Diffuse agricultural pollution is a major contributor to poor water quality in many parts of the world. Consequently agri-environment policy promotes the use of riparian buffer strips and/or denitrifying wetlands to intercept and remove diffuse NO3--N pollution. However, these methods have the potential to cause ‘pollution swapping’: the exchange of one form of pollution as a result of measures implemented to reduce another. Thus the benefits of intercepting NO3--N could be offset by enhanced emissions of the potent greenhouse gases, nitrous oxide (N2O) and methane (CH4), from buffer strips and wetlands. This research aimed to: (1) quantify the direct N2O emissions from an irrigated buffer strip (IBS), using nitrate-rich agricultural drainage water, compared to a non-irrigated control (CP); (2) improve the understanding of N2O production and consumption within soils using controlled soil monolith experiments; (3) assess the effectiveness of a small (60 m2) instream wetland at intercepting and removing diffuse NO3--N pollution, and quantify pollution swapping in the form of CH4 and N2O emissions; (4) assess the production of CH4 and N2O within the sediment, and their emissions as well as inorganic-N concentrations in the overlying water column in response to temperature and turbulence, using intact wetland sediment and membrane inlet mass spectrometry (MIMS). The research focused on mitigating diffuse NO3--N pollution from grazed pasture at a farm in north-east England. Annual N2O-N emissions from the IBS and CP were not statistically different (P > 0.05): 509 and 263 g N2O-N ha-1, respectively, in 2007 and 375 and 500 g N2O-N ha- 1 year-1, respectively, in 2008. Irrigation of the IBS increased spatial variability in flux and generated hotspots of denitrification compared to the CP. However, these changes were short-lived. Direct N2O emission factors (EF1) calculated using the available NO3--loading data (September 2007 - December 2008) for the IBS were lower (c.0.1%) than those calculated for the CP assuming N input from biological N fixation only (<1.9%). Soil monolith experiments under a variety of irrigation and NO3--N loading regimes confirmed low direct and indirect (of dissolved N2O-N in leachate) emissions (<3.1 and <2.3% of applied NO3--N emitted as N2O-N, respectively), similar to the IPCC default emission factors. However, N loss in leachate was high, up to 82% of added NO3--N with concentrations reaching 24 mg NO3--N L-1. Therefore even though no pollution swapping occurred the high leachate losses indicate irrigation of buffer strips are not effective mitigation methods. Monitoring for 2 years of the instream wetland that received median NO3--N concentrations of c. 6 mg N L-1, but up to c. 20 mg N L-1, showed it to be ineffective at intercepting diffuse NO3- pollution: likely a result of the relatively high discharge and short water residence time, as well as the direct input of NO3--N to the wetland from secondary sources: field drains and/or overland flow. The wetland was a net source of NH4+-N in both 2007 and 2008, and a net sink of NO3--N in 2007 only. Annual wetland CH4 and N2O emissions were 713 and 237 mg CH4 m-2 year-1, and 3.5 and 1.9 mg N2O-N m-2 year-1, for 2007 and 2008, respectively and were highly variable between seasons. N pollution swapping was minimal from either direct or indirect emissions, but CH4 emissions were found to be of greater importance at a net cost of ~ £600 ha-1 over the study period (2007 to 2008), compared to N2O emissions (~ £60 ha-1) and low NO3--N interception savings (~ £24 ha-1). Incubation experiments suggest that spatially variable microsites of nitrifying, denitrifying or methanogenic activity and CH4 oxidation occur within the wetland sediment. Therefore off-line, larger wetland systems offer the best prospects of enhanced NO3--N interception and potentially reduced CH4 emissions by maintaining shallow water depths (increased CH4 oxidation) and long residence times (increased opportunity for denitrification), within the wetland or wetland cells.

