Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.

Downstream emissions of CH4 and CO2 from hydroelectric reservoirs (Tucuruí, Samuel, and Curuá-Una) in the Amazon basin.

Carbon dioxide (CO2) and methane (CH4) generated in reservoirs are released downstream of dams, and few studies have considered these downstream emissions. Fluxes downstream of 3 Amazon hydroelectric reservoirs (Tucuruí, Samuel, and Curuá-Una) are reported here. Degassing through turbines was calculated as the difference between intake and outflow concentrations. Additional releases along the Tocantins, Jamari, and Curuá rivers were measured at were liberated at the turbine outflow. The total downstream emissions are sufficiently large to require consideration in assessments of greenhouse gas emissions from hydroelectric reservoirs.

Efeito da aplicação de diferentes pré-tratamentos na gasificação de cepos de Eucalyptus globulus. Densificação, torrefação e torrefação combinada com densificação

Mestrado em Engenharia Florestal e dos Recursos Naturais - Instituto Superior de Agronomia - UL

Composting of different agro-food wastes: Effects of the phenolic and lignocellulosic fractions on greenhouse gases emissions

Currently, society faces a number of challenges related to the large amounts of organic wastes generated and accumulated by the increasing expansion of agroindustrial activities1. Most of these wastes are rich in lignocellulosic compounds, which represents a major fraction of all plant biomass (of above 90%), so, its degradation is crucial for global carbon cycle2. These organic wastes may be introduced directly on agriculture sector as soil organic amendment, however, these might contain phytochemicals, such as phenolic compounds which may introduce toxic effects to soil and to beneficial organisms. Transformation and degradation of these renewable organic wastes into composts (COMPOSTING) is a possible solution for these problems and an environmentally friendly processes that allows make use of natural resources efficiently3. The main potential handicap is generation and emission of greenhouse gases such as carbon dioxide (CO2 ), methane (CH4 ) and nitrous oxide (N2O) and another ones which may led serious problems like nitric oxide (NO) and ammonia (NH3) 4. For this reason, quantification of GHG emissions from composting and finding possible relations with the chemical and structural composition of the wastes used is crucial to the development of technologies for mitigating emissions and should help to make decisions concerning waste management.

Dairy cattle-slurry treatment technologies: towards an integrating approach of crop production, animal feeding and environmental impacts

Dairy cattle farms have a well-known environmental impact that affects all ecological compartments: air, soil, water and biosphere [1]. Dairy cattle farming are a significant source of anthropogenic gases from enteric fermentation, manure storage and land application, mainly ammonia (NH3), nitric oxide (NO), nitrous oxide (N2O), carbon dioxide (CO2) and methane (CH4). The emission of such gases represents not only an environmental problem but also leads to energy and nitrogen (N) losses in ruminant production systems [2-5]. Several efforts are required on the development of new technologies and strategies that mitigate gaseous emissions, N losses and improve the efficiency of the energy and N cycles [6, 7]. In the Northwest of Portugal, dairy cattle production has a major impact on the economy, with strong repercussions at national scale. Therefore, our Ph.D. thesis project aims to: a) Study natural supplements as additives in the dairy cattle diet towards a decrease in GHG emissions from feeding operations; b) Compare commercial dairy cattle diets with and without additives on gaseous emissions from manure deposited in a simulated concrete floor; c) Assess the concentrations and emissions of NH3 and greenhouse gases from commercial dairy cattle facilities; d) Evaluate the effects of different additives on lowering gaseous emissions from dairy cattle excreta, using a laboratory system simulating a dairy house concrete floor.

A comparative study of the structural, mechanical and tribological characteristics of TiSiC-Cr coatings prepared in CH4 and C2H2 reactive atmosphere by cathodic vacuum arc

