NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

Soil Apparent Electrical Conductivity (EC<Subscript>a</Subscript>) as a Means of Monitoring Changesin Soil Inorganic N on Heterogeneous Morainic Soils in SE Norway During Two Growing Seasons

An efficient method to monitor changes in soil inorganic N content during crop growth would be a useful means to guide N fertilization to ensure high yields and low N losses to the environment. In this study, soil apparent electrical conductivity (EC_a) measured by the widely used conductivity meter EM38 was tested as an indirect measurement of available N in spring barley during two cropping seasons at two sites with morainic loam in SE Norway. The experiment was constructed to maximize soil variation. In spite of the ȁ8noiseȁ9 caused by the soil heterogeneity, concentrations of inorganic N (cN_inorg) or NO₃-N were most strongly correlated with EC_a in both years and at both locations (with one exception). The measurements of EC_a reflected well the temporal variation in inorganic N content (N_inorg), and a ranking of the treatments based on EC_a fitted very well with a ranking based on N_inorg at the first three sampling times after fertilizing. The best subset of sensor variables (i.e. variables which can be measured ȁ8on-the-goȁ9 by sensor techniques in the field) described 27–69% (average 47%) of the variation in topsoil cN_inorg. When expanding the regression models to include pH as well, the degree of explanation increased significantly. In conclusion, the method of using EC_a appears to be quite robust in terms of detecting relative differences in cN_inorg, whereas a determination of absolute levels of cN_inorg with the method is unreliable.     

Nitrogen dynamics during till and no-till pasture restoration sequences in Rondônia,Brazil

The clearing of tropical rain forest in the Amazon basin has created large areas of cattle pasture that are now declining in productivity. Practices adopted by ranchers to restore productivity to degraded pastures have the potential to alter soil N availability and gaseous N losses from soils. We examined how soil inorganic N pools, net N mineralization and net nitrification rates, nitrification potential and NO and N₂O emissions from soils of a degraded pasture responded to the following restoration treatments: (1) soil tillage followed by replanting of grass and fertilization, (2) no-till application of non-selective herbicide, planting of rice, harvest followed by no-till replanting of grass and fertilization, and (3) the same no-till sequence with soybeans instead of rice. Tillage increased soil NH₄⁺ and NO₃^? pools but NH₄⁺ and NO₃^? pools remained relatively constant in the control and no-till treatments. Cumulative rates of net N mineralization and net nitrification during the first 6 months after treatment varied widely but were hightest in the tilled treatment. Emissions of NO and N₂O fluxes increased with tillage and with N fertilization. There were no clear relationships among rates of N fertilizer application, net N mineralization, net nitrification, NO, N₂O and total N oxide emissions. Our results indicate that pasture restoration sequences involving tilling and fertilizing will increase emissions of N oxides, but the magnitude of the increase is likely to differ based on timing of fertilizer application relative to the presence of plants and the magnitude of plant N demand. Emissions of N oxides appear to be decreased by the use of restoration sequences that minimize reductions in pasture grass cover.     

Effect of catalysts in the quality of syngas and by-products obtained by co-gasification of coal and wastes. 1. Tars and nitrogen compounds abatement

The aim of this work is to analyse the possibility of using co-gasification technology to process coal mixed with wastes to take profit of its energy content and at the same time to minimize the environmental impact associated with the use of wastes and to diminish the costs of flue gas treatment. The addition to coal of different types of materials, like: pine based waste, petcoke and polyethylene (PE), was not found to give rise to any operational problems, regarding both the feeding system and gasification process and led to higher energy conversions, however, the gas presented higher tars and hydrocarbons content. Several catalysts were tested, such as, dolomite, olivine, nickel and magnesium oxides, zinc oxides and cobalt and molybdenum oxides. Catalyst action was analysed in tars release and also in ammonia compounds reduction. The presence of catalysts allowed increasing hydrogen release, whilst there was a decrease in hydrocarbons and tars contents. A nickel-magnesium oxide was the catalyst that led to the highest reduction in hydrocarbons and tars. This catalyst also led to the lowest NH₃ content in the fuel gas produced, due to the catalyst efficiency in NH₃ destruction.     

