N2O emission from cropland in China

Based on the regionalization of uplands and paddy fields in China, the crop intensity in each region and the available field measurements, N₂O emission from cropland in China in 1995 was estimated to be 398 Gg N, in which, 310 Gg N was from uplands, accounting for 78% of the total. 88 Gg N–N₂O was emitted from paddy fields with 35 Gg N emitted during the rice growing season and 53 Gg N emitted during upland crop season. N₂O emission from upland and from paddy field during upland land crop season accounted for 91% of the total emission.     

Using a boundary line approach to analyze N2O flux data from agricultural soils

Predicting the N₂O flux from soils is difficult because of the complex interplay of the various processes involved. In this study a boundary line approach was used to apply results from mechanistic experiments to N₂O flux data resulting from measurements on field scale in southern Germany. Boundary lines were fitted to the rim of the data points in scattergrams depicting readily obtainable soil variables against the measured N₂O flux. The boundary line approach is based on the hypothesis that this line depicts the functional dependency between the two variables. For determining these boundary lines a novel method was applied. The function best representing the relationship between the N₂O flux and soil temperature had a maximum above 23 °C and the one between the N₂O flux and the water filled pore space (WFPS, to represent water content) had a maximum at 72% WFPS. In the range of 0–20 mg N kg^-1 the relationship between N₂O flux and nitrate in the soil was best described by a linear function, whereas in the range of 0–35 mg N kg^-1 a Michaelis–Menten function was more appropriate. The boundary lines specified in this study are in agreement with existing theoretical concepts as well as experimental results obtained under controlled and field conditions as reported in the literature. Therefore, the boundary line approach can be used to improve empirical models for predicting the N₂O flux in the field.     

Anthropogenic emissions of NOX, NH3 and N2O in India

Emissions of NO_x, NH₃ and N₂O from anthropogenic activities in India have been estimated based on actual field measurements as well as available default methodologies. The NO_x emissions are mainly from the transport sector and contribute about 5% of the global NO_x emission from fossil fuel. NH₃ emissions from urea seems to be highly uncertain. However, emissions of NH₃ from fertilizers and livestock are estimated to be 1175 Gg and 1433 Gg, respectively. N₂O emissions seem to be derived predominantly from fertilizer applications, resulting in the release of 199–279 Gg N₂O. Other sources of N₂O, viz. agricultural residue burning, biomass burning for energy and nitric acid production are estimated to be 3, 35–187 and 2–7 Gg, respectively.     

The temperature-programmed desorption of N2 from a Ru/MgO catalyst used for ammonia synthesis

The temperature-programmed desorption (TPD) of N₂ from a Ru/MgO catalyst used for ammonia synthesis was studied in a microreactor flow system operating at atmospheric pressure. Saturation with chemisorbed atomic nitrogen (N-*) was achieved by exposure to N₂ at 573 K for 14 h and subsequent cooling in N₂ to room temperature. With a heating rate of 5 K/min in He, a narrow and fairly symmetric N₂ TPD peak at about 640 K results. From experiments with varying heating rates a preexponential factor A_des = 1.5×10¹⁰ molecules/(site s) and an activation energy E_des = 158 kJ/mol was derived assuming secondorder desorption. This rate constant of desorption is in good agreement with results obtained with a Ru(0001) single crystal surface in ultra-high vacuum (UHV). The rate of dissociative chemisorption was determined by varying the N₂ exposure conditions. Determination of the coverage of N-^* was based on the integration of the subsequently recorded N₂ TPD traces yielding A_ads = 2×10^–6 (Pa s)^–1 and E_ads = 27 kJ/mol. The corresponding sticking coefficient of about 10^–14 at 300 K is in agreement with the inertness of Ru(0001) in UHV towards dissociative chemisorption of N₂. However, if the whole catalytic surface were in this state, then the resulting rate of N₂ dissociation would be several orders of magnitude lower than the observed rate of NH₃ formation. Hence only a small fraction of the total Rumetal surface area of Ru/MgO seems to be highly active dominating the rate of ammonia formation.     

