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.     

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.     

Low temperature selective catalytic reduction of NO by NH3 over V2O5 supported on TiO2–SiO2–MoO3

The V₂O₅ catalysts supported on TiO₂–SiO₂–MoO₃ (TSM) prepared by the coprecipitation method were investigated for the selective catalytic reduction (SCR) of NO by NH₃ at low temperatures. The V₂O₅/TSM catalyst with 7–13 wt% SiO₂ was found to exhibit a superior SCR activity and a good sulfur tolerance at low temperatures (<250 °C). The presence of highly active polymeric vanadates formed by the incorporation of MoO₃ to TiO₂–SiO₂ and superior redox properties seems to enhance SCR activity, and furthermore the very lower SO₂ oxidation activity due to the higher acidity leads to the remarkable improvement of sulfur tolerance.     

Wire-mesh honeycomb catalysts for selective catalytic reduction of NO with NH3

Both flat and corrugated wire mesh sheets were coated with aluminum powder by using electrophoretic deposition (EPD) method. Controlled thermal sintering of coated samples yielded uniform porous aluminum layer with a thickness of 100 μm that was attached firmly on the wire meshes. Subsequent controlled calcination formed a finite thickness of Al₂O₃ layer on the outer surface of each deposited aluminum particles, which resulted in the formation of Al₂O₃/Al double-layered composite particles that were attached firmly on the wire surface to form a certain thickness of porous layer. A rectangular-shaped wire-mesh honeycomb (WMH) module with triangular-shaped channels was manufactured by packing alternately the flat sheet and corrugated sheet of the Al₂O₃/Al-coated wire meshes. This WMH was further coated with V₂O₅-MoO₃-WO₃ catalyst by wash-coating method to be applied for the selective catalytic reduction (SCR) of NO with NH₃. With an optimized catalyst loading of 16 wt%, WMH catalyst module shows more than 90% NO conversion at 240 °C and almost complete NO conversion at temperatures higher than 300 °C at GHSV 5,000 h⁻¹. When compared with conventional ceramic honeycomb catalyst, WMH catalyst gives NO conversion higher by 20% due to reduced mass transfer resistance by the existence of three dimensional opening holes in WMH.     

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.     

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.     

An assessment of N loss from agricultural fields to the environment in China

Using the 1997 IPCC Guidelines for National Greenhouse Gas Inventory Methodology, and statistical data from the China Agricultural Yearbook, we estimated that the direct N₂O emission from agricultural fields in China in 1990 was 0.282 Tg N. Based on micro-meteorological field measurement of NH₃ volatilization from agricultural fields in different regions and under different cropping systems, the total NH₃ volatilization from agricultural fields in China in 1990 was calculated to be 1.80 Tg N, which accounted for 11% of the applied synthetic fertilizer N. Ammonia volatilization from agricultural soil was related to the cropping system and the form of N fertilizer. Ammonia volatilization from paddy fields was higher than that from uplands, and NH₄HCO₃ had a higher potential of NH₃ volatilization than urea. N loss through leaching from uplands in north China accounted for 0.5–4.2% of the applied synthetic fertilizer N. In south China, the leaching of applied N and soil N from paddy fields ranged from 6.75 to 27.0 kg N ha^-1 yr^-1, while N runoff was between 2.45 and 19.0 kg N ha^-1 yr^-1.     

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.     

The Synergistic Effect of Adsorption-Photocatalysis for Removal of Organic Pollutants on Mesoporous Cu2V2O7/Cu3V2O8/g-C3N4 Heterojunction

Cu₂V₂O₇/Cu₃V₂O₈/g-C₃N₄ heterojunctions (CVCs) were prepared successfully by the reheating synthesis method. The thermal etching process increased the specific surface area. The formation of heterojunctions enhanced the visible light absorption and improved the separation efficiency of photoinduced charge carriers. Therefore, CVCs exhibited superior adsorption capacity and photocatalytic performance in comparison with pristine g-C₃N₄ (CN). CVC-2 (containing 2 wt% of Cu₂V₂O₇/Cu₃V₂O₈) possessed the best synergistic removal efficiency for removal of dyes and antibiotics, in which 96.2% of methylene blue (MB), 97.3% of rhodamine B (RhB), 83.0% of ciprofloxacin (CIP), 86.0% of tetracycline (TC) and 80.5% of oxytetracycline (OTC) were eliminated by the adsorption and photocatalysis synergistic effect under visible light irradiation. The pseudo first order rate constants of MB and RhB photocatalytic degradation on CVC-2 were 3 times and 10 times that of pristine CN. For photocatalytic degradation of CIP, TC and OTC, it was 3.6, 1.8 and 6.1 times that of CN. DRS, XPS VB and ESR results suggested that CVCs had the characteristics of a Z-scheme photocatalytic system. This study provides a reliable reference for the treatment of real wastewater by the adsorption and photocatalysis synergistic process.     

