Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

The role of carbon surface chemistry in N2O conversion to N2 over Ni catalyst supported on activated carbon

The effect of acidic treatments on N2O reduction over Ni catalysts supported on activated carbon was systematically studied. The catalysts were characterized by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). It is found that surface chemistry plays an important role in N2O-carbon reaction catalyzed by Ni catalyst. HNO3 treatment produces more active acidic surface groups such as carboxyl and lactone, resulting in a more uniform catalyst dispersion and higher catalytic activity. However, HCl treatment decreases active acidic groups and increases the inactive groups, playing an opposite role in the catalyst dispersion and catalytic activity. A thorough discussion of the mechanism of the N2O catalytic reduction is made based upon results from isothermal reactions, temperature-programmed reactions (TPR) and characterization of catalysts. The effect of acidic treatment on pore structure is also discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

Indirect Emissions from Biofuels: How Important?

A global biofuels program will lead to intense pressures on land supply and can increase greenhouse gas emissions from land-use changes. Using linked economic and terrestrial biogeochemistry models, we examined direct and indirect effects of possible land-use changes from an expanded global cellulosic bioenergy program on greenhouse gas emissions over the 21st century. Our model predicts that indirect land use will be responsible for substantially more carbon loss ( up to twice as much) than direct land use; however, because of predicted increases in fertilizer use, nitrous oxide emissions will be more important than carbon losses themselves in terms of warming potential. A global greenhouse gas emissions policy that protects forests and encourages best practices for nitrogen fertilizer use can dramatically reduce emissions associated with biofuels production.

Denitrification, leaching and immobilisation of N-15-labelled nitrate in winter under windrowed harvesting residues in hoop pine plantations of 1-3 years old in subtropical Australia

A field study was carried out to investigate the impacts of windrowed harvesting residues on denitrification, immobilisation and leaching of N-15-labelled nitrate applied at 20 kg N ha(-1) to microplots in second-rotation hoop pine (Araucaria cunninghamii) plantations of 1-3 years old in southeast Queensland, Australia. The PVC microplots were 235 mm in diameter and 150 mm. long, and driven into the 100 mm soil. There were three replications of such microplots for each of the six treatments which were areas just under and between 1-, 2- and 3-year-old windrows of harvesting residues. Based on gaseous N losses estimated by the difference between the recoveries of bromide (Br) applied at 100 kg Br ha(-1) and N-15-labelled nitrate, denitrification was highest (23% based on N-15 loss) in the areas just under the 1-year-old windrows 25 days after a simulated 75 mm rainfall and following several natural rainfall events. There was no significant difference in N-15 losses (14-17%) among the other treatments. The N-15 immobilisation rate was highest for microplots in the areas between the 1-year-old windrows and generally higher for microplots in the areas just under the windrows (30-39%) than that (26-30%) between the windrows. Direct measurement of N-15 gas emissions (N-15(2) + (N2O)-N-15) confirmed that the highest denitrification rate occurred in the microplots under the 1-year-old windrows although the gaseous N-15 loss calculated by gas emission was only about one-quarter that estimated by the N-15 mass balance method. A significant, positive linear relationship (P < 0.05) existed between the gaseous N-15 losses measured by the two methods used. The research indicates that considerable mineral N could be lost via denitrification during the critical inter-rotation period and early phase of the second rotation. However, the impacts of windrowed harvesting residues on N losses via denitrification might only last for a period of about 2 years. Published by Elsevier Science B.V.

Fate of N-15-labelled nitrate in a wet summer under different residue management regimes in young hoop pine plantations

A field study was conducted to investigate the fate of N-15-labelled nitrate applied at 20 kg N ha(-1) in a wet summer to microplots installed in areas under different residue management regimes in second-rotation hoop pine (Araucaria cunninghamii) plantations aged 1-3 years in south-east Queensland, Australia. PVC microplots of 235 mm diameter and 300 mm long were driven into 250 mm soil. There were three replications of each of eight treatments. These were areas just under and between 1-year-old windrows (ca. 2-3 m in width) of harvesting residues spaced 15 m apart, and with and without incorporated foliage residues (20 t DM ha(-1)); the areas just under and between 2- or 3-year-old windrows spaced 10 m apart. Only 7-29% of the added N-15 was recovered from the top 750 mm of the soil profile with the leaching loss estimated to be 70-86% over the 34-day period. The N-15 loss via denitrification was 3.7-6.3% by directly measuring the N-15 gases emitted. The microplots with the incorporated residues at the 1-year-old site had the highest N-15 loss (6.3%) as compared with the other treatments. The N-15 mass balance method together with the use of bromide (Br) tracer applied at 100 kg Br ha(-1) failed to obtain a reliable estimate of the denitrification loss. The microplots at the 1-year-old site had higher N-15 immobilisation rate (7.5-24.7%) compared with those at 2- and 3-year-old sites (2.1-3.6%). Incorporating the residues resulted in an increase in N-15 immobilisation rate (24.5-24.7%) compared with the control without the incorporated residues (8.4-14.3%). These findings suggest that climatic conditions played important roles in controlling the N-15 transformations in the wet summer season and that the residue management regimes could also significantly influence the N-15 transformations. Most of the N-15 loss occurred through leaching, but a considerable amount of the N-15 was lost through denitrification. Bromide proved to be an unsuitable tracer for monitoring the N-15 leaching and movement under the wet summer conditions. (C) 2002 Elsevier Science B.V. All rights reserved.

