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Data for Impacts of Legacy and Contemporary Nitrogen Inputs on N2O and CO2 Emissions in Miscanthus and Maize Cultivated Soils

Nutrient inputs influence the sustainability of bioenergy crop production through contemporary (shortly after addition) and legacy effects (persisting over years) on microbial nitrogen (N) and carbon cycling, which contribute to greenhouse gas emissions. However, the relative importance of contemporary and legacy effects and how that could vary by crop functional types is poorly understood. Considering its rhizomatous roots and perennial growth, we hypothesized that Miscanthus × giganteu s ( M × g ) would be more sensitive to legacy N fertilization and the historical context of its environment than an annual crop like maize. To test this hypothesis, we examined the effects of legacy and contemporary N inputs on nitrous oxide (N2O) and carbon dioxide (CO2) emissions, as well as key N cycling genes in soils where M × g and maize were grown. A 150-day soil incubation experiment was conducted using soils from a long-term M × g and maize fertility experiment with three historic N fertilization rates (0, 112, and 336 kg N ha−1 year−1) and a contemporary amendment (60 mg N kg−1) with negative control (0 mg N kg−1). We observed significant increases in cumulative N2O emissions in M × g soils relative to maize soils, particularly at higher legacy fertilization rates, while contemporary N had no significant effect. Bacterial amoA gene abundance, which plays a significant role in nitrification in nutrient-rich soils, also increased with higher legacy fertilization rates in M × g soils but was unaffected by the contemporary N. In maize soils, legacy and contemporary N did not significantly affect N2O emissions, but cumulative CO2 emissions and amoA gene abundance significantly increased. The abundances of norB genes were not significantly influenced by either legacy fertilization or contemporary N amendments in either soil. Our findings demonstrate the greater importance of fertilization history over contemporary N in mediating soil N2O emissions, particularly for perennial bioenergy crops.

Carbon

Biologically produced volatile compounds: N2O emissions from the soil and the N2O global budget

N2O dynamics were studied at the soil-atmosphere interface and their effects on the global N2O budget. Troposphere nitrous oxide (N2O) concentration has increased by 0.2 to 0.4 pct. per year over the period 1975 to 1982, amounting to a net addition to the atmosphere of 2.8 to 5.6 Tg N2O-N per year. This perturbation, if continued into the future, will affect stratospheric chemical cycles, and the thermal balance of the Earth. In turn it will have direct and indirect global effects on the biosphere. The only well documented heat sinks identified to date are the stratospheric photolytic decomposition processes. However, quantitatively, they do not account for all the known sources. Emission from soils is the least understood and most variable component in the N2O budget. An automated field station that will measure N2O fluxes and interchanges over long periods of time is being developed. At each station, the source/sink relations of N2O at the soil-atmosphere interface will be measured and their relations to environmental conditions are documented and quantified. The results from the perennial measurements will generate the data base on which global budgets for N2O will be constructed and related to ecosystem parameters.

Banin, A.

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Abel, Robert W.

N2O fluxes at the soil-atmosphere interface in various ecosystems and the global N2O budget

The overall purpose of this research task is to study the effects of soil properties and ecosystem variables on N2O exchanges at the soil-atmosphere interface, and to assess their effects on the globle N2O budget. Experimental procedures are implemented in various sites to measure the source/sink relations of N2O at the soil-atmosphere interface over prolonged periods of time as part of the research of biogeochemical cycling in terrestrial ecosystems. A data-base for establishing quantitative correlations between N2O fluxes and soil and environmental parameters that are of potential use for remote sensing, is being developed.

Banin, Amos

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.

Estupinan, E. G.

Generating Breathable Air Through Dissociation of N2O

A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS includes one or more "destroyer" subsystems for removing any nitrogen oxides that remain downstream of the main N2O-dissociation reactor. A destroyer includes a carbon bed in series with a catalytic reactor, and is in thermal contact with the main N2O-dissociation reactor. The gas mixture that leaves the main reactor first goes through a carbon bed, which adsorbs all of the trace NO and most of the trace NO2. The gas mixture then goes through the destroyer catalytic reactor, wherein most or all of the remaining NO2 is dissociated. A NOBOSS can be designed to regulate its reactor temperature across a range of flow rates. One such system includes three destroyer loops; these loops act, in combination with a heat sink, to remove heat from the main N2O-dissociation reactor. In this system, the N2O and product gases play an additional role as coolants; thus, as needed, the coolant flow increases in proportion to the rate of generation of heat, helping to keep the main-reactor temperature below 540 C.