Texas’ Mass Emission Cap and Trade program is a mandatory Nitrous Oxide (NOx) abatement program for medium and large stationary sources located in the Houston-Galveston ozone non-attainment area. Effected companies are required to upgrade equipment to meet the current best achievable NOx control technology (BACT) standards or to purchase emission credits in sufficient quantity to cover the difference in emissions between existing equipment and equipment meeting the BACT standard. With over 260 participating companies, the market for emission credits is ever changing, making it difficult to evaluate whether the lowest cost decision is to upgrade equipment or to purchase NOx emission credits. Because equipment upgrades are capital investments, a well informed, rational decision can have a significant impact on the corporate balance sheet. The objective of this research is to aid the decision maker by predicting credit prices based on a Geometric Brownian Motion model based on historical NOx emission credit transactions. The predicted credit price is useful in evaluating the likelihood of the equipment upgrade option being a favorable or unfavorable decision. For the examined cases, modeled results indicate that equipment upgrade is the more cost effective option. / text

The aim of this study was to investigate the effects of biochar amendment on soil greenhouse gas (GHG) emissions and to elucidate the mechanisms behind these effects. I investigated the suppression of soil carbon dioxide (CO2) and nitrous oxide (N2O) emissions in a bioenergy and arable crop soil, at a range of temperatures and with or without wetting/drying cycles. More detailed investigation on the underlying mechanisms focused on soil N2O emissions. I tested how biochar altered soil physico-chemical properties and the subsequent effects on soil N2O emissions. In addition, 15N pool dilution techniques were used to investigate the effect of biochar on soil N transformations. Biochar amendment significantly suppressed soil GHG emissions for two years within a bioenergy soil in the field and for several months in an arable soil. I hypothesised that soil CO2 emissions were suppressed under field conditions by a combination of mechanisms: biochar induced immobilisation of soil inorganic-N (BII), increased C-use efficiency, reduced C-mineralising enzyme activity and adsorption of CO2 to the biochar surface. Soil CO2 emissions were increased for two days following wetting soil due to the remobilisation of biochar-derived labile C within the soil. Soil N2O emissions were suppressed in laboratory incubations within several months of biochar addition due to increased soil aeration, BII or increased soil pH that reduced the soil N2O: N2 ratio; effects that varied depending on soil inorganic-N concentration and moisture content. These results are significant as they consistently demonstrate that fresh hardwood biochar has the potential to reduce soil GHG emissions over a period of up to two years in bioenergy crop soil, while simultaneously sequestering C within the soil. They also contribute greatly to understanding of the mechanisms underlying the effect of biochar addition on soil N transformations and N2O emissions within bioenergy and arable soils. This study supports the hypothesis that if scaled up, biochar amendment to soil may contribute to significant reductions in global GHG emissions, contributing to climate change mitigation. Further studies are needed to ensure that these conclusions can be extrapolated over the longer term to other field sites, using other types of biochar.

Nitrous oxide (N2O) is a potent greenhouse gas mainly emitted from agriculture. In the biological process of denitrification, intermediates of the nitrogen cycle are reduced under oxygen limiting conditions thereby releasing N2O. Denitrification is influenced by various environmental factors and both bacteria and fungi are capable of denitrification. The ultimate aim of this thesis was to determine the significance of fungal and bacterial denitrification in arable soil and to investigate influences of soil pH and physical disturbance on potential denitrification rates and denitrifying communities. Long-term pH plots combined with a disturbance gradient have been utilised to investigate fungal and bacterial denitrification distinguished by application of selective inhibitors. Highest N2O production was measured from slightly acidic soil and soil with reduced disturbance. Fungi and bacteria contributed to N2O production with bacterial denitrification as dominant source. Fungal denitrification remained unaffected by soil pH and disturbance whereas bacterial denitrification was influenced by these factors. Bacterial denitrification was positively correlated with concentrations of fatty acids which suggested that these fatty acids were common to bacteria involved in N2O production in the soils investigated here. Bacterial community structure changed with soil pH and disturbance whereas fungal community structure was only influenced by disturbance. Bacterial denitrifier communities (nitrite reductases nirK and nirS) changed over the pH gradient but only the nirK community was affected by disturbance. This indicated that groups of bacterial denitrifiers follow different ecological strategies. Gene abundance of nirK and nirS was also correlated to concentrations of the fatty acids associated with denitrifying bacteria in the soils investigated here. In conclusion, fungal denitrification was significant in arable soil but remained unchanged by soil pH and disturbance. Therefore, fungal denitrification is important in agricultural ecosystems and should be considered when developing mitigation strategies for N2O production especially under conditions favourable for fungal denitrification.

