<p>Whether through sea level rise, farmland abandonment, or wetland restoration, agricultural soils in coastal areas will be inundated at increasing rates, renewing connections to sensitive surface waters and raising critical questions related to environmental tradeoffs. Wetland restoration in particular is often implemented not only to promote wildlife habitat, but also to improve water quality through nutrient removal, especially in agricultural catchments. The microbial process of denitrification is the central mechanism of nitrogen removal in wetlands and flooded soils, and can be seen as a potential environmental benefit of flooding agricultural lands. While denitrification undoubtedly can remove nitrogen from soil and surface water, higher soil moisture or flooding in wetland soils can also increase the production of greenhouse gases, specifically nitrous oxide and methane, representing a potential environmental tradeoff. Understanding the likely benefits of denitrification and the likely greenhouse gas costs of wetland restoration could help inform environmental policies concerning wetland restoration. </p> <p>Determining whether restored wetlands are larger sources of greenhouse gases compared to contrasting land use types (agriculture and forested wetlands) was the first goal of this dissertation (Chapter 2). We measured gas fluxes from soil and water to the atmosphere, and related environmental variables, in four sites over two years to estimate fluxes of the three major greenhouse gases. We found that carbon dioxide was the major contributor to the radiative balance across all sites, but that in the agricultural site and one of the forested wetland reference sites, nitrous oxide was the second most important contributor. Many studies have shown that methane is more important that nitrous oxide in most freshwater wetlands, as we found in the other forested wetland reference site and in flooded parts of the restored wetland. Overall, we did not find higher greenhouse gas fluxes in the restored wetland compared to agricultural soils or forested wetlands.</p> <p>The controls over nitrous oxide are especially complex, because it can be produced by two complementary processes, nitrification and denitrification, which generally occur under different conditions in the environment. In Chapter 3, we determined the soil and environmental factors that best predicted nitrous oxide fluxes for a subset of our data encompassing gas fluxes measured in November 2007. We found that soil temperature and soil carbon dioxide flux, along with ammonium availability and denitrification potential, were good predictors of nitrous oxide (adj R<super>2</super>=0.81). Although the nitrous oxide model did not perform as well when applied to data from another sampling period, we expect to further develop our modeling efforts to include possible non-linear temperature effects and a larger range of environmental conditions. </p> <p>In Chapter 4, we present results of a stable isotope tracer experiment to determine the relative contribution of nitrification and denitrification to nitrous oxide fluxes in these different land use types, and to determine the response of these processes to changing soil moisture. We added two forms of nitrogen-15 to intact soil cores to distinguish nitrification from denitrification, and subjected the cores to drainage or to a simulated rain event. We found that across the range of soil moisture, the fraction of nitrous oxide produced by denitrification did not change, but within each soil type there was a response to the simulated rain. In mineral soils, the nitrous oxide fraction increased with increasing soil moisture, with the highest mole fraction [N₂O/(N₂+N₂O)] in the agricultural soils, while in the organic soils there was no change or even a decrease. The fraction of nitrous oxide derived from coupled nitrification-denitrification increased with increasing soil moisture, and was much higher than that from denitrification alone in the more organic soils. This suggests that, in these saturated acid-organic soils, nitrification plays an important and underappreciated role in contributing to nitrous oxide fluxes from freshwater wetlands. The results from the laboratory experiment were consistent with patterns we saw in the field and help explain the differential contribution of nitrification and denitrification to nitrous oxide fluxes in different land use types in coastal plain wetlands of North Carolina. </p> <p>Overall, we found that both nitrification and denitrification contribute to nitrous oxide fluxes in coastal plain wetlands in North Carolina, and that nitrification is an especially important source in acid-organic soils under both field-moist and saturated conditions. Although freshwater wetlands, with an average nitrous oxide mole fraction of 0.08, are generally seen as being insignificant sources of nitrous oxide, our study sites ranged from 0.10 to 0.30, placing them closer to agricultural fields (0.38; Schlesinger 2009). Although the ecosystems in our study produced more nitrous oxide than expected for freshwater wetlands, we found no significant tradeoff between the local water quality benefits conferred by denitrification and the global greenhouse gas costs in the restored wetland. These results suggest that, from a nitrogen perspective, wetland restoration in coastal agricultural lands has a net environmental benefit.</p> / Dissertation

Nitrous oxide decomposition on Ag51, Au51, Pt22, Rh51 and Ir51 clusters representing (111) surface were studied quantum mechanically by using the method of ONIOM with high layer DFT region and low layer of molecular mechanics region utilizing universal force field (UFF). The basis set employed in the DFT calculations is the Los Alamos LANL2DZ effective core pseudo-potentials (ECP) for silver, gold, platinum, rhodium and iridium and 3-21G** for nitrogen, oxygen and hydrogen. Nitrous oxide was decomposed on the all metal surfaces investigated in this study by leaving oxygen atom adsorbed as supported by experimental findings. Activation energies of nitrous oxide decomposition on Ag51, Au51, Pt22, Rh51 and Ir51 representing (111) surface are calculated as 14.48 kcal/mol, 15.72 kcal/mol, 7.02 kcal/mol, 3.76 kcal/mol and 5.51 kcal/mol, respectively. Based on these results, decomposition of nitrous oxide occurs on Rh more easily than other metals.