Agroecological analysis and economic benefit of organic resources and fertiliser in till and no-till sorghum production after a 6-year fallow in semi-arid West Africa

A field experiment was conducted in Gampela (Burkina Faso) in 2000 and 2001 to assess the impact of organic and mineral sources of nutrients and combinations thereof in optimising crop production in till and no-till systems and to assess the economic benefit of these options. The study showed that under conditions of rainfall deficiency, the use of a single organic resource at an equivalent dose of 40 kg N ha⁻¹ better secured crop yield than the application of an equivalent amount as urea-N, while a combination of organic resources and fertiliser was better in increasing crop yield than the application of the same N amount in the form of urea. In a year of rainfall deficiency, a mix of organic resources and fertiliser in both till and no-till systems increased crop water use efficiency, with the result that the farmer was able to purchase only half of the normal quantity of N fertiliser to obtain a higher yield that he would have done when all of the N was supplied in the form of urea. Under conditions where soil N is deficient, an economic benefit was achieved when urea was combined with easily decomposable organic material (e.g. sheep dung); mixing the urea at a dose of 40 kg N ha⁻¹ with maize straw was not sufficient in alleviating the negative interaction due to the enhanced N immobilisation. The results demonstrate that the use of N fertiliser alone was risky and that a higher yield, with the accompanying economic benefit, was scarcely achieved under the prevailing rainfall conditions. The application of soil and water conservation measures can contribute greatly to increasing the economic benefit of mineral, organic or combined organic and mineral-derived nutrient application under semi-arid conditions.     

The effect of grazing intensity and the presence of a forage legume on nitrogen dynamics in Brachiaria pastures in the Atlantic forest region of the south of Bahia, Brazil

It has been shown that with careful grazing management and addition of Pand K, but not N, fertilisers Brachiaria pastures are ableto maintain sustainable live weight gains over many years. However, standardon-farm practice, which generally involves high stocking rates, leads after afew years to pasture decline due mainly to N deficiency for grass regrowth. Togenerate an understanding of the mechanism of pasture decline and possiblemanagement options to mitigate this process, a study was performed in theAtlantic forest region of the south of Bahia state to study the N dynamics inpastures of Brachiaria humidicola subject to threedifferent stocking rates of beef cattle, with and without the presence of theforage legume Desmodium ovalifolium. Despite the fact thatthe C:N ratio of the deposited litter was high (60 to 70) the rate ofdecomposition was very rapid (k –0.07 gg^–1 day^–1) and annual rates of Nturnover through the litter pathway were between 105 and 170 kg Nha^–1 year^–1. In the grass-onlypasturesas stocking rate increased from 2 to 3 head ha^–1, N recycledinthe litter decreased by 11%, but a further increase to 4 headha^–1 decreased N recycling by 30% suggesting thatbeyonda certain critical level higher grazing stocking rates would lead to pasturedecline if there was no N addition. High stocking rates decreased theproportionof the legume in the sward, but at all rates the concentration of N in both thegreen and dead grass in the forage on offer and in the litter was higher in themixed sward. The presence of the legume caused a decrease in the C:N ratio ofthe microbial biomass while both soil N mineralisation and nitrificationincreased. This increased rate of turnover of the microbial biomass and thecontribution of N₂ fixation to the legume resulted in largeincreasesin the N recycled via litter deposition ranging from 42 to 155 kg Nha^–1 year^–1.     