Master of Science / Department of Agronomy / Peter J. Tomlinson / Growing cover crops (CCs) in rotation with cash crops has become popular in recent years for their many agroecosystem benefits, such as influencing nutrient cycling and reducing nutrient losses. This study aimed to (i) determine the long-term effects of no-till with CCs and varying nitrogen (N) rates on subsequent sorghum [Sorghum bicolor (L.) Moench] yield and yield components, (ii) assess how CCs affect the N dynamic in the soil-crop relationship during the growing season and N use efficiency (NUE) of sorghum, and (iii) define and evaluate important periods of nitrous oxide (N₂O) losses throughout the cropping system. Field experiments were conducted during the 2014-15 and 2015-16 growing season in a three-year no-till winter wheat (Triticum aestivum L.) – sorghum – soybean [Glycine max (L.) Merr] rotation. Fallow management consisted of a chemical fallow (CF) control plus four CCs and a double-crop soybean (DSB) grown after wheat harvest. Nitrogen fertilizer was subsurface banded at five rates (0, 45, 90, 135, and 180 kg ha⁻¹) after sorghum planting. On average, DSB and late-maturing soybean (LMS) provided one-third and one-half of the N required for optimum economic grain yield (90 kg N ha⁻¹), respectively; resulting in increased grain yield when compared to the other CCs and CF with 0-N application. Crimson clover (Trifolium incarnatum L.) and daikon radish (Raphanus sativus L.) had no or negative effects on sorghum yield and N uptake relative to CF across all N rates. Sorghum-sudangrass (SS) (Sorghum bicolor var. sudanese) significantly reduced N uptake and grain yield, even at higher N rates. Sorghum following CF had the lowest NUE at optimum grain yield when compared to all CC treatments, suggesting that CCs have a tendency to improve NUE. Cover crops reduced N₂O emissions by 65% during the fallow period when compared to CF; however, DSB and SS increased emissions when N was applied during the sorghum phase, indicating that N fertilization might be the overriding factor. Moreover, about 50% of the total N₂O emissions occurred within 3 weeks after N application, regardless of the cover crop treatment, indicating the importance of implementing N management strategies to reduce N₂O emissions early in the growing season. Overall, these results show that CC selection and N fertilizer management can have significant impacts on sorghum productivity and N₂O emissions in no-till cropping systems.