El Ni&#x00F1;o is now a focal point for global climate change research, but its influence on the Western Pacific is still uncertain. Taiwan Strait is an important pathway, which connects the South China Sea and the East China Sea, and is strongly influenced by the monsoon. Generally, in winter, the strong winter monsoon brings the cold and nutrient-rich Changjiang Diluted Water¡]CDW¡^southward. While during the El Ni&#x00F1;o event, because of the weakened south wind in northern Taiwan, more cold CDW moves southward, and hence the decreased seawater temperature in spring and fall. The trend is opposite in summer. There is a high salinity signal in the seas outside of Hsin-Chu, suggesting sea water coming from the Kuroshio, which has circumvented the northeast tip of Taiwan. Meanwhile, there is a front which separates this Kuroshio water and CDW. During the El Ni&#x00F1;o, the front moves eastward, especially in summer. The salinity east of the front decreases gradually from spring to winter water, the center of upwelling located at the eastern side of the front in spring, and at or near the front from summer to winter. Furthermore, The N/P ratio of the northern Taiwan Strait water became higher after the Three Gorges Dam (TGD) became operational. The nitrous oxide (N2O) is a long-lived greenhouse gas. Unfortunately, in Taiwan, there are few data about N2O emission from rivers, lakes and coastal areas. This research also studies the N2O distribution in natural waters around Taiwan. The average surface water concentration and sea to air flux in the Taiwan Strait¡]7.81¡Ó1.28nM¡F0.28¡Ó0.38£gmol/m2/hr¡^is higher than in the South China Sea¡]SCS¡F7.55¡Ó2.45 nM¡F0.21¡Ó0.27£gmol/m2/hr¡^and the West Philippine Sea¡]WPS¡F5.3¡Ó0.62nM¡F-0.20¡Ó0.25£gmol/m2/hr¡^, which displays a rare sink signal in the world oceans. There is an N2O maximum observed around 1000m in the WPS, and another shollower one around 700m in the SCS, presumably because of the intenive upwelling and vertical mixing in the SCS basin. There are some rather high N2O concentrations (N2O>30nM) in the SCS, observed near the continental slope. We assume that these are released from sediments on the continental slope. Although the sea-to-air flux of N2O is much lower than the flux of CO2, N2O emission in the SCS contributes more than two times the greenhouse effect than CO2 does. Besides, The N2O concentration during El Ni&#x00F1;o is lower than usual, probably due to a smaller amount of the CDW. Finally, the average N2O concentrations of river and submarine groundwater discharge in Taiwan are about 32.3¡Ó43.3nM and 9.72¡Ó13.2 nM, respectively.

Plants (macrophytes) growing in lake and wetland sediments are known mediators of greenhouse gases (GHG), specifically methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O). Current studies have emphasized the potential risk of underestimation regarding emissions of plant-mediated GHGs from terrestrial systems including lakes, streams and other freshwater bodies. In order to differentiate the possible sources and sinks of atmospheric carbon and nitrogen in aquatic environments, this study aims to investigate the spatial variability of GHG fluxes in stands of common wetland macrophytes. Field samplings were carried out in the summer of 2012 where 24-hour diel measurements were conducted with the static chamber method in a boreal lake in south western Sweden. Two macrophyte communities were studied; one mixed-species stand and one species-specific stand of water horsetail (Equisetum fluviatile). Spatial variability was confirmed at several stages, both between and within stands. The species-specific stand emitted more CH4 than the mixed stand, from 0.17 to 8.99 mmol m-2 h-1, compared to 0.63 – 1.95 mmol m-2 h-1 maximum measured. Within stand variability was confirmed as variable CH4 flux per strand of E. fluviatile was established. No significant differences were observed regarding CO2 and N2O, other than weak correlation in diel patterns, e.g. daytime uptake and night time respiration/emission for both gases.