Zubrin, Robert

Surface Nitrification: A Major Uncertainty in Marine N2O Emissions

The ocean is responsible for up to a third of total global nitrous oxide (N2O) emissions, but uncertainties in emission rates of this potent greenhouse gas are high (approaching 100%). Here we use a marine biogeochemical model to assess six major uncertainties in estimates of N2O production, thereby providing guidance in how future studies may most effectively reduce uncertainties in current and future marine N2O emissions. Potential surface N2O production from nitrification causes the largest uncertainty in N2O emissions (estimated up to approximately 1.6 Tg N/yr (sup -1) or 48% of modeled values), followed by the unknown oxygen concentration at which N2O production switches to N2O consumption (0.8 Tg N/yr (sup -1)or 24% of modeled values). Other uncertainties are minor, cumulatively changing regional emissions by less than 15%. If production of N2O by surface nitrification could be ruled out in future studies, uncertainties in marine N2O emissions would be halved.

N2O

Excited ozone is a possible source of atmospheric N2O

Consideration is given to the possibility that internally excited ozone formed in the three-body recombination reaction between oxygen atoms and molecules may be a potential source of atmospheric N2O through a gas-phase reaction with nitrogen molecules. Determinations of the wavelength dependence of the quantum yield for N2O formation from the photolysis of dilute solutions of O3 in liquid N2 and of the O(1D) quantum yield in the gas-phase photolysis of O3 are interpreted as suggesting the possibility of the excited ozone reaction, and a new expression for N2O quantum yield is derived. An expression for the production rate of N2O through the proposed reaction is then obtained and used to calculate atmospheric concentrations and fluxes of N2O. The theoretical profile obtained is found to agree better with experimental data than that obtained without the excited ozone reaction taken into account and to demonstrate a wide variability in N2O mixing ratios. In addition, the existence of the new N2O source is noted to imply a significantly smaller flux of N2O from surface microbiological activities, and provide a possible physical basis for latitudinal and temporal N2O variations and an additional stability for the ozone layer.

Prasad, S. S.

3-D Atmospheric Modeling of the Global Budget of N2O and its Isotopologues for 1980-2019: The Impact of Anthropogenic Emissions

Nitrous oxide (N2O) is the third most important anthropogenic greenhouse gas (GHG) and a major ozone-depleting substance (ODS). Its main sources include anthropogenic activities (mostly agriculture) and natural emissions from ocean and soils. However, emission estimates for individual sources are highly variable due to uncertainties in N2O lifetime estimates and partitioning among sources. We derive annual global N2O emissions for 1990-2019 using NOAA Global Monitoring Laboratory (GML) surface N2O observations and the N2O lifetime calculated in the NASA GEOS-5 chemistry climate model (CCM). The inferred global mean N2O emissions has gradually increased from ~15.8 TgN/yr in the early 1990s to ~17.8 TgN/yr in the 2010s. This implies that anthropogenic N2O emissions have grown rapidly from ~6.7 TgN/yr in the 1990s to about ~8.7 TgN/yr in the 2010s, a ~30% increase. With specially designed N2O isotopic tracers in 3-D GEOSCCM, we estimate that, on global average, stratospheric enrichment contributes about +7.7‰/yr, +7.6‰/yr, +8.0‰/yr to tropospheric N(sup α)-δ(sup 15), N(sup β)-δ(sup 15), and O-δ(sup 18) budget, respectively. To balance the global mean isotopic signature for pre-industrial terrestrial sources of N(sup α)-δ(sup 15) ~ 6.7‰, N(sup β)-δ(sup 15) ~ -12.6‰, O-δ(sup 18) ~ 35.4‰, our 3-D isotopic budget simulation using the GEOSCCM suggests global mean anthropogenic isotopic signatures in the recent decades are N(sup α)-δ(sup 15) ~ -18‰, N(sup β)-δ(sup 15) ~ -20‰, O-δ(sup 18) ~ 19‰. These anthropogenic isotopic estimates are significantly lighter than results from one-box atmospheric model-based estimates with the largest difference seen for N(sup β)-δ(sup 15). More surface isotopic measurements are needed to better quantify the N2O isotopic signatures.