Photocatalytic reduction of N2O on metal-supported TiO2 powder at room temperature in the presence of H2O and CH3OH vapor

Ag- and Cu-supported TiO₂ photocatalysts showed high activity for the reduction of N₂O to N₂ at room temperature in the presence of CH₃OH and H₂O vapor. The suppression by H₂O on the activity was not observed in the present photocatalyst system. The remarkable behavior of the Ag and Cu co-catalysts for TiO₂ photocatalysts agreed well with that of electro- and thermal catalyses. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Highly Efficient Fe-silicalite Zeolite in Direct Propane Ammoxidation with N2O and O2

A novel process for the direct ammoxidation of propane over steam-activated Fe-silicalite at 723–823 K is reported. Yields of acrylonitrile (ACN) and acetonitrile (AcCN) below 5% were obtained using N₂O or O₂ as the oxidant. Co-feeding N₂O and O₂ boosts the performance of Fe-silicalite compared to the individual oxidants, leading to AcCN yields of 14% and ACN yields of 11% (propane conversions of 40% and products selectivity of 25–30%). The beneficial effect of O₂ on the propane ammoxidation with N₂O contrasts with other N₂O-mediated selective oxidations over iron-containing zeolites (e.g. hydroxylation of benzene and oxidative dehydrogenation of propane), where a small amount of O₂ in the feed dramatically reduces the selectivity to the desired product. It is shown that the productivity of ACN and especially AcCN, expressed as mol product h⁻¹ kg_cat⁻¹, is significantly higher over Fe-silicalite than over active propane ammoxidation catalysts reported in the literature. Our results open new perspectives to improve the performance of alkane ammoxidation catalysts.     

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.     

NH3 removal using the dielectric barrier discharge plasma-V-TiO2 photocatalytic hybrid system

This study investigates the photocatalytic performance of V-TiO₂ for removal of highly concentrated ammonia (1,000 ppm) in the dielectric barrier discharge (DBD), plasma-photocatalytic, hybrid system. The V (1.0, 5.0, 10.0 mol-%)-TiO₂ photocatalysts were prepared by using the conventional sol-gel method. Their surface areas were decreased with increasing vanadium component. The UV-visible absorption band slightly shifted to more visible wavelengths in V-TiO₂ compared to that in pure TiO₂. The NH₃-TPD result confirmed that the ability of NH₃ adsorption on the surface of V-TiO₂ increased with increasing vanadium content, and was maximized for 5.0-mol% V-TiO₂. The NH₃ decomposition was enhanced with the photocatalyst compared to the decomposition rate without catalysts, while the decomposition was further increased with the applied plasma voltage. The NH₃ decomposition reached 90% after 400 min at an applied plasma voltage of 10.0 kV, and various intermediates, such as-NH₂,-NH, and NO, were also identified by using the Fourier transform infrared (FT-IR) spectra. In addition, the NH₃ decomposition reached 100% in the plasma-5.0 mol% V-TiO₂, photocatalytic, hybrid system after 25 min, compared to 98% in the pure V-TiO₂ photocatalytic system after 150 min. In addition, the various undesirable byproducts were depressed when V-TiO₂ photocatalyst was used compared to that in the non-catalytic system.     

Isotopic Study of N2O Decomposition on an Ion-Exchanged Fe-Zeolite Catalyst: Mechanism of O2 Formation

N₂O decomposition on an ion-exchanged Fe-MFI catalyst has been studied using an ¹⁸O-tracer technique in order to reveal the reaction mechanism. N₂ ¹⁶O was pulsed onto an ¹⁸O₂-treated Fe-MFI catalyst at 693 K, and the O₂ molecules produced were monitored by means of mass spectrometry. The ¹⁸O fraction in the produced oxygen had almost half the value of that on the surface oxygen, and ¹⁸O¹⁸O was not detected. The result shows that O₂ formation proceeds via the Eley–Rideal mechanism (N₂ ¹⁶O + ¹⁸O(a) N₂ + ¹⁶O¹⁸O).     