TiSiC-Cr coatings, with Cr and Si as additional elements, were deposited on Si, C 45 and 316 L steel substrates via cathodic arc evaporation. Two series of coatings with thicknesses in the range of 3.6–3.9 μm were produced, using either CH4 or C2H2 as carbon containing gas. For each series, different coatings were prepared by varying the carbon rich gas flow rate between 90 and 130 sccm, while maintaining constant cathode currents (110 and 100 A at TiSi and Cr cathodes, respectively), substrate bias (–200 V) and substrate temperature (∼320 °C). The coatings were analyzed for their mechanical characteristics (hardness, adhesion) and tribological performance (friction, wear), along with their elemental and phase composition, chemical bonds, crystalline structure and cross-sectional morphology. The coatings were found to be formed with nano-scale composite structures consisting of carbide crystallites (grain size of 3.1–8.2 nm) and amorphous hydrogenated carbon. The experimental results showed significant differences between the two coating series, where the films formed from C2H2 exhibited markedly superior characteristics in terms of microstructure, morphology, hardness, friction behaviour and wear resistance. For the coatings prepared using CH4, the measured values of crystallite size, hardness, friction coefficient and wear rate were in the ranges of 7.2–8.2 nm, 26–30 GPa, 0.3–0.4 and 2.1–4.8 × 10−6 mm3 N−1 m−1, respectively, while for the coatings grown in C2H2, the values of these characteristics were found to be in the ranges of 3.1–3.7 nm, 41–45 GPa, 0.1–0.2 and 1.4–3.0 × 10−6 mm3 N−1 m−1, respectively. Among the investigated coatings, the one produced using C2H2 at the highest flow rate (130 sccm) exhibited the highest hardness (45.1 GPa), the lowest friction coefficient (0.10) and the best wear resistance (wear rate of 1.4 × 10−6 mm3 N−1 m−1).

Efluxo de metano (CH4) em dois solos do RS sob cultivo de arroz irrigado por alagamento.

O aumento da concentração de gases na atmosfera, decorrente da atividade humana, gera um aceleramento significativo do efeito estufa. Dentre os gases, o metano (CH4) é um dos que têm grande potencial em causar o efeito estufa, destacando-se como fonte geradora as áreas de várzea cultivadas com arroz irrigado por alagamento. Estima-se que estas áreas têm contribuído com até 45% da emissão de CH4 de origem antropogênica. O objetivo deste trabalho foi avaliar o efluxo de CH4 em dois solos, cultivados com arroz irrigado, no Estado do RS. O primeiro local avaliado foi uma lavoura na área experimental da Universidade Federal de Santa Maria (UFSM), Santa Maria - RS e o segundo na Estação Experimental do Arroz no Instituto Rio Grandense do Arroz (IRGA), Cachoeirinha - RS. Durante a safra do arroz realizaram-se coletas semanais de amostras de ar em câmaras coletoras com o auxílio de seringas plásticas de polipropileno aos 5, 10, 15, 20 e 25 minutos após o fechamento da câmara. Durante as coletas, foi registrada a temperatura do ar, da água de alagamento e do solo (0,05m de profundidade) para o cálculo das emissões. Os picos de emissão de CH4 em Santa Maria e Cachoeirinha ocorreram, respectivamente, aos 30 e 69 dias após o alagamento do solo, sendo que em Cachoeirinha os picos de emissão tiveram menor intensidade. O desencontro entre os picos de máxima emissão nas duas unidades de coleta e a menor intensidade de emissão na unidade de Cachoeirinha pode estar associado com as características dos solos, temperatura, como também, pelo uso de diferentes cultivares de arroz irrigado. Existe a necessidade de se conhecer melhor os fatores que influenciam as taxas de emissão de metano como também avaliar formas de manejo da cultura visando uma menor emissão deste gás, reduzindo os impactos da rizicultura sobre o efeito estufa.

A new sward management strategy to mitigate the methane (CH4) emissions by grazing ruminants.

2016

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

Vascular Response Of Ruthenium Tetraamines In Aortic Ring From Normotensive Rats.