Nitrous oxide

Comparison of N2O Emissions from Soils at Three Temperate Agricultural Sites

Nitrous oxide (N2O) flux simulations by four models were compared with year-round field measurements from five temperate agricultural sites in three countries. The field sites included an unfertilized, semi-arid rangeland with low N2O fluxes in eastern Colorado, USA; two fertilizer treatments (urea and nitrate) on a fertilized grass ley cut for silage in Scotland; and two fertilized, cultivated crop fields in Germany where N2O loss during the winter was quite high. The models used were daily trace gas versions of the CENTURY model, DNDC, ExpertN, and the NASA-Ames version of the CASA model. These models included similar components (soil physics, decomposition, plant growth, and nitrogen transformations), but in some cases used very different algorithms for these processes. All models generated similar results for the general cycling of nitrogen through the agro-ecosystems, but simulated nitrogen trace gas fluxes were quite different. In most cases the simulated N20 fluxes were within a factor of about 2 of the observed annual fluxes, but even when models produced similar N2O fluxes they often produced very different estimates of gaseous N loss as nitric oxide (NO), dinitrogen (N2), and ammonia (NH3). Accurate simulation of soil moisture appears to be a key requirement for reliable simulation of N2O emissions. All models simulated the general pattern of low background fluxes with high fluxes following fertilization at the Scottish sites, but they could not (or were not designed to) accurately capture the observed effects of different fertilizer types on N2O flux. None of the models were able to reliably generate large pulses of N2O during brief winter thaws that were observed at the two German sites. All models except DNDC simulated very low N2O fluxes for the dry site in Colorado. The US Trace Gas Network (TRAGNET) has provided a mechanism for this model and site intercomparison. Additional intercomparisons are needed with these and other models and additional data sets; these should include both tropical agro-ecosystems and new agricultural management techniques designed for sustainability.

Frolking, S. E.

Production of NO2/-/ and N2O by nitrifying bacteria at reduced concentrations of oxygen

The influence of oxygen concentration on the production of NO2(-) and N2O by nitrifying marine bacteria of the genus Nitrosomonas is investigated. Pure cultures of the ammonium-oxiding bacteria isolated from the Western Tropical Atlantic Ocean were grown at oxygen partial pressures from 0.005 to 0.2 atm, and concentrations of N2O in the air above the growth medium and dissolved NO2(-) were determined. Decreasing oxygen concentrations are observed to induce a marked decrease in NO2(-) production rates and increase in N2O evolution, leading to an increase of the relative yield of N2O with respect to NO2(-) from 0.3% to nearly 10%. Similar yields of N2O at atmospheric oxygen levels are found for nitrifying bacteria of the genera Nitrosomonas, Nitrosolobus, Nitrosospira and Nitrosococcus, while nitrite-oxydizing bacteria and a dinoflagellate did not produce detectable quantities of N2O. Results support the view that nitrification is a major source of N2O in the environment.

Goreau, T. J.

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Slanger, Tom G.

More About N2O-Based Propulsion and Breathable-Gas Systems

A concept was evaluated of using nitrous oxide as (1) a monopropellant in thrusters for space suits and spacecraft and (2) a source of breathable gas inside space suits and spacecraft, both by exploiting the controlled decomposition of N2O into N2 and O2. Relative to one prior monopropellant hydrazine, N2O is much less toxic, yet offers comparable performance. N2O can be stored safely as a liquid at room temperature and unlike another prior monopropellant hydrogen peroxide does not decompose spontaneously. A prototype N2O-based thruster has been demonstrated. It has also been proposed to harness N2O-based thrusters for generating electric power and to use the N2 + O2 decomposition product as a breathable gas. Because of the high performance, safety, and ease of handling of N2O, it can be expected to be economically attractive to equip future spacecraft and space suits with N2O-based thrusters and breathable-gas systems.