Nitrous oxide emissions from agricultural soils

This paper addresses three topics related to N₂O emissions from agricultural soils. First, an assessment of the current knowledge of N₂O emissions from agricultural soils and the role of agricultural systems in the global N₂O are discussed. Secondly, a critique on the methodology presented in the OECD/OCDE (1991) program on national inventories of N₂O is presented. Finally, technical options for controlling N₂O emissions from agricultural fields are discussed.The amount of N₂O derived from nitrogen applied to agricultural soils from atmospheric deposition, mineral N fertilizer, animal wastes or biologically fixed N, is not accurately known. It is estimated that the world-wide N₂O emitteddirectly from agricultural fields as a result of the deposition of all the above nitrogen sources is 2–3 Tg N annually. This amounts to 20–30% of the total N₂O emitted annually from the earth's surface. An unknown, but probably significant, amount of N₂O is generated indirectly in on and off farm activities associated with food production and consumption.Management options to limitdirect N₂O emissions from N-fertilized soils should emphasize improving N-use efficiency. Such management options include managing irrigation frequency, timing and quantity; applying N only to meet crop demand through multiple applications during the growing season or by using controlled release fertilizers; applying sufficient N only to meet crop needs; or using nitrification inhibitors. Most of these options have not been field tested. Agricultural management practices may not appreciably affect indirect N₂O emissions.     

Effect of low-sulfur fuels upon NH3 and N2O emission during operation of commercial three-way catalytic converters

The use of low-sulfur fuel is known to improve the performance of the three-way catalytic converter (TWC). However, in this work we report how low-sulfur operation of commercial TWC also favors formation of N₂O and NH₃ as by products. We found that low-sulfur rich operation above 300 °C increases the production of NH₃, inhibiting the formation of N₂O characteristic of high-sulfur operation. During lean operation, the production of N₂O near the stoichiometric point is not significantly affected by the sulfur level. The large production of N₂O observed during light-off is not affected by SO₂ when the operation is lean, but under rich conditions N₂O is produced up to 575 °C. The increased production of NH₃ and N₂O in TWC as a result of the introduction of low-sulfur gasoline is an area that requires further analysis because of its implication upon public health in large urban settings.     

Ammonia and nitrous oxide emissions from grass and alfalfa mulches

Ammonia (NH₃) and nitrous oxide (N_-2O) emissions were measured in the field for three months from three different herbage mulches and from bare soil, used as a control. The mulches were grass with a low N-content (1.15% N in DM), grass with a high N-content (2.12% N in DM) and alfalfa with a high N-content (4.33% N in DM). NH₃ volatilization was measured using a micrometeorological technique. N_-2O emissions were measured using closed chambers. NH₃ and N_-2O emissions were found to be much higher from the N-rich mulches than from the low-N grass and bare soil, which did not differ significantly. Volatilization losses of NH₃ and N_-2O occurred mainly during the first month after applying the herbage and were highest from wet material shortly after a rain. The extent of NH₃-N losses was difficult to estimate, due to the low frequency of measurements and some problems with the denuder technique, used on the first occasions of measurements. Nevertheless, the results indicate that NH₃-N losses from herbage mulch rich in N can be substantial. Estimated losses of NH₃-N ranged from the equivalent of 17% of the applied N for alfalfa to 39% for high-N grass. These losses not only represent a reduction in the fertilizer value of the mulch, but also contribute appreciably to atmospheric pollution. The estimated loss of N_-2O-N during the measurement period amounted to 1% of the applied N in the N-rich materials, which is equivalent to at least 13 kg N_-2O-N ha^-1 lost from alfalfa and 6 kg ha^-1 lost from high-N grass. These emission values greatly exceed the 0.2 kg N_-2O-N ha^-1 released from bare soil, and thus contribute to greenhouse gas emissions.     