Nitrous oxide emission from upland crops and crop-soil systems in northeastern China

Although it is known that crops can directly emit N₂O, their contribution to the total N₂O emission from crop-soil systems under field conditions is not well understood. This study was conducted to study the contribution of crops to total N₂O emission from soybean-soil and maize-soil systems in northeastern China. The effects of N fertilization on N₂O emission and NO ₃ ⁻ -N concentration in plants were also studied. The emission from crop-soil systems was measured with the closed chamber method, whereas the direct emission from crops was measured with the soil surface-sealed method. The addition of fertilizer N significantly increased the NO ₃ ⁻ -N concentration in crops and enhanced the N₂O emission from crop-soil systems and from crops alone. The amount of N₂O emitted directly from soybean plants accounted for 6 to 11% of the total soybean-soil emission. Similarly, the amount of N₂O emitted directly from maize plants accounted for 8.5 to 16% of the total maize-soil emission. The proportion of the applied N lost through direct N₂O emission from plants ranged from 0.19 to 0.34%, whereas the proportion of the applied N lost through N₂O emission from the crop-soil system ranged from 1.1 to1.9%. These results suggest that the use of chambers that do not include plants may lead to an underestimation of the total N₂O emission from crop-soil systems. This revised version was published online in November 2006 with corrections to the Cover Date.     

NO emission of oxygen-enriched CH4/O2/N2 premixed flames under electric field

This work investigates the electric field effect on nitrogen oxide (NO) pollutant formation and emission composition of premixed flames in order to provide better insight on the mechanism of controlling the combustion process by electro-physical means. The present study aims to investigate experimentally the effect of radial DC electric field on premixed laminar methane flame. The electric field effect on flame shape, emission composition and NO emission index of flame is investigated experimentally under the action of direct-current electric field under varying equivalence ratio and level of oxygen enrichment. The results show that ionic wind effects cause the distortion in flame shape. The ionic wind effects diminish with increasing flow rate and level of oxygen enrichment. Minimal effects on NO are measured for flames under the influence of electric field and vanished as the level of oxygen enrichment is increased. This was well supported by the temperature profile measurement in the post flame gas showing no field-induced modification also. It seemed that the action of an electric field on a flame with a geometry that remains practically undeformed produces very minimal effect on pollutant emission.     

Late season nitrogen fertilization of soybeans: effects on leaf senescence, yield and environment

Nitrogen demand from soybean seeds during seed filling is very high and has been proposed as the cause of nitrogen remobilization and leaf senescence. Previous research has not shown consistent effects of late season fertilization on seed yield, while its effects on leaf senescence have not been evaluated. Two field experiments were performed to determine the effects of a late season N fertilization on leaf senescence and fall, seed yield and its components, and residual soil nitrate, and to evaluate the potential risk of groundwater contamination. Two rates of nitrogen (50 and 100 kg N ha^–1) were applied at the R3 and R5 development stages. Nitrogen fertilization, either at R3 or R5, increased soil nitrate availability during the seed-filling period. Seed yield, seed number and protein content were not affected by N fertilization. The addition of 100 kg N ha^–1 produced a small delay of 1–2 days in the leaf fall, and slightly increased seed size (3.6%). Our results suggest that increasing soil N availability during the seed-filling period is not an effective way to delay leaf senescence or to increase seed growth and yield of soybean. Nitrogen fertilization increased the level of residual nitrate in the top soil at one site (the one with lowest seed yield), increasing the risk of nitrate leaching during subsequent fallow.     

Predicting N mineralized in a Georgia Coastal Plain field

The N mineralized from soil organic matter provides an important portion of N available for crop production. The objective of this study was to determine the amount of spatial variability in N mineralization potential in a field and to evaluate three different methods that might be used to estimate this variability. The three methods tested included predicting the N mineralized from surface soil properties as well as from a biological and a chemical procedure. Three soils varying in N mineralization potential were selected for the study from a field in the Georgia Coastal Plain. The N mineralized from these soils was determined by an N balance of unfertilized and cropped plots. The amount of N mineralized could not be reliably predicted from surface soil organic C, although surface soil clay concentration was positively correlated with the N mineralized. The N mineralized that was predicted using mineralization parameters determined by aerobic incubation, adjusted daily for soil water content and temperature, was approximately 50% of the field measurements of N mineralized. The values of NH₄-N extracted with hot 2 M KCl were related significantly to N mineralized in the field (r²= 0.60) and also to the zero order rate constant of mineralization, k₀ (r²= 0.77), determined from the N mineralized in the aerobic laboratory incubation.