent spatial trends. There was a disconnect between the subsurface variables and the fluxes at the surface, in that N2O emissions did not reflect the N2O concentrations produced in the shallow soil profile (150 cm deep), nor were they significantly related to the geochemical environment at each position. The lack of visible spatial trends in N2O fluxes may have been due to an “oxic blanket” effect which may divide the surface from the subsurface soil profile. As N2O fluxes in this study (-0.28 to 1.3 nmol m-2 s-1) were within the range observed at other, similar study sites, the oxic blanket doesn’t appear to impede concentrations of N2O reaching the soil-atmosphere interface. This may suggest that the N2O released as a flux was being produced in the very shallow soil profile (0 – 5 cm), above the soil gas profile arrays installed at this site. Subsurface concentrations of N2O were fairly high at certain depths and times, which was not reflected in the fluxes. This may have resulted from nitrifier denitrification reducing N2O to N2 before it reached the surface, in aerobic zones above the water table. Another potential reason for the lack of connection between subsurface processes and surface emissions was the high heterogeneity observed across the RZ, which may have overshadowed potential differences between positions. Physical soil properties like porosity and bulk density across the RZ also potentially impacted the N2O movement through the soil profile, resulting in similar fluxes among positions, and over time. The missing connection between subsurface N2O concentrations, ground water nutrients, and the surface fluxes was not a hypothesized result, and requires further research and analysis for a better understanding of the production and consequent movement of N2O.

Despite the spatial significance of Canadas boreal forest, there is very little known about greenhouse gas emissions within it. The primary objective of this project was to study the atmosphere-soil exchange of CH4 and N2O in the boreal forest of central Saskatchewan. In the summers of 2006 and 2007, greenhouse gas emissions were measured along transects in three different mature forest stands (trembling aspen, black spruce and jack pine) using a sealed chamber method. In addition, the gross rates of mineralization and nitrification, and the relative contribution of nitrification and denitrification to N2O emissions, were measured at the trembling aspen site using a stable isotope technique in which 15N-enriched nitrate and ammonium were injected into intact soil cores. The amount of 14N found in the labeled pools was used to measure the gross rates, and the amount of 15N found in the emitted N2O was used to determine the relative contribution of the different N pathways to total N2O emissions. Results indicated that the jack pine and black spruce sites were slight sinks of CH4 (-1.23 kg CH4-C ha-1 yr-1and -0.17 kg CH4-C ha-1 yr-1 respectively in 2006 and -0.95 kg CH4-C ha-1 yr-1and 0.45 kg CH4-C ha-1 yr-1 respectively in 2007), whereas the trembling aspen site was a net source (46.7 kg CH4-C ha-1 yr-1 in 2006 and 196.0 kg CH4-C ha-1 yr-1 in 2007). All three sites had very low cumulative N2O emissions, ranging from -0.02 to 0.14 kg N2O-N ha-1 yr-1 in both years. Of the environmental controls examined for CH4, consumption at the jack pine site was correlated positively with organic carbon and negatively with water-filled pore space. Black spruce CH4 emissions were correlated negatively with both organic carbon and clay content, and emissions at the trembling aspen site were positively correlated with soil temperature and organic carbon, while also related to the presence of standing water (2006 and 2007 had very high precipitation, causing a high water table and ponding in depressions). The N2O emissions were not correlated with any of the environmental parameters measured at the jack pine or black spruce sites, but clay content was positively related to emissions at the trembling aspen site. The 15N results indicated that N cycling at the trembling aspen site was very rapid, allowing little N to escape the system as N2O; the majority of emissions that did occur were due to a nitrification-related process.

The Gulf of Mexico hypoxic zone is created by strong persistent water stratification and nutrient loading from the Mississippi River which fuels primary production and bacterial decomposition. The Texas-Louisiana shelf becomes seasonally oxygen depleted and hypoxia (O2 less than or equal to 1.4 ml l-1) occurs. Low oxygen environments are conducive for the microbial production of nitrous oxide (N2O), a powerful greenhouse gas found in the atmosphere in trace amounts (319 ppbv). Highly productive coastal areas contribute 61% of the total oceanic N2O production and currently global sources exceed sinks. This study is the first characterization of N2O produced in the Gulf of Mexico hypoxic zone. Because of enhanced microbial activity and oxygen deficiency, it is hypothesized that the Gulf of Mexico hypoxic zone is a source of N2O to the atmosphere. Seasonal measurements of N2O were made during three research cruises in the Northern Gulf of Mexico (Sept. 2007, April 2008, and July 2008). Water column N2O profiles were constructed from stations sampled over time, and bottom and surface samples were collected from several sites in the hypoxic zone. These measurements were used to calculate atmospheric flux of N2O. The Gulf of Mexico hypoxic zone was a source of N2O to the atmosphere, and N2O production was highest during times of seasonal hypoxia. N2O was positively correlated with temperature and salinity, and negatively correlated with oxygen concentration. Atmospheric fluxes ranged from -11.27 to 153.22 umol m-2 d-1. High accumulations of N2O in the water column (up to 2878 % saturated) were associated with remineralization of organic matter at the base of the pycnocline and oxycline. Seasonal hypoxia created a source of N2O to the atmosphere (up to 2.66 x 10-3 Tg N2O for the month of September 2007), but there was a slight sink during April 2008 when hypoxia did not occur. Large fluxes of N2O during the 3 to 5 month hypoxic period may not be counterbalanced by a 7 to 9 month sink period indicating the Gulf of Mexico hypoxic zone may be a net source of N2O to the atmosphere.