<p>Wetland ecosystems provide many valuable ecosystem services, including carbon (C) storage and improvement of water quality. Yet, restored and managed wetlands are not frequently evaluated for their capacity to function in order to deliver on these values. Specific restoration or management practices designed to meet one set of criteria may yield unrecognized biogeochemical costs or co-benefits. The goal of this dissertation is to improve scientific understanding of how wetland restoration practices and waterfowl habitat management affect critical wetland biogeochemical processes related to greenhouse gas emissions and nutrient cycling. I met this goal through field and laboratory research experiments in which I tested for relationships between management factors and the biogeochemical responses of wetland soil, water, plants and trace gas emissions. Specifically, I quantified: (1) the effect of organic matter amendments on the carbon balance of a restored wetland; (2) the effectiveness of two static chamber designs in measuring methane (CH4) emissions from wetlands; (3) the impact of waterfowl herbivory on the oxygen-sensitive processes of methane emission and coupled nitrification-denitrification; and (4) nitrogen (N) exports caused by prescribed draw down of a waterfowl impoundment.</p><p>The potency of CH4 emissions from wetlands raises the concern that widespread restoration and/or creation of freshwater wetlands may present a radiative forcing hazard. Yet data on greenhouse gas emissions from restored wetlands are sparse and there has been little investigation into the greenhouse gas effects of amending wetland soils with organic matter, a recent practice used to improve function of mitigation wetlands in the Eastern United States. I measured trace gas emissions across an organic matter gradient at a restored wetland in the coastal plain of Virginia to test the hypothesis that added C substrate would increase the emission of CH4. I found soils heavily loaded with organic matter emitted significantly more carbon dioxide than those that have received little or no organic matter. CH4 emissions from the wetland were low compared to reference wetlands and contrary to my hypothesis, showed no relationship with the loading rate of added organic matter or total soil C. The addition of moderate amounts of organic matter (< 11.2 kg m-2) to the wetland did not greatly increase greenhouse gas emissions, while the addition of high amounts produced additional carbon dioxide, but not CH4. </p><p>I found that the static chambers I used for sampling CH4 in wetlands were highly sensitive to soil disturbance. Temporary compression around chambers during sampling inflated the initial chamber CH4 headspace concentration and/or lead to generation of nonlinear, unreliable flux estimates that had to be discarded. I tested an often-used rubber-gasket sealed static chamber against a water-filled-gutter seal chamber I designed that could be set up and sampled from a distance of 2 m with a remote rod sampling system to reduce soil disturbance. Compared to the conventional design, the remotely-sampled static chambers reduced the chance of detecting inflated initial CH4 concentrations from 66 to 6%, and nearly doubled the proportion of robust linear regressions from 45 to 86%. The new system I developed allows for more accurate and reliable CH4 sampling without costly boardwalk construction. </p><p>I explored the relationship between CH4 emissions and aquatic herbivores, which are recognized for imposing top-down control on the structure of wetland ecosystems. The biogeochemical consequences of herbivore-driven disruption of plant growth, and in turn, mediated oxygen transport into wetland sediments, were not previously known. Two growing seasons of herbivore exclusion experiments in a major waterfowl overwintering wetland in the Southeastern U.S. demonstrate that waterfowl herbivory had a strong impact on the oxygen-sensitive processes of CH4 emission and nitrification. Denudation by herbivorous birds increased cumulative CH4 flux by 233% (a mean of 63 g CH4 m-2 y-1) and inhibited coupled nitrification-denitrification, as indicated by nitrate availability and emissions of nitrous oxide. The recognition that large populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle nitrogen is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that annual emissions of 23 Gg of CH4 y-1 from ~55,000 ha of publicly owned waterfowl impoundments in the Southeastern U.S. could be tripled by overgrazing. </p><p>Hydrologically controlled moist-soil impoundment wetlands provide critical habitat for high densities of migratory bird populations, thus their potential to export nitrogen (N) to downstream waters may contribute to the eutrophication of aquatic ecosystems. To investigate the relative importance of N export from these built and managed habitats, I conducted a field study at an impoundment wetland that drains into hypereutrophic Lake Mattamuskeet. I found that prescribed hydrologic drawdowns of the impoundment exported roughly the same amount of N (14 to 22 kg ha-1) as adjacent fertilized agricultural fields (16 to 31 kg ha-1), and contributed approximately one-fifth of total N load (~45 Mg N y-1) to Lake Mattamuskeet. Ironically, the prescribed drawdown regime, designed to maximize waterfowl production in impoundments, may be exacerbating the degradation of habitat quality in the downstream lake. Few studies of wetland N dynamics have targeted impoundments managed to provide wildlife habitat, but a similar phenomenon may occur in some of the 36,000 ha of similarly-managed moist-soil impoundments on National Wildlife Refuges in the southeastern U.S. I suggest early drawdown as a potential method to mitigate impoundment N pollution and estimate it could reduce N export from our study impoundment by more than 70%.</p><p>In this dissertation research I found direct relationships between wetland restoration and impoundment management practices, and biogeochemical responses of greenhouse gas emission and nutrient cycling. Elevated soil C at a restored wetland increased CO2 losses even ten years after the organic matter was originally added and intensive herbivory impact on emergent aquatic vegetation resulted in a ~230% increase in CH4 emissions and impaired N cycling and removal. These findings have important implications for the basic understanding of the biogeochemical functioning of wetlands and practical importance for wetland restoration and impoundment management in the face of pressure to mitigate the environmental challenges of global warming and aquatic eutrophication.</p> / Dissertation