Reclamation success is highly dependent upon final soil quality of stockpiled soils, such as those found Cold Lake Oil Sands Region. Stockpiled soils, however, are generally poor in quality. Soils were amended with, biochar (BC), humalite (HU), a sub-bituminous coal; and peat (PT), as well as 50:50 blends of biochar:humalite (BCH) and biochar:peat (BCP). These amendments were applied at rates of 0, 6.55, 13.1 and 26.2 g C kg-1 each. Biochar, PT, and BCP applied at the rate of 26.2 g C kg-1 were found to reduce N2O emissions by 34, 54, and 70%, respectively, relative to the control. Within the bioassay, BC and PT amendment resulted in a 38 and 40% increase in dry matter yield (DMY) respectively. Finally, amendment typically resulted in significant net decreases in Olsen P values, while nitrate and ammonium concentrations were high in PT amended soils. In general, PT had the best overall performance. / October 2015

It has been estimated that over 200,000 healthcare professionals may be exposed to waste anesthetic gases and are at risk of occupational injury. In 1977, the National Institute for Occupational Safety and Health (NIOSH) issued the publication: Criteria for a Recommended Standard....Occupational Exposure to Waste Anesthetic Gases and Vapors. This publication was based primarily on scientific evidence from human and animal studies suggesting that chronic exposures to anesthetic gases increases the risk of both spontaneous abortion and congenital abnormalities in offspring among female workers and wives of male workers exposed to waste anesthetic gases. In this recommended standard, NIOSH defines the recommended exposure limits (REL) for nitrous oxide and halogenated anesthetics. NIOSH recommended a time-weighted average (TWA) REL of 25 parts per million (ppm) for nitrous oxide over the period of administration. The REL for halogenated anesthetic gases is a ceiling limit of two ppm.In this study, waste anesthetic gas exposures to seven Post Anesthesia Care Unit (PACU) nurses were quantified during one day of air sampling within their breathing zones. Nitrous Oxide was sampled using a ChemExpressTM Personal Monitor (Assay Technology, Inc. Pleasanton, CA) attached to the nurse's lapel for approximately three hours. A total of 15 samples were collected. Isoflurane, desflurane, and sevoflurane were sampled using a ChemExpressTM Personal Monitor (Assay Technology, Inc. Pleasanton, CA) attached to the nurse's lapel for approximately three hours. A total of 15 samples were collected. In addition, Isoflurane, desflurane, and sevoflurane were also sampled using Anasorb© 747 sorbent tubes (SKC, Inc. Eighty Four, PA) to compare the passive and active sampling methods. The tubes were attached to the nurses lapel for one hour. A total of 15 samples were collected. The exposures to nitrous oxide and halogenated anesthetics were below the NIOSH RELs. An Analysis of Variance (ANOVA) showed a statistically significant difference (p < 0.05) in the active and passive sampling methodologies.

Globally, an estimated 25% of the CO2 and 90% of the N2O is believed to come from agroecosystems. The objective of this study was to investigate the dynamics of the below-ground CO 2 and N2O concentrations and efflux in corn and soybean systems. In our field study, changes in the below-ground concentrations of CO 2 and N2O were closely related to seasonal changes in soil moisture, with the first two months of the growing season being particularly critical to the production of these gases. Tillage significantly increased CO2 content in the soil profile, however, this effect was greater in the soybean plots than in the corn plots. In our greenhouse studies, an average of about 79% of the soil respiration in corn came from rhizosphere respiration, compared to an estimated 58% in the case of soybean. Specific rhizosphere respiration was significantly higher in soybean (0.29 mg C g -1 root h-1) than corn (0.09 mg C g-1 root h-1), which supports previous observations made with regards to slower-growing plants (e.g. soybean) having relatively higher root respiration than faster growing plants. We observed a nonsignificant difference between N2O efflux in the soybean-planted soil and unplanted bulk soil, which is in contrast to the perception that legumes could stimulate more N 2O production from the soil by increasing the N pool through N 2 fixation. While corn had the greatest uptake of fertilizer N, N 2O efflux in corn pots was higher (2.84 mug N pot-1 h-1) than the soybean pots (0.06 mug N pot-1 h-1). In the laboratory setting, denitrification in the microaggregates proceeded at about 4.4 to 39.6 times higher rate than in large macroaggregates, small macroaggregates or the bulk soil, and showed the greatest response to high moisture levels (80% WFPS).