Catalytic Conversion of N2O to N2 over Metal-Based Catalysts in the Presence of Hydrocarbons and Oxygen

The catalytic conversion of N₂O to N₂ in the presence or the absence of propene and oxygen was studied. The catalysts examined in this work were synthesized impregnating metals (Rh, Ru, Pd, Co, Cu, Fe, In) on different supports (Al₂O₃, SiO₂, TiO₂, ZrO₂ and calcined hydrotalcite MgAl₂(OH)₈·H₂O). The experimental results varied both with the type of the active site and with the type of the support. Rh and Ru impregnated on -alumina exhibited the highest activity. The performance of the above most promising catalysts was studied using various hydrocarbons (CH₄, C₃H₆, C₃H₈) as reducing agents. These experimental results showed that the type of reducing agent does not affect the reaction yield. The temperature where complete conversion of N₂O to N₂ was measured was independent of the reductant type. The activity of the most active catalysts was also measured in the presence of SO₂ and H₂O in the feed. A shift of the N₂O conversion versus temperature curve to higher temperatures was observed when SO₂ and H₂O were added, separately or simultaneously, to the feed. The inhibition caused by SO₂ was attributed to the formation of sulfates and that caused by water to the competitive chemisorption of H₂O and N₂O on the same active sites.     

Nitrous oxide emissions from agricultural fields during winter and spring thaw as affected by management practices

Highest rates of N₂O emissions from fertilized as well as natural ecosystems have often been measured at spring thaw. But, it is not clear if management practices have an effect on winter and spring thaw emissions, or if measurements conducted over several years would reveal different emission patterns depending on winter conditions. In this study, we present N₂O fluxes obtained using the flux-gradient approach over four winter and spring thaw periods, spanning from 1993 to 1996, at two locations in Ontario, Canada. Several agricultural fields (bare soil, barley, soybean, canola, grass, corn) subjected to various management practices (manure and nitrogen fertilizer addition, alfalfa ploughing, fallowing) were monitored. Nitrous oxide emissions from these fields from January to April over four years ranged between 0 and 4.8 kg N ha^-1. These thaw emissions are substantial and should be considered in the nitrous oxide budgets in regions where thaw periods occur. Our study indicates that agricultural management can play a role in mitigating these emissions. Our data show that fallowing, manure application and alfalfa incorporation in the fall lead to high spring emissions, while the presence of plants (as in the case of alfalfa or grass) can result in negligible emissions during thaw. This presents an opportunity for mitigation of N₂O emissions through the use of over-wintering cover crops.     

An investigation into the effect of Cs promotion on the catalytic activity of NiO in the direct decomposition of N2O

A series of Cs promoted NiO catalysts have been prepared and tested for direct decomposition of N₂O. These catalysts are characterized by BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of N₂O (TPD-N₂O) and X-ray photo electron spectroscopy (XPS). The Cs promoted NiO catalysts exhibit higher activity for the decomposition of N₂O compared to bulk NiO. The catalyst with Cs/Ni ratio of 0.1 showed highest activity. The enhancement in catalytic activity of the Cs promoted catalysts is attributed to the change in the electronic properties of NiO. The characterization techniques suggest weakening of Ni–O bond thereby the desorption of oxygen becomes more facile during the reaction. The Cs promoted NiO catalyst is effective at low reaction temperature and also in the presence of oxygen and steam in the feed stream. IICT Communication No: 070523.     

Preliminary studies on N2O emission fluxes from upland soils and paddy soils in China

In this paper, we presented the preliminary results of N₂O fluxes from Chinese upland and rice paddy fields. The mean N₂O flux from upland fields of North China is 30.6 μg N₂O-N m^-2 h^-1; the average N₂O flux from Chinese rice paddy field is 39.5 μg N₂O-N m^-2 h^-1. The effects of cropping system, water management and application of N fertilizer and organic manure on N₂O emission from rice paddy field have also been presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparing a process-based agro-ecosystem model to the IPCC methodology for developing a national inventory of N2O emissions from arable lands in China