Background: Ruthenium (Ru) tetraamines are being increasingly used as nitric oxide (NO) carriers. In this context, pharmacological studies have become highly relevant to better understand the mechanism of action involved. Objective: To evaluate the vascular response of the tetraamines trans-[RuII(NH3)4(Py)(NO)]3+, trans-[RuII(Cl)(NO) (cyclan)](PF6)2, and trans-[RuII(NH3)4(4-acPy)(NO)]3+. Methods: Aortic rings were contracted with noradrenaline (10-6 M). After voltage stabilization, a single concentration (10-6 M) of the compounds was added to the assay medium. The responses were recorded during 120 min. Vascular integrity was assessed functionally using acetylcholine at 10-6 M and sodium nitroprusside at 10-6 M as well as by histological examination. Results: Histological analysis confirmed the presence or absence of endothelial cells in those tissues. All tetraamine complexes altered the contractile response induced by norepinephrine, resulting in increased tone followed by relaxation. In rings with endothelium, the inhibition of endothelial NO caused a reduction of the contractile effect caused by pyridine NO. No significant responses were observed in rings with endothelium after treatment with cyclan NO. In contrast, in rings without endothelium, the inhibition of guanylate cyclase significantly reduced the contractile response caused by the pyridine NO and cyclan NO complexes, and both complexes caused a relaxing effect. Conclusion: The results indicate that the vascular effect of the evaluated complexes involved a decrease in the vascular tone induced by norepinephrine (10-6 M) at the end of the incubation period in aortic rings with and without endothelium, indicating the slow release of NO from these complexes and suggesting that the ligands promoted chemical stability to the molecule. Moreover, we demonstrated that the association of Ru with NO is more stable when the ligands pyridine and cyclan are used in the formulation of the compound.Fundamento: As tetra-aminas de rutênio cada vez mais se destacam como carreadoras da molécula de óxido nítrico. Desse modo, estudos farmacológicos tornam-se altamente relevantes, afim de melhor compreender o mecanismo de ação envolvido. Objetivo: Avaliar a resposta vascular das tetra-aminas trans-[RuII(NH3)4(Py)(NO)]3+, trans-[RuII(Cl)(NO)(Cyclan)](PF6)2 e trans-[RuII(NH3)4(4-acPy)(NO)]3+. Métodos: Anéis de aorta foram pré-contraídos com noradrenalina (10-6M). Após estabilização da tensão, concentração única (10-6M) dos compostos foi adicionada ao banho de incubação. As respostas foram registradas ao longo de 120 minutos. A integridade vascular foi avaliada funcionalmente (acetilcolina 10-6M; nitroprussiato de sódio 10-6M) e histologicamente Resultados: A análise histológica confirmou a presença ou não de células endoteliais nos tecidos analisados. Todos os complexos alteraram a resposta contrátil induzida pela noradrenalina, resultando em aumento de tônus seguido de efeito relaxante. Em anéis com endotélio, a inibição do óxido nítrico endotelial causou redução do efeito contrátil da piridina óxido nítrico. Não foram observadas respostas significativas em anéis com endotélio referente ao composto cyclan óxido nítrico. Por outro lado, em anéis sem endotélio, a inibição da guanilato ciclase reduziu significativamente a resposta contrátil dos complexos piridina óxido nítrico e cyclan óxido nítrico, levando ambos os compostos a um efeito relaxante. Conclusão: Os resultados obtidos demonstram que o efeito vascular dos complexos avaliados apresentaram diminuição no tônus vascular induzido pela noradrenalina (10-6M) ao final do tempo de incubação, em anéis com e sem endotélio, indicando liberação lenta da molécula de óxido nítrico do composto estudado e sugerindo que os ligantes causaram estabilidade química à molécula. Demonstramos que a ligação rutênio óxido nítrico é mais estável quando utilizamos os ligantes piridina e cyclan para a formulação do composto.

Changes in ruminal fermentation and mineral serum level in animals kept in high temperature environments

In order to evaluate the effect of environmental temperature on ruminal fermentation and on mineral levels of growing ruminants, it was used 12 male calves (initial average weight 82.9 ± 7.7 kg, 100 days of age), were employed in a randomized block design (by weight) experiment, with repeated weight measurement and two environmental temperatures: thermoneutral (24ºC) and heat-stressed (33ºC), during 38 days. The animals exposed to 33ºC presented lower dry matter ingestion, lower T3 (triiodothyronine) serum level, higher ammoniacal nitrogen (NH3-N) level in the rumen liquid, and higher rectal and body temperatures during all the experimental period when compared to the animals kept in thermoneutral environment (24ºC). The animals kept under heat stress environment (33ºC) presented higher calcium serum level, which was the highest on 31st day and the lowest on the 38th day of the experiment; phosphorus level was the lowest during all the experimental period; sodium level was lower on the 17th, 31st and 38th experimental days. Potassium and zinc levels were lower after 24 days; copper level was lower until the 24th day; magnesium level was higher until the 17th day, if compared to the ones from the animals kept in thermoneutral environment (24ºC). The heat-stressed animals presented higher levels of ammoniacal nitrogen in the ruminal liquid and a decrease in the phosphorus, sodium, potassium and zinc serum levels. These results show the necessity of changes on feed management to ruminants in temperatures over the thermal comfort limits so that performance loss is decreased.