While breeding for increased oil yield has generated new lines of spring canola (Brassica napus L.) for biodiesel production, emissions of N2O from fertilized canola fields threaten to undermine the climate change mitigation benefits of canola as a biodiesel alternative to conventional diesel. This study determined the response of N2O emissions to canola line and N treatment in a maritime setting (Truro, Nova Scotia). Tissue N uptake was measured to determine whether differences in N uptake between the lines could explain any observed effect of canola line. Nitrate Exposure (the summation of daily soil NO3- concentrations over a growing season, serving as an integrated measure of the exposure of soil biomass to nitrate over the growing season) was determined to investigate its potential as a predictor of N2O emissions. Four spring canola lines (‘Topaz’, ‘Sentry’, ‘Polo’, and 04C204, in order of increasing seed oil content) were paired with five N treatments (40, 60, 80, 100, and 120 kg N ha-1) in an incomplete two-factor factorial design over two growing seasons (2008 and 2009). N2O emissions were determined using a non-steady state vented chamber method. N2O emissions peaks closely followed increases in soil water content in both years, indicating that limited aerobicity was the trigger for N2O emissions events, and suggesting that denitrification was the predominant microbial process responsible for N2O emissions. The magnitude of average N2O emissions both years was considerably low when compared to other studies (0.55 and 0.56 kg N2O ha-1 in 2008 and 2009 respectively). Increasing N treatment resulted in significantly increased N2O emissions in 2008. Though the same trend was observed in 2009, it was not found to be significant. Differences in weed cover, soil C, soil N supplying capacity, and elevation between the sites may have contributed to the inability to detect an N2O emissions response to N treatment in 2009. Canola line had no effect on N2O emissions in either study year, though heavy competition by weeds significantly affected canola plant health and survival in 2009. Tissue N uptake increased with increasing N treatment, but did not change with choice of line, which is consistent with the observation of no N2O emissions response to line. Nitrate Exposure was found to be strongly correlated with N2O emissions in a linear relationship, supporting the conclusion that Nitrate Exposure can be a promising indicator of N2O emissions when they are limited by soil N. Finally, FluxPerOil, the ratio of N2O emissions per unit oil yield (kg N2O kg-1 oil) was found to decrease with decreased N treatment in 2008, though only very little, indicating a marginal abatement of N2O emissions at a significant cost of oil. FluxPerOil was unreliable in 2009 due to weeds compromising the line effect and therefore oil yield.

A field experiment was carried out in Ontario, Canada to compare independently measured soil N2O profile concentration and surface N2O flux measurements overwinter and at spring thaw, to estimate the soil N2O content accumulation overwinter, and to estimate the magnitude of the contribution of the physical release of trapped N2O to surface fluxes at spring thaw. Gas samples at various depths were taken and N2O concentrations determined, soil profile gaseous N2O content was calculated by estimating the air-filled pore-space from soil condition measurements, and soil aqueous N2O content was calculated using liquid water content measurements and applying Henry’s Law. Soil N2O content was found to reach a maximum of ~25 mg N2O m-2, and by comparing changes in soil N2O content to surface fluxes measured using the micrometeorological flux-gradient technique, the physical release of previously produced N2O was estimated to contribute up to 47% of spring thaw N2O surface fluxes.

A two-year field study and two incubation studies were conducted to evaluate incorporating urea with a urease and nitrification inhibitor to reduce N2O and N losses from fall banded fertilizer. In each year of the field experiment, five fertilizer treatments (fall banded NBPT-DCD urea, conventional urea, calcium nitrate, spring banded conventional urea and control) were applied at three sites. The effect of incorporating urease and nitrification inhibitors with urea was not consistent in our studies. The application of fall banded NBPT and DCD did not result in greater agronomic performance. Moreover, the addition of inhibitors to urea did not reduce nitrous oxide emissions in the field. The addition of inhibitors resulted in significantly less cumulative nitrous oxide emissions compared to conventional urea in only one of two laboratory experiments. In conditions where fertilizer was not generally susceptible to large losses, the effects of urease and nitrification inhibitors may not be evident.

Through the 21st century, global-mean stratospheric ozone abundances are projected to increase due to decreasing chlorine and bromine concentrations (as a consequence of the Montreal Protocol for Substances that Deplete the Ozone Layer), and continued CO₂-induced cooling of the stratosphere. Along with CO₂, anthropogenic emissions of the greenhouse gases N₂O and CH₄ are projected to increase, thus increasing their atmospheric concentrations. Consequently, reactive nitrogen species produced from N₂O and reactive hydrogen species produced from CH₄ are expected to play an increasingly important role in determining stratospheric ozone concentrations. Chemistry-climate model simulations were performed using the NIWA-SOCOL (National Institute of Water and Atmospheric Research - SOlar Climate Ozone Links) model, which tracks the contributions to ozone loss from a prescribed set of catalytic cycles, including the ozone-depleting nitrogen and hydrogen cycles, over latitude, longitude, pressure and time. The results provide a comprehensive picture of how stratospheric ozone may evolve through the 21st century under a range of greenhouse gas emissions scenarios, and quantitatively extend concepts that had previously been understood only qualitatively.