Nations are now obligated to assess their greenhouse gas emissions under the protocols of Article 4 of the United Nations Framework Convention on Climate Change. The IPCC has developed `spreadsheet-format' methodologies for countries to estimate national greenhouse gas emissions by economic sector. Each activity has a magnitude and emission rate and their product is summed over all included activities to generate a national total (IPCC, 1997). For N₂O emissions from cropland soils, field studies have shown that there are important factors that influence N₂O emissions at specific field sites that are not considered in the IPCC methodology. We used DNDC, a process-oriented agroecosystem model, to develop an unofficial national inventory of direct N₂O emissions from cropland in China. We assembled county-scale data on soil properties, daily weather, crop areas, N-fertilizer use, livestock populations (for manure inputs to cropland), and agricultural management for the 2500 counties in mainland China. Total 1990 cropland area was 0.95 million km². Total N-fertilizer use in China in 1990 was 16.6 Tg N. The average fertilization rate was 175 kg N ha⁻¹ cropland. One-year simulations with DNDC were run for each crop type in each county to generate estimates of direct N₂O emissions from soils. National totals were the sum of results for all crop simulations across all counties. Baseline simulations estimated that total N₂O emission from arable land in China in 1990 was 0.31 Tg N₂O-N yr⁻¹. We also ran simulations with zero N-fertilizer input; the difference between the zero-fertilizer and the baseline run is an estimate of fertilizer-induced N₂O emissions. The fertilizer-induced emission was 0.13 Tg N₂O-N yr⁻¹, about 0.8% of total N-fertilizer use (lower than the mean but within the IPCC range of 1.25±1.0%). We compared these results to our estimates of county-scale IPCC methodology emissions. Total emissions were similar but geographical patterns were quite different. This revised version was published online in August 2006 with corrections to the Cover Date.     

Diffusion analysis of N2O cycling in a fertilized soil

The behavior of nitrous oxide (N₂O) in fertilized soil was studied in terms of soil fluxes, the production rates at various depths and the turnover in soil. The diffusive losses of N₂O to the atmosphere calculated from soil N₂O profile compared favorably with the flux directly determined with a closed chamber technique. The estimate of N₂O production rates at several depths demonstrated that the sites of N₂O production was only near the soil surface. The calculated residence time of N₂O in the entire soil column studied was only 1.4 hour during active emission period and less than 1 day even in the later period having trace N₂O emission. The prolonged N₂O emission observed after the active phase was due likely to a lasting N₂O production rather than a supply from the soil N₂O reservoir. The results suggested that most N₂O in soil was emitted quite promptly to the atmosphere after its production. A minor role of soil as an N₂O reservoir is emphasized from the viewpoint of the origin of groundwater N₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparison of N2O emissions from soils at three temperate agricultural sites: simulations of year-round measurements by four models

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 N₂O 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.     

NO and N2O emissions from savanna soils following the first simulated rains of the season

Data on the emissions of oxides of nitrogen from the soil during the early part of the wet season are reported for nutrient-rich and nutrient-poor sandy soils at Nylsvley, South Africa. The emissions of NO_x and N₂O following the first wetting event of the season are elevated relative to subsequent events. The observed high emission rates (76 ng N-NO m^-2 s^-1) are partially attributed to the sandiness of the soil, which permits NO to diffuse out of the soil rapidly. The pulse of high emissions following wetting is maintained for approximately 72 hours, thereafter continuing at around 20 ng NO m^-2 s^-1 while the soil remains moist. The initial pulse is suggested to be due to the accumulation of a substrate pool during the dry period, coupled with an inability of plants and microbes to use it effectively during the first few days after wetting. There were no significant differences in the peak or subsequent emission rates for either NO or N₂O between two sites of differing nitrogen mineralisation potentials. N₂O emissions averaged 8% of NO_x emissions. The enhanced emissions of NO_x which follow the first wetting after a prolonged dry period do not make a very large contribution to the annual gaseous N emission budget, but could be a significant contributor to the high tropospheric ozone levels observed over southern Africa in springtime.     

Light fraction organic N, ammonium, nitrate and total N in a thin Black Chernozemic soil under bromegrass after 27 annual applications of different N rates