Zubrin, Robert

Effects of N2O narcosis on the contraction and repayment of an oxygen debt

The oxygen deficit, oxygen debt, and the difference between them were measured in five male and three female subjects during and after exercise while breathing either air or a normoxic mixture containing 33% N2O and nitrogen. With the exception of a higher respiratory quotient at rest in N2O, there were no statistically significant differences for oxygen consumption, carbon dioxide production, expired gas volume, heart rate or blood lactate while breathing N2O during rest, exercise, or recovery. An appreciably, but not statistically, greater mean oxygen deficit was found in N2O along with a significantly greater mean oxygen debt; deficit-debt difference was unaffected by N2O. It was speculated that N2O narcosis did not affect the ability to utilize oxygen but that the response to the greater oxygen need of exercise may have been slowed with perhaps a concomitant greater depletion of stored high energy compounds.

Schatte, C. L.

Nitrous oxide in fresh water systems: An estimate for the yield of atmospheric N2O associated with disposal of human waste

The N2O content of waters in the Potomac and Merrimack Rivers was measured on a number of occasions over the period April to July 1977. The concentrations of dissolved N2O exceeded those which would apply in equilibrium with air by factors ranging from about 46 in the Potomac to 1.2 in the Merrimack. Highest concentrations of dissolved N2O were associated with sewage discharges from the vicinity of Washington, D. C., and analysis indicates a relatively high yield, 1.3 to 11%, for prompt conversion of waste nitrogen to N2O. Measurements of dissolved N2O in fresh water ponds near Boston demonstrated that aquatic systems provide both strong sources and sinks for atmospheric N2O.

Kaplan, W. A.

Correlation of N2O and ozone in the southern polar vortex during the Airborne Antarctic Ozone Experiment

The correlation of N2O and ozone in the Antarctic stratosphere during the late austral winter was investigated using measurements of N2O mixing ratios obtained by an airborne laser spectrometer and in situ measurements of ozone for latitudes between 53 and 72 deg S. In addition, airborne N2O and O3 measurements taken between 13 and 20 km in the mid-latitudes (37 deg N and 53 deg S) were correlated. It was found that, while the mid-latitude ozone-N2O corelation was negative, poleward of 53 deg S, the N2O and O3 mixing ratios often showed a strong positive correlation, which approximately coincided with the edge of the polar vortex as defined by the wind-speed maximum. Inside the vortex, in lower wind speed regions, the N2O-O3 correlation became negative again, with the lowest ozone mixing ratios usually found near the boundary with the positively correlated region.

Strahan, S. E.

Use of satellite data to constrain the model-calculated atmospheric lifetime for N2O - Implications for other trace gases

Model calculations of the zonal-mean concentrations of N2O in the upper stratosphere are presented showing that about 80 percent of N2O is removed in the stratosphere between 30 deg N and 30 deg S. A comparison of calculated N2O values with remote data on N2O concentrations obtained from Nimbus 7 SAMS instrument indicated that the two-dimensional model of Ko and Sze (1982) may have underestimated the concentration of N2O in the tropical lower stratosphere. It is concluded that the calculated lifetimes for N2O and chlorofluorocarbon-source gases could be 30 percent shorter than previously reported values.

Ko, Malcolm K. W.

Simulation of stratospheric N2O in the NCAR CCM2: Comparison with CLAES data and global budget analyses

Global variability and budgets of stratospheric nitrous oxide (N2O) are studied using output from a stratospheric version of the National Center for Atmospheric Research Climate Model (CCM2). The model extends over 0-80 km, incorporating an N2O-like tracer with tropospheric source and upper-stratospheric photochemical sink, the latter parameterized using linear damping rates obtained from detailed two-dimensional model calculations. Results from the model over several seasonal cycles are compared with observations of N2O from the Cryogenic Limb Array Etalon Spectrometer (CLAES) instrument on the Upper Atmosphere Research Satellite (UARS). The model produces N2O structure and variability that is in reasonable agreement with the observations. Global budgets of stratospheric N2O are furthermore analyzed using model output, based on the transformed Eulerian-mean, zonal-mean framework. These budgets are used to quantify the importance of planetary wave constituent transport in the stratosphere, for both slow seasonal variations and fast planetary wave events. These results demonstrate that such wave fluxes act to form and sharpen the strong subtropical N2O gradients observed in satellite measurements.

Randel, William J.