A study was conducted in 2004 and 2005 to determine the effect of liquid hog manure fertilization on greenhouse gas emissions from the surface of a grassland pasture in south-eastern Manitoba. The objectives of this research were to determine the effects of manure application, itstiming and soil moisture on greenhouse gas emissions from pasture soil, cattle dung and urine patches. Nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) emissions were determined from grassland soil surface, and from cattle dung and artificial urine patches. Liquid hog manure treatments were no manure (Control); 153 kg ha-1 of available-nitrogen (N) (two year average) in spring (Spring); and 149 kg ha-1 as half-rate applications in fall and spring (Split). Four field experiments were conducted on grassland plots. The static-vented chamber technique was used to estimate gas emission rates. Two of the experiments focused on the effects of manure application timing and soil moisture on greenhouse gas emissions from the grassland soil surface. The other two experiments focused on the effects of manure application and soil moisture on greenhouse gas emissions from cattle dung and artificial urine patches. Fresh cattle dung was collected from steers grazing adjacent pastures receiving the same three manure treatments. Artificial cattle urine treatments were generated by converting blood urea concentrations of the steers into urine-N concentrations. Manure application increased (P≤0.01) cumulative N2O emissions from the grassland soil surface with Control, Split and Spring treatments averaging 7, 43 and 120 mg N2O-N m-2, respectively. Of the two manure treatments, the Spring treatment emitted higher (P≤0.10) N2O emissions than the Split treatment. Soil moisture was a major factor influencing the quantity and type of greenhouse gas emissions, with saturated areas emitting CH4 during warm periods, whereas drier areas emitted N2O. Nitrous oxide emissions from these dry areas were higher in manure-treated plots. Spring application increased root density by 45% in the top 5 cm of soil compared to the Control. An increase in soil organic carbon with root density may offset any increase in greenhouse gas emissions caused by manure treatment. Cattle dung from Split and Spring treatments had higher cumulative N2O emissions (30 and 82 mg N2O-N m-2, respectively) compared to dung from Control pastures (6 mg N2O-N m-2) over two study years. Dung from the Spring treatment emitted more N2O (P≤0.01) than the other two treatments. All cattle dung patches emitted CH4 after deposition though unaffected by manure treatment. Artificial urine having highest N concentration had greater (P≤0.05) cumulative N2O emissions (690 mg N2O-N m-2) than urine with the lowest N concentration (170 mg N2O-N m-2). Drier soil locations emitted more N2O from cattle dung and artificial urine patches than wetter areas. This study demonstrated that Split application of liquid hog manure to grassland emitted less N2O than a complete application in spring. Moisture greatly affected the location of N2O and CH4 emissions. Drier areas emitted more N2O than wetter ones. Particularly, the findings indicate a need to assess grassland on periodically saturated soils as sources rather than sinks for CH4. Application of manure increased greenhouse gas emissions from cattle dung and urine patches with urine potentially having the greatest impact because of their higher emissions of N2O. An increase in root growth seems to offset greenhouse gas emissions from manure application.

Agriculture contributes significantly to national and global greenhouse gas (GHG) inventories but there is considerable control over management decisions and changes in production methods could lead to a significant reduction and possible mitigation of emissions from the sector. For example, conservation tillage practices have been suggested as a method of sequestering atmospheric carbon dioxide (CO2), however, many questions remain unanswered regarding the short-term efficacy of the production method and knowledge gaps exist regarding possible interactions with essential nutrient cycles, and the production of non-CO2 GHGs, such as nitrous oxide (N2O). Between autumn 2005 and 2009, a micrometeorological flux system was used to determine net CO2 and N2O exchange from an annual cropping system situated on clay soil in the Red River Valley of southern Manitoba. Four plots (4-ha each) were independently evaluated and planted to corn in 2006 and faba bean in 2007; in 2008, two spring wheat plots were monitored. As well, during the non-growing season in 2006-2007 following corn harvest, a second micrometeorological flux system capable of simultaneously measuring stable C isotopologue (12CO2 and 13CO2) fluxes was operated at the site. Tillage intensity and crop management practices were examined for their influence on GHG emissions. Significant inter-annual variability in CO2 and N2O fluxes as a function of crop and related management activities was observed. Tillage intensity did not affect GHG emissions from the site. After accounting for harvest removals, the net ecosystem C budgets were 510 (source), 3140 (source) and -480 (sink) kg C/ha/year for the three respective crop years, summing to a three-year loss of 3170 kg C/ha. Stable C isotope flux measurements during the non-growing season following corn harvest indicated that approximately 70 % and 20 – 30 % of the total respiration flux originated from crop residue C during the fall of 2006 and spring of 2007, respectively. The N2O emissions at the site further exacerbated the net global warming potential of this annual agroecosystem.

A study was conducted to examine the impact of diet and cold weather on the excretion of nitrogen (N) and phosphorus (P) from beef cows, and the potential for these nutrients to be lost to waterways or as greenhouse gases (GHG). Feces and urine were collected from mature cows fed low-quality forage supplemented with DDGS to 0%, 10%, and 20% ww-1 in the fall of 2008 and winter of 2009. A detailed nutrient analysis was performed to determine forms of N and fractions of P in excreta. Feces, urine, and a simulated bedding pack were then applied to grassland to determine soil GHG emission. Cattle receiving DDGS supplementation excreted greater proportions of labile P in feces and greater concentrations of P in urine. The 20% DDGS diets had greater nitrous oxide emission from urine patches and greater proportions of available N in urine and feces.