Anadequate supply of N for a crop depends among others on the amounts of N thataremineralized from the soil organic matter plus the supply of ammonium andnitrateN already present in the soil. The objective of this study was to determine thebehaviour of light fraction organic N (LFN), NH₄-N, NO₃-Nand total N (TN) in soil in response to different rates of fertilizer Napplication. The 0–5, 5–10, 10–15 and 15–30cm layers of a thin Black Chernozemic soil under bromegrass(Bromus inermis Leyss) at Crossfield, Alberta, Canada,weresampled after 27 annual applications of ammonium nitrate at rates of 0, 56,112,168, 224 and 336 kg N ha^–1. The concentration andmass of TN and LFN in the soil, and the proportion of LFN mass within the TNmass usually increased with N rates up to 224 kg Nha^–1. The increase in TN mass and LFN mass per unit ofNadded was generally maximum at 56 kg N ha^–1 anddeclined with further increases in the rate of N application. The percentchangein response to N application was much greater for the LFN mass than for the TNmass for all the N rates and all soil depths that were sampled. Mineral N intheform of NH₄-N and NO₃-N did not accumulate in the soil at 112 kg N ha^–1 rates, whereas theiraccumulation increased markedly with rates of 168 kg Nha^–1. In conclusion, long-term annual fertilization at 112 kg N ha^–1 to bromegrass resulted insubstantial increase in the TN and LFN in soil, with no accumulation ofNH₄-N and NO₃-N down the depth. The implication of thesefindings is that grasslands for hay can be managed by appropriate Nfertilization rates to increase the level of organic N in soil.     

Possible role of nitrite/nitrate redox cycles in N2O decomposition and light-off over Fe-ZSM-5

Surface nitrite/nitrate redox cycles were proposed to explain light-off behavior that was observed during the decomposition of N₂O over Fe-ZSM-5. Further study has demonstrated that while the nitrite/nitrate model can explain the original observations as an isothermal, mechanistic phenomenon, the light-off behavior is thermal, and not a mechanistic effect. Nonetheless, a pathway involving nitrite/nitrate redox cycles appears to be more consistent with experimental observation than the simple two-step pathway involving cation redox cycles. In particular, the nitrite/nitrate pathway can explain the effect of added NO upon the reaction kinetics and the reported isotopic product composition when unlabeled N₂O reacts over an oxygen-labeled catalyst. Further, a nitrite/nitrate pathway is consistent with the steady-state kinetics as well as published thermal desorption and infrared spectroscopic results.     

The state of adsorbed oxygen species formed in the decomposition of N2O on CaO

Temperature programmed desorption, FT-IR spectra and hydrolysis of adsorbed oxygen species revealed that a considerable amount of adsorbed peroxide species were formed on CaO by decomposition of N₂O, whereas no adsorbed species were formed by molecular oxygen.     

N2O and NO emissions from grassland soils after the application of cattle and swine excreta

N₂O and NO fluxes from grassland soil after the application of cattle and swine excreta were measured by a closed chamber method in the autumn and winter of 1994 to 1995. Fresh excrement and urine were spread on the grassland experimental plots and these gas fluxes were measured one or two times a week. In the autumn experiment, N₂O and NO fluxes began to increase several days after the application, the NO flux reaching a maximum after 16 days. In the winter experiment, N₂O and NO fluxes began to increase 45 days after the application and reached a maximum after 80 days. Nitrous oxide flux was influenced by soil water content, high water content leading to high N₂O flux. The ratio of NO-N/N₂O-N in the flux was in the range of 1.1 to 13.7, and negatively correlated to the soil water content. In the winter experiment, the total emission rate of NO was 0.48% and 0.45% of total nitrogen in the applied cattle and swine excreta, respectively. The total emission rate of N₂O was 0.085% and 0.098% in the applied cattle and swine excreta, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nitrous oxide emissions from paddy soil in three rice-based cropping systems in China

Rice-flooding fallow, rice-wheat, and double rice-wheat systems were adopted in pot experiment in an annual rotation to investigate the effects of cropping system on N₂O emission from rice-based cropping systems. The annual N₂O emission from the rice-wheat and the double rice-wheat cropping systems were 4.3 kg N ha^–1 and 3.9 kg N ha^–1, respectively, higher than that from rice-flooding fallow cropping system, 1.4 kg N ha^–1. The average N₂O flux was 115 and 118 g N m^–2 h^–1 for rice season in rice-wheat system and early rice season in double rice-wheat system, respectively, 68.6 and 35.3 g N m^–2 h^–1 for the late rice season in double rice-wheat system and rice season in rice-flooding fallow, respectively, and only 3.1–5.3 g N m^–2 h^–1 for winter wheat or flooding fallow season. Temporal variations of N₂O emission during rice growing seasons differed and high N₂O emission occurred when soil conditions changed from upland crop to flooded rice.