Methane and nitrous oxide fluxes in annual and perennial land-use systems of the irrigated areas in the Aral Sea Basin

Land use and agricultural practices can result in important contributions to the global source strength of atmospheric nitrous oxide (N2O) and methane (CH4). However, knowledge of gas flux from irrigated agriculture is very limited. From April 2005 to October 2006, a study was conducted in the Aral Sea Basin, Uzbekistan, to quantify and compare emissions of N2O and CH4 in various annual and perennial land-use systems: irrigated cotton, winter wheat and rice crops, a poplar plantation and a natural Tugai (floodplain) forest. In the annual systems, average N2O emissions ranged from 10 to 150 μg N2O-N m−2 h−1 with highest N2O emissions in the cotton fields, covering a similar range of previous studies from irrigated cropping systems. Emission factors (uncorrected for background emission), used to determine the fertilizer-induced N2O emission as a percentage of N fertilizer applied, ranged from 0.2% to 2.6%. Seasonal variations in N2O emissions were principally controlled by fertilization and irrigation management. Pulses of N2O emissions occurred after concomitant N-fertilizer application and irrigation. The unfertilized poplar plantation showed high N2O emissions over the entire study period (30 μg N2O-N m−2 h−1), whereas only negligible fluxes of N2O (<2 μg N2O-N m−2 h−1) occurred in the Tugai. Significant CH4 fluxes only were determined from the flooded rice field: Fluxes were low with mean flux rates of 32 mg CH4 m−2 day−1 and a low seasonal total of 35.2 kg CH4 ha−1. The global warming potential (GWP) of the N2O and CH4 fluxes was highest under rice and cotton, with seasonal changes between 500 and 3000 kg CO2 eq. ha−1. The biennial cotton–wheat–rice crop rotation commonly practiced in the region would average a GWP of 2500 kg CO2 eq. ha−1 yr−1. The analyses point out opportunities for reducing the GWP of these irrigated agricultural systems by (i) optimization of fertilization and irrigation practices and (ii) conversion of annual cropping systems into perennial forest plantations, especially on less profitable, marginal lands.

Reducing nitrous oxide emissions while supporting subtropical cereal production in Oxisols

This is the first study to investigate alternative fertilisation strategies to increase cereal production while reducing greenhouse gas emissions from the most common soil type in subtropical regions. The results of this research will contribute to define future farming practices to achieve global food security and mitigate climate change. The study established that introducing legumes in cropping systems is the most agronomically viable and environmentally sustainable fertilisation strategy. Importantly, this strategy can be widely adopted in subtropical regions since it is economically accessible, requires little know-how transfer and technology investment, and can be profitable in both low- and high-input cropping systems.

Effect of nitrification inhibitors (DMPP and 3MP+ TZ) on soil nitrous oxide emissions from a sub-tropical vegetable production system in Queensland, Australia

The use of nitrification inhibitors, in combination with ammonium based fertilisers, has been promoted recently as an effective method to reduce nitrous oxide (N2O) emissions from fertilised agricultural fields, whilst increasing yield and nitrogen use efficiency. Vegetable cropping systems are often characterised by high inputs of nitrogen fertiliser and consequently elevated emissions of nitrous oxide (N2O) can be expected. However, to date only limited data is available on the use of nitrification inhibitors in sub-tropical vegetable systems. A field experiment investigated the effect of the nitrification inhibitors (DMPP & 3MP+TZ) on N2O emissions and yield from a typical vegetable production system in sub-tropical Australia. Soil N2O fluxes were monitored continuously over an entire year with a fully automated system. Measurements were taken from three subplots for each treatment within a randomized complete blocks design. There was a significant inhibition effect of DMPP and 3MP+TZ on N2O emissions and soil mineral N content directly following the application of the fertiliser over the vegetable cropping phase. However this mitigation was offset by elevated N2O emissions from the inhibitor treatments over the post-harvest fallow period. Cumulative annual N2O emissions amounted to 1.22 kg-N/ha, 1.16 kg-N/ha, 1.50 kg-N/ha and 0.86 kg-N/ha in the conventional fertiliser (CONV), the DMPP treatment, the 3MP+TZ treatment and the zero fertiliser (0N) respectively. Corresponding fertiliser induced emission factors (EFs) were low with only 0.09 - 0.20% of the total applied fertiliser lost as N2O. There was no significant effect of the nitrification inhibitors on yield compared to the CONV treatment for the three vegetable crops (green beans, broccoli, lettuce) grown over the experimental period. This study highlights that N2O emissions from such vegetable cropping system are primarily controlled by post-harvest emissions following the incorporation of vegetable crop residues into the soil. It also shows that the use of nitrification inhibitors can lead to elevated N2O emissions by storing N in the soil profile that is available to soil microbes during the decomposition of the vegetable residues over the post-harvest phase. Hence the use of nitrification inhibitors in vegetable systems has to be treated carefully and fertiliser rates need to be adjusted to avoid excess soil nitrogen during the postharvest phase.