Nitrous oxide (N2O) is a powerful greenhouse gas and a major contributor to ozone layer depletion. The application of nitrogenous fertilisers to agricultural soils is a major source of N2O on a global scale. Arable soils receive significant rates of synthetic nitrogen (N) and thus have a considerable N2O footprint. The reduction of the N2O footprint of agricultural systems is a key target for those countries that seek to reduce their contribution to climate change and achieve a more sustainable agriculture. These twin targets are part of Scotland's agro-environmental policy. Because soil N2O emissions vary significantly both temporally and spatially, measuring N2O emissions across wide agricultural areas is impractical. However, the quantification of the N2O footprint of important agricultural regions is very valuable to scientists, farmers and policymakers alike. In this context, agro-ecosystem biogeochemistry models are scientific tools, which are developed using in-depth knowledge on the underlying processes, and are used to quantify N2O emissions across spatial and temporal scales. In Scotland, arable agriculture is concentrated at the Eastern part of the country where wheat, barley and oilseed rape are the most widely cultivated crops. The main aim of this study was to quantify the amount of N2O that is emitted from arable soils due to the cultivation of these three crops in Eastern Scotland by using the Landscape-DNDC model. Landscape-DNDC is a mechanistic biogeochemistry model that describes the flows of energy, water and nutrients in agricultural ecosystems. As part of the study, the parametric sensitivities of key model outputs have been quantified using well-established sensitivity analysis methods, which were tailored in order to consider the particularities of N cycling in arable soils. Driven by the fact that the existence of spatiotemporal uncertainties around field-measured soil N2O data complicates the evaluation of model performance, a novel model evaluation algorithm has been developed and was used to assess the model's predictive accuracy. By combining the knowledge of the model's parametric sensitivity with the abilities of the evaluation algorithm, nine key parameters of Landscape-DNDC were calibrated to UK edaphoclimatic conditions (using the Metropolis-Hastings Bayesian calibration algorithm). Model calibration led to improved prediction of field-measured soil N2O emissions at a set of sites. The model was then coupled to geographically explicit data on climate, soil N2O and crop management and used to simulate N2O emissions from the arable soils of Eastern Scotland. The results show that, on average, 0.59 % of the applied fertiliser N (kg N ha-1) was lost to the atmosphere as N2O. This factor is much lower than the generic N2O emission factor (EF) of 1% and closer to the UK cropland-specific N2O EF (i.e. 0.79%). The predicted annual N2O was the combined result of different drivers (i.e. fertiliser rate, soil and climate variables) but the geographic distribution of the estimated N2O EFs revealed some hotspots of high N2O EF (larger than 1%). Interestingly, these hotspots were caused by the cultivation of winter oilseed rape on soils with high bulk density and clay content. The comparison of the simulated yields per hectare with respective measured data and of the simulated nitrate (NO-3 ) leaching and crop N uptake factors with respective literature-based values showed that the prediction of soil N2O was not made at the expense of realistic prediction of other important aspects of agro-ecosystem biogeochemistry. Also, the study found that the simulated N2O is almost twice as sensitive to soil input uncertainty as the simulated NO-3 is, while, crop N uptake is rather insensitive to this source of uncertainty. Finally, the study shows that the uncertainty around the nine calibrated model parameters affects the prediction of NO-3 leaching strongly but its role in regards to the simulation of N2O emissions is small.

No description available.

Nitrous oxide (N2O) oxidizes vitamin B12. disrupting deoxyribonucleic acid (DNA) synthesis. Occupational exposures to subanesthetic levels of the gas have been documented that may result in suppressed proliferative cell activities. Male CD-I mice were exposed to 0, 50, 500, and 5000 parts of N2O per million parts of air (ppm) for 6 hr/day, 5 days/week for 2 and 13 weeks. Splenic lymphocytes were assayed for responsiveness to mitogens and for the ability to produce interleukin-2 (lL-2) . Tritiated-thymidine ([3H]-TdR) uptake was measured in CD-I splenic lymphocytes cultured in a mixed-lymphocyte culture (MLC). Cytolytic cell activity was measured by 51chromium release assay. Antibody-mediated immunocompetency was determined for sheep red blood cell (SRBC)-sensitized animals by plaque-forming cell (PFC) assay and sera anti-SRBC antibody titer. Deoxyuridine suppression tests (dUdRST) were performed on bone marrow cells. Serum adrenocorticotropic hormone and corticosterone levels were determined. There was significantly decreased splenic lymphocyte uptake of [3H)-TdR by cells cultured with mitogenic substances and in MLC following 2-week animal exposures to 5000 ppm. After 13-week exposures, the animals' splenic lymphocytes showed decreased [3H]-TdR uptake following low N20 dosing and nonsignificantly increased responsiveness at the higher gas exposures in both the blastogenic and MLC assays. Compared to control animals, the 5000- ppm-exposure group had significantly depressed PFC activity and circulating anti-SRBC immunoglobulin M levels following 13-week gas exposures, and all three subchronic exposure groups demonstrated both decreased liver weights and leukopenia. Bone marrow activity at these dosing levels was dose-responsively depressed following subchronic gas exposures.No hormonal effect appears to be attributable to N20 exposure.

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.