Características de fermentação da silagem de seis variedades de milho indicadas para a região semiárida Brasileira

Avaliaram-se as características fermentativas e a qualidade das silagens de seis variedades de milho, de ciclos precoce e superprecoce - BRS Caatingueiro, BRS Assum Preto, BR 5033 Asa Branca, BR 5028 São Francisco, Gurutuba e BRS 4103 - indicadas para a região semiárida brasileira. Foram utilizados silos experimentais, em delineamento inteiramente ao acaso, com seis tratamentos (variedades) e quatro repetições. Avaliaram-se: matéria seca (MS), matéria orgânica (MO), proteína bruta (PB), fibra em detergente neutro (FDN), fibra em detergente ácido (FDA), extrato etéreo (EE), carboidratos totais (CHO), carboidratos não fibrosos (CNF), pH, nitrogênio amoniacal como parte do nitrogênio total (N-NH3/NT), ácidos orgânicos e digestibilidade in vitro da matéria seca (DIVMS) das silagens. Os valores médios encontrados para a silagem foram: MS= 28,7%; MO= 94,9%; PB= 8,3%; FDN= 49,9%; FDA= 27,5%; EE= 3,8%; CHO= 82,7%; CNF= 32,8%; pH= 3,8; N-NH3/NT= 2,9%/NT; ácido láctico = 7,6%; ácido acético = 0,6%; ácido butírico = 0,3% e DIVMS= 57,9%. As variedades BR 5028 - São Francisco e Gurutuba destacaram-se das demais em relação ao teor de matéria seca. A variedade BRS Caatingueiro apresentou maior teor de carboidratos não fibrosos em relação às demais. As silagens de todas as variedades foram classificadas como de excelente qualidade, por apresentarem potencial para ensilagem no semiárido brasileiro

Evaluation of elephant grass silage with the addition of cassava scrapings

The objective of this experiment was to evaluate the effects of adding cassava scrapings on gas and effluent losses, dry matter recovery, pH, contents of N-NH3, organic acids and volatile fatty acids and the bromatological composition of elephant grass silages. It was used a randomized complete design, with four levels of cassava scrapings (0, 7, 15 or 30% natural matter) each one with four replications per level. The grass was cut at 50 days of regrowth and ensiled in 15-L silos, equipped with a Bunsen valve to allow gas outflow. The gas losses decreased quadratically with the addition of cassava scrapings, whereas effluent losses decreased linearly. Dry matter recovery increased quadratically with the addition of cassava scrapings. Dry matter (DM) concentration increased but crude protein (CP), neutral detergent fiber (NDF), acid detergent fiber (ADF) and hemicellulose (HEM) decreased linearly with the addition of cassava scrapings. The pH value and lactic acid concentration increased quadratically with the addition of cassava scrapings. Contents of N-NH3 and butyric acid decreased quadratically with the addition of cassava scrapings, whereas acetic acid content decreased linearly. Addition of cassava scrapings reduced gas and effluent losses and improved the fermentation profile of elephant grass silages and the level of 7% already ensures this improvement.

Suplementação nitrogenada com ureia comum ou encapsulada sobre parâmetros ruminais de novilhos alimentados com feno de baixa qualidade

Foi realizado um experimento de suplementação com novilhos fistulados no rúmen com o objetivo de verificar a utilização de ureia encapsulada como fonte de nitrogênio de liberação mais lenta e uniforme ao longo do tempo, bem como seu efeito sobre a degradabilidade da parede celular do feno. Os tratamentos foram: Feno + sal mineralizado (SM); Feno + suplemento proteico com ureia comum (SU); Feno + suplemento proteico com ureia encapsulada fórmula 1 (UE1); e Feno + suplemento proteico com ureia encapsulada fórmula 2 (UE2). O volumoso utilizado foi feno de Tifton (Cynodon dactylon L.) de baixa qualidade (PB: 4,62% e FDN: 83,46%). Foram realizadas medidas de pH e N-NH3 ruminais e parâmetros de degradação ruminal da FDN do volumoso. Verificou-se efeito (P<0,05) da suplementação nitrogenada sobre a concentração de nitrogênio amoniacal no rúmen; no entanto, a ureia encapsulada não foi diferente (P>0,05) da ureia comum. Os valores de pH e degradabilidade in situ não foram afetados pelos tratamentos (P>0,05), ao serem comparados os suplementados ou não suplementados com proteína degradável no rúmen e ao serem comparadas fontes de nitrogênio não proteico. A ureia encapsulada não demonstrou superioridade sobre a ureia comum, provavelmente pela baixa eficiência da sua proteção. A utilização de ureia encapsulada e a suplementação de proteína degradável não foram eficientes em aumentar a degradabilidade da parede celular do volumoso utilizado.