Virtues of marginally metallic oxides

Transition-metal oxides at the metal-insulator boundary, especially those belonging to the perovskite family, exhibit fascinating phenomena such as insulator-metal transitions controlled by composition, high-temperature superconductivity and giant magnetoresistance (GMR), Interestingly, many of these marginally metallic oxides obey the established criteria for metallicity and have a finite density of states at the Fermi;level. The perovskite manganates exhibiting GMR, on the other hand, are unusual in that they possess very high resistivities in the 'metallic' state and show no significant density of states at the Fermi level, Marginal metallicity in oxide systems is a problem of great complexity and contemporary interest and its understanding is of crucial significance to the diverse phenomena exhibited by these materials.

Energy band engineering of complex metal oxides

This doctoral studies focused on the development of new materials for efficient use of solar energy for environmental applications. The research investigated the engineering of the band gap of semiconductor materials to design and optimise visible-light-sensitive photocatalysts. Experimental studies have been combined with computational simulation in order to develop predictive tools for a systematic understanding and design on the crystal and energy band structures of multi-component metal oxides.

Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Action of Transition Metal Oxides on Composite Solid Propellants

The catalytic effects of Fe2O3, Ni2O3, MnO2, and Co2O3 transition metal oxides (TMO) on the combustion of polystyrene and carboxyl-terminated polybutadiene were investigated. The order of activity of TMO's was explained by the presence of Co and absence of Fe and Ni in their lattice systems along with a reduced electron-transfer process; in systems which induce the metal ions to enter the lattice, the electron transfer process is much greater. The thermal decomposition of ammonium perchlorate propellants was enhanced to a greater extent by Co2O3 and MnO2 than by Fe2O3 and Ni2O3.

Evaluation of residence time on nitrogen oxides removal in non-thermal plasma reactor

Non-thermal plasma (NTP) has been introduced over the last few years as a promising after- treatment system for nitrogen oxides and particulate matter removal from diesel exhaust. NTP technology has not been commercialised as yet, due to its high rate of energy consumption. Therefore, it is important to seek out new methods to improve NTP performance. Residence time is a crucial parameter in engine exhaust emissions treatment. In this paper, different electrode shapes are analysed and the corresponding residence time and NOx removal efficiency are studied. An axisymmetric laminar model is used for obtaining residence time distribution numerically using FLUENT software. If the mean residence time in a NTP plasma reactor increases, there will be a corresponding increase in the reaction time and consequently the pollutant removal efficiency increases. Three different screw thread electrodes and a rod electrode are examined. The results show the advantage of screw thread electrodes in comparison with the rod electrode. Furthermore, between the screw thread electrodes, the electrode with the thread width of 1 mm has the highest NOx removal due to higher residence time and a greater number of micro-discharges. The results show that the residence time of the screw thread electrode with a thread width of 1 mm is 21% more than for the rod electrode.