Simultaneous nitrification, denitrification, and phosphorus removal in a lab-scale sequencing batch reactor

Simultaneous nitrification and denitrification (SND) via the nitrite pathway and anaerobic-anoxic-enhanced biological phosphorus removal (EBPR) are two processes that can significantly reduce the energy and COD demand for nitrogen and phosphorus removal. The combination of these two processes has the potential of achieving simultaneous nitrogen and phosphorus removal with a minimal requirement for COD. A lab-scale sequencing batch reactor (SBR) was operated in alternating anaerobic-aerobic mode with a low dissolved oxygen (DO) concentration (0.5 mg/L) during the aerobic period, and was demonstrated to accomplish nitrification, denitrification, and phosphorus removal. Under anaerobic conditions, COD was taken up and converted to poly-hydroxyalkanoates (PHAs), accompanied by phosphorus release. In the subsequent aerobic stage, PHA was oxidized and phosphorus was taken up to

Anemia Megaloblástica Aguda por Inalação de Óxido Nitroso em Doente com Patologia Autoimune Múltipla

As anemias megaloblásticas são habitualmente vistas como doenças crónicas de aparecimento insidioso. No entanto, um estado megaloblástico pode aparecer em apenas alguns dias devido à deficiência aguda de ácido fólico ou vitamina B12. Uma das causas mais comuns, embora pouco relatada, é acção tissular do óxido nitroso (NO2), substancia volátil utilizada comummente em anestesia. Efectivamente, o N02 inactiva a metilcobalamina, levando ao rápido desenvolvimento de uma hematopoiese megaloblástica. Este fenómeno pode ocorrer mesmo em doentes sem défice prévio de vitamina B12, sendo no entanto frequente e mais grave quando há um estado carencial de base. Apresentamos o caso clínico de uma doente com fractura do colo do fémur, que desenvolveu anemia aguda no pós-operatório cuja investigação permitiu identificar uma anemia pemiciosa latente e patologia tiroideia autoimune em doente com vitiligo desde longa data.

Enzymatic activity mastered by altering metal coordination spheres

J Biol Inorg Chem (2008) 13:1185–1195 DOI 10.1007/s00775-008-0414-3

Does nitrogen availability have greater control over the formation of tropical heath forests than water stress?A hypothesis based on nitrogen isotope ratios

Global scale analyses of soil and foliage δ15N have found positive relationships between δ15N and ecosystem N loss (suggesting an open N cycle) and a negative relationship between δ15N and water availability. We show here that soils and leaves from tropical heath forests are depleted in 15N relative to 'typical' forests suggesting that they have a tight N cycle and are therefore limited by N rather than by, often suggested, water availability.

Estudi de les càrregues ambientals del compostatge casolà. Simulació d'un sistema de compostatge domèstic i determinació d'emissions de gasos contaminants

Aquest treball s’enfoca cap l’anàlisi de les emissions de gasos amb un potencial impacte negatiu sobre l’entorn que es poden emetre a l’atmosfera durant el compostatge casolà com són el metà i l’òxid nitrós pel seu paper de gasos d’efecte hivernacle i l’amoníac, però sense oblidar el seguiment dels paràmetres del procés en si i la determinació de la qualitat del compost produït. Durant poc més de 6 mesos s’ha simulat un sistema de compostatge casolà tal i com podria donar‐se en un domicili particular i s’ha confirmat la seva eficàcia en la reducció en pes del residu tractat així com l’obtenció d’un producte final altament estable i d’una qualitat més que acceptable. Pel que fa a les emissions de gasos, les quantitats determinades no són menyspreables. L’experiment s’ha realitzat per triplicat. Les emissions són molt erràtiques i no s’han trobat patrons clars en la seva evolució durant el procés de compostatge més enllà d’una certa correlació entre les emissions d’amoníac i la diferència de temperatures entre l’ambient i l’interior dels compostadors. Cal destacat un elevat grau de biaix en la determinació d’emissions gasoses a petita escala, com és el cas del compostatge casolà. Finalment constatar que la generació de lixiviats en el compostatge domèstic pot ser important donat el contingut en aigua de la matèria orgànica tractada a nivell casolà i el limitat accés a material estructurant sec que es té per a compensar‐les.

Anaerobic activation of the entire denitrification pathway in Pseudomonas aeruginosa requires Anr, an analog of Fnr.