亚硝酸盐对聚磷菌反硝化除磷代谢及N2O产生的影响

以乙酸钠/丙酸交替为碳源的强化生物除磷(enhance biological phosphorus removal, EBPR)系统为研究对象,母反应器内种泥在厌氧/好氧的运行条件下已培养340 d,聚磷菌富集纯度达到92%±3%,考察了不同浓度亚硝酸盐氮(44.64、70.3、94.33、112.36 mg NO₂^--N·L^-1)为电子受体对聚磷菌缺氧吸磷代谢的影响。结果表明,从未经缺氧驯化的高纯度聚磷菌也可以进行反硝化除磷代谢。在缺氧反应过程中NO₂^--N还原速率、PO₄^3--P吸收速率、PHA降解速率随着亚硝酸浓度升高呈下降趋势,但是在初始亚硝酸盐氮浓度最高为112.36 mg NO₂^--N·L^-1条件下,代谢并未停止,此时亚硝酸盐还原速率与磷酸盐吸收速率仍可以分别达到2.61 mg NO₂^--N·(g MLSS)^-1·h^-1和3.0 mg PO₄^3--P·(g MLSS)^-1·h^-1。聚磷菌在以细胞内PHA作为碳源以NO₂^--N作为电子受体反硝化除磷代谢过程中,由于初始亚硝酸盐的抑制作用使NO₂^--N还原速率大于N₂O还原速率,从而产生大量的N₂O积累。初始投加NO₂^--N浓度为44.64、70.3、94.33、112.36 mg NO₂^--N·L^-1时,产生的N₂O占TN的比例分别为63.5%、49.0%、30.2%、24.0%。在底物充足的条件下,代谢中积累的N₂O可以通过延长缺氧搅拌时间,使其转化为N₂。     

Two-year field study on the emission of N2O from coarse and middle-textured Belgian soils with different land use

In the following study N₂O emissions from 3 different grasslands and from 3 different arable lands, representing major agriculture areas with different soil textures and normal agricultural practices in Belgium, have been monitored for 1 to 2 years. One undisturbed soil under deciduous forest was also included in the study. Nitrous oxide emission was measured directly in the field from vented closed chambers through photo-acoustic infrared detection. Annual N₂O emissions from the arable lands ranged from 0.3 to 1.5 kg N ha⁻¹ y⁻¹ and represent 0.3 to 1.0% of the fertilizer N applied. Annual N₂O emissions from the intensively managed grasslands and an arable land sown with grass were significantly larger than those from the cropped arable lands. Emissions ranged from 14 to 32 kg N ha⁻¹ y⁻¹, representing fertilizer N losses between 3 and 11%. At the forest soil a net N₂O uptake of 1.3 kg N₂O-N ha⁻¹ was recorded over a 2-year period. It seems that the N₂O-N loss per unit of fertilizer N applied is larger for intensively managed and heavily fertilized (up to 500 kg N ha⁻¹) grasslands than for arable lands and is substantially larger than the 1.25% figure used for the global emission inventory. Comparison of the annual emission fluxes from the different soils also indicated that land use rather than soil properties influenced the N₂O emission. Our results also show once again the importance of year-round measurements for a correct estimate of N₂O losses from agricultural soils: 7 to 76% of the total annual N₂O was emitted during the winter period (October–February). Disregarding the emission during the off-season period can lead to serious underestimation of the actual annual N₂O flux. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3)PbI3

A new nanocrystalline sensitizer with the chemical formula (CH₃CH₂NH₃)PbI₃ is synthesized by reacting ethylammonium iodide with lead iodide, and its crystal structure and photovoltaic property are investigated. X-ray diffraction analysis confirms orthorhombic crystal phase with a = 8.7419(2) Å, b = 8.14745(10) Å, and c = 30.3096(6) Å, which can be described as 2 H perovskite structure. Ultraviolet photoelectron spectroscopy and UV-visible spectroscopy determine the valence band position at 5.6 eV versus vacuum and the optical bandgap of ca. 2.2 eV. A spin coating of the CH₃CH₂NH₃I and PbI₂ mixed solution on a TiO₂ film yields ca. 1.8-nm-diameter (CH₃CH₂NH₃)PbI₃ dots on the TiO₂ surface. The (CH₃CH₂NH₃)PbI₃-sensitized solar cell with iodide-based redox electrolyte demonstrates the conversion efficiency of 2.4% under AM 1.5 G one sun (100 mW/cm²) illumination.     

Selective catalytic reduction of NO by NH3 on Cu (II) ion-exchanged offretite prepared by different methods

The influence of the preparation method on the NO–SCR by NH₃ activity of Cu-OFF catalysts has been studied on presence of oxygen. The catalysts structure and the nature of copper species have been investigated by XRD, ²⁷Al MAS NMR, UV-visible spectroscopy and H₂-TPR. Among the examined preparation methods, the ionic exchange in aqueous solution gives the highest efficient catalyst in NO-SCR. It is shown that Cu cationic species are formed in large extent with this method despite the presence of minor amounts of small oxide clusters.     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.