High-temperature superconductivity in La- and Lu-substituted YBa2,Cu3,O7, and related oxides

The perovskites, Y0.75La0.25Ba2Cu3O7 and Y0.75Lu0.25Ba2Cu3O7, show high-Tc superconductivity (with zero resistance at or above 80 K), just as the parent compound YBa2Cu3O7. The Lu-substituted oxide, with the smallest unit-cell parameters, shows the highest Tc besides exhibiting a 100% Meissner effect. Hc1, in these oxides is around 25 mT, but the Hc2, is large. The thermopower of YBa2Cu3O7 shows a sharp transition to zero at the superconducting transition, reinforcing the bulk nature of the superconductivity. Preliminary studies show that ErBa2Cu3O7 and Er0.5Y0.5Ba2Cu3O7 are both high-temperature superconductors with zero resistance in the 82-90 K range.

HIGH-Tc superconductivity in perovskite oxides of the Y-Ba-Cu-O system

Several biphasic compositions of the type Y3-xBa3+xCu6O14 show an onset of superconductivity in the 90-115K range, attaining zero resistance in the 70-85K range. The phase responsible for superconductivity in these compositions is a perovskite oxide of composition YBa2Cu3 O7. This oxide annealed in oxygen shows the onset of superconductivity at 120K and zero resistance at 87K. YBa2,Cu3O7 shows the highest Meissner effect of all oxide superconductors. The superconducting behaviour of the two perovskite oxides, Y0.95Ba1.95,Cu3O7 and Y1.05Ba1.95Cu3O7 show interesting features; a marked decrease in resistivity is observed from room temperature itself in the former oxide with zero resistance at 89K. Electron microscopy and infrared spectra of these oxides are briefly discussed.

Mechanism of catalytic activity of metal oxides and chromites on ammonium perchlorate pyrolysis

This study investigates the mechanism of action of transition metal chromites on the decomposition of ammonium perchlorate.

HNbWO6 and HTaWO6: Novel oxides related to ReO3 formed by ion exchange of rutile-type LiNbWO6 and LiTaWO6

Both LiNbWO6 and LiTaWO6 undergo ion exchange in hot aqueous H2SO4 yielding the hydrates HMWO6 · H2O (M = Nb or Ta). The reaction is accompanied by a structural transformation from the rutile to the ReO3 structure. The cell constants are a = 3.783(3)Å for HNbWO6 · H2O and a = 3.785(5)Å for HTaWO6 · H2O. The ReO3 structure is retained by the dehydration products HMWO6 and MWO5.5 as well. HMWO6 phases yield H1+xMWO6 hydrogen bronzes on exposure to hydrogen in the presence of platinum catalyst.

Studies on vacuum pyrolysis of ammonium perchlorate and ammonium perchlorate/polystyrene propellant in the presence of transition metal oxides

Vacuum pyrolysis of ammonium perchlorate (AP) and ammonium perchlorate/polystyrene (PS) propellant has been studied by differential thermal analysis (DTA) in order to observe the effect of transition metal oxides on sublimation. Sublimation and decomposition being competitive processes, their proportions depend on the pressure of the pyrolysis chamber. The enthalpies for complete decomposition and complete sublimation are available from the literature and by using these data together with DTA area measurements, the extents of sublimation and decomposition have been calculated for AP and the propellant system. The effect of the metal ions on the extent and rate of sublimation depends on their nature. For AP the extent of sublimation increases with a decrease in particle size. For the propellants the powder sublimes more readily than the bulk material, but in the presence of metal ions the bulk material sublimes more readily than the powder. To substantiate this finding, the effect of MnO2 on AP sublimation as a function of particle size was examined, and it was observed that the extent of sublimation decreases as the particle size decreases.

The role of transition metal oxides in the decomposition and explosion of arylammonium perchlorates

The influence of MnO2, CuO, and NiO on the thermal decomposition and explosivity of arylammonium perchlorates has been studied by differential thermal analysis (DTA) and explosive sensitivity measurements. The metal oxides considerably sensitize both decomposition and explosion and the sensitizing effect is in the order NiO < CuO < MnO2. The accelerated decomposition or explosion seems to occur via the formation of an intermediate, metal perchlorate arylamine complex. The experimental evidence for the mechanism put forward has been included.