The Pseudomonas aeruginosa gene anr, which encodes a structural and functional analog of the anaerobic regulator Fnr in Escherichia coli, was mapped to the SpeI fragment R, which is at about 59 min on the genomic map of P. aeruginosa PAO1. Wild-type P. aeruginosa PAO1 grew under anaerobic conditions with nitrate, nitrite, and nitrous oxide as alternative electron acceptors. An anr deletion mutant, PAO6261, was constructed. It was unable to grow with these alternative electron acceptors; however, its ability to denitrify was restored upon the introduction of the wild-type anr gene. In addition, the activities of two enzymes in the denitrification pathway, nitrite reductase and nitric oxide reductase, were not detectable under oxygen-limiting conditions in strain PAO6261 but were restored when complemented with the anr+ gene. These results indicate that the anr gene product plays a key role in anaerobically activating the entire denitrification pathway.

CO2, CH4 and N2O fluxes in an Ultisol treated with sewage sludge and cultivated with castor bean

Organic residue application into soil alter the emission of gases to atmosphere and CO2, CH4, N2O may contribute to increase the greenhouse effect. This experiment was carried out in a restoration area on a dystrophic Ultisol (PVAd) to quantify greenhouse gas (GHG) emissions from soil under castor bean cultivation, treated with sewage sludge (SS) or mineral fertilizer. The following treatments were tested: control without N; FertMin = mineral fertilizer; SS5 = 5 t ha-1 SS (37.5 kg ha-1 N); SS10 = 10 t ha-1 SS (75 kg ha-1 N); and SS20 = 20 t ha-1 SS (150 kg ha-1 N). The amount of sludge was based on the recommended rate of N for castor bean (75 kg ha-1), the N level of SS and the mineralization fraction of N from SS. Soil gas emission was measured for 21 days. Sewage sludge and mineral fertilizers altered the CO2, CH4 and N2O fluxes. Soil moisture had no effect on GHG emissions and the gas fluxes was statistically equivalent after the application of FertMin and of 5 t ha-1 SS. The application of the entire crop N requirement in the form of SS practically doubled the Global Warming Potential (GWP) and the C equivalent emissions in comparison with FertMin treatments.

Nitrogen fluxes from irrigated common‑bean as affected by mulching and mineral fertilization

The objective of this work was to measure the fluxes of N2O‑N and NH3‑N throughout the growing season of irrigated common‑bean (Phaseolus vulgaris), as affected by mulching and mineral fertilization. Fluxes of N2O‑N and NH3‑N were evaluated in areas with or without Congo signal grass mulching (Urochloa ruziziensis) or mineral fertilization. Fluxes of N were also measured in a native Cerrado area, which served as reference. Total N2O‑N and NH3‑N emissions were positively related to the increasing concentrations of moisture, ammonium, and nitrate in the crop system, within 0.5 m soil depth. Carbon content in the substrate and microbial biomass within 0.1 m soil depth were favoured by Congo signal grass and related to higher emissions of N2O‑N, regardless of N fertilization. Emission factors (N losses from the applied mineral nitrogen) for N2O‑N (0.01-0.02%) and NH3‑N (0.3-0.6%) were lower than the default value recognized by the Intergovernmental Panel on Climate Change. Mulch of Congo signal grass benefits N2O‑N emission regardless of N fertilization.

Ensimmäisen ja toisen sukupolven nestemäisten liikennebiopolttoaineiden kasvihuonekaasupäästöjenvertailu

Elinkaariarviointia voidaan käyttää ensimmäisen ja toisensukupolven nestemäisten liikennebiopolttoaineiden kasvihuonekaasupäästöjen ja primäärienergian kulutuksen vertailuun. Elinkaariarviointia käyttämällä pyritään tuottamaan luotettavaa tietoa koko elinkaaren ajalta. Nestemäisiä liikennebiopolttoaineita käsittelevissä tutkimuksissa elinkaari jaetaan yleensä kahteen osaan,joista suurempi painoarvo on elinkaaren alkuosalla. Tässä diplomityössä tehdään yksinkertaistettu elinkaariarviointi selluloosaetanolin ja Fischer-Tropsch-dieselin elinkaaren alkuosalle ja verrataan niitä sitten ohraetanoliin ja rypsimetyyliesteriin. Tässä työssä keskitytään primäärienergian kulutukseen sekä hiilidioksidi-, metaani- ja dityppioksidipäästöihin. Selluloosaetanolin raaka-aineena tarkasteltiin ruokohelpeä, Fischer-Tropsch-dieselin raaka-aineena metsätähdettä. Diplomityö osoitti, että toisen sukupolven nestemäisten liikennebiopolttoaineiden tuotannossa kuluu vähemmän primäärienergiaa ja syntyy vähemmän kasvihuonekaasupäästöjä kuin ensimmäisen sukupolven nestemäisten liikennebiopolttoaineiden tuotannossa. Sama tulos on saatu myös muissa aihetta käsittelevissä tutkimuksissa.