Análise da combustão e emissões em motores a bio-diesel.

A rápida evolução do mercado automotivo, em função de maiores restrições sobre as emissões, impulsionou a utilização de várias alternativas para melhorias dos motores diesel, entre elas as mudanças nos seus componentes com o auxílio de ferramentas de modelagem e a utilização de combustíveis alternativos. As características dos combustíveis afetarão a queima e, assim, alteram os resíduos do processo de combustão. Novos combustíveis podem também ser utilizados como uma alternativa para veículos de gerações anteriores com o intuito de reduzir as emissões. Este estudo mostra os efeitos da utilização do Biodiesel B20 e do Biodiesel Amyris em motores de combustão interna. Para isso, foram realizados testes de motores em salas dinamométricas, e seus resultados confrontados e discutidos. Além disso, são abordados os efeitos do combustível no processo da combustão. Esta Dissertação está concentrada, principalmente, na emissão de NOx e de material particulado, que são poluentes mais restritivos perante a Legislação brasileira de emissões CONAMA P7.

(Table 1) Cadmium and nutrient concentration of surface waters sampled during POLARSTERN cruise ANT-XXIV/III

The High Nutrient Low Chlorophyll (HNLC) Southern Ocean plays a key role in regulating the biological pump and the global carbon cycle. Here we examine the efficacy of stable cadmium (Cd) isotope fractionation for detecting differences in biological productivity between regions. Our results show strong meridional Cd isotope and concentration gradients modulated by the Antarctic Fronts, with a clear biogeochemical divide located near 56°S. The coincidence of the Cd isotope divide with the Southern Boundary of the Antarctic Circumpolar Current (ACC),together with evidence for northward advection of the Cd signal in the ACC, demonstrate that Cd isotopes trace surface ocean circulation regimes. The relationships between Cd isotope ratios and concentrations display two negative correlations, separating the ACC and Weddell Gyre into two distinct Cd isoscapes. These arrays are consistent with Rayleigh fractionation and imply a doubling of the isotope effect due to biological consumption of Cd during water transport from the Weddell Gyre into the ACC. The increase in magnitude of Cd isotope fractionation can be accounted for by differences in the phytoplankton biomass, community composition, and their physiological uptake mechanisms in the Weddell Gyre and ACC, thus linking Cd isotope fractionation to primary production and the global carbon cycle.

Seawater carbonate chemistry, and Lithophyllum sp. and Feldmannia spp. coverage and dry weight during experiments, 2009

Climate-driven change represents the cumulative effect of global through local-scale conditions, and understanding their manifestation at local scales can empower local management. Change in the dominance of habitats is often the product of local nutrient pollution that occurs at relatively local scales (i.e. catchment scale), a critical scale of management at which global impacts will manifest. We tested whether forecasted global-scale change [elevated carbon dioxide (CO2) and subsequent ocean acidification] and local stressors (elevated nutrients) can combine to accelerate the expansion of filamentous turfs at the expense of calcifying algae (kelp understorey). Our results not only support this model of future change, but also highlight the synergistic effects of future CO2 and nutrient concentrations on the abundance of turfs. These results suggest that global and local stressors need to be assessed in meaningful combinations so that the anticipated effects of climate change do not create the false impression that, however complex, climate change will produce smaller effects than reality. These findings empower local managers because they show that policies of reducing local stressors (e.g. nutrient pollution) can reduce the effects of global stressors not under their governance (e.g. ocean acidification). The connection between research and government policy provides an example whereby knowledge (and decision making) across local through global scales provides solutions to some of the most vexing challenges for attaining social goals of sustainability, biological conservation and economic development.

Benthic cyanobacterial mat (BCM) abundance on samples from the coast of Curacao

Benthic cyanobacterial mats (BCMs) are impacting coral reefs worldwide. However, the factors and mechanisms driving their proliferation are unclear. We conducted a multi-year survey around the Caribbean island of Curaçao, which revealed highest BCM abundance on sheltered reefs close to urbanised areas. Reefs with high BCM abundance were also characterised by high benthic cover of macroalgae and low cover of corals. Nutrient concentrations in the water-column were consistently low, but markedly increased just above substrata (both sandy and hard) covered with BCMs. This was true for sites with both high and low BCM coverage, suggesting that BCM growth is stimulated by a localised, substrate-linked release of nutrients from the microbial degradation of organic matter. This hypothesis was supported by a higher organic content in sediments on reefs with high BCM coverage, and by an in situ experiment which showed that BCMs grew within days on sediments enriched with organic matter (Spirulina). We propose that nutrient runoff from urbanised areas stimulates phototrophic blooms and enhances organic matter concentrations on the reef. This organic matter is transported by currents and settles on the seabed at sites with low hydrodynamics. Subsequently, nutrients released from the organic matter degradation fuel the growth of BCMs. Improved management of nutrients generated on land should lower organic loading of sediments and other benthos (e.g. turf and macroalgae) to reduce BCM proliferation on coral reefs.

Ambient Air Quality Monitoring in Metropolitan City of Lagos, Nigeria

Twenty one sampling locations were assessed for carbon monoxide (CO), carbondioxide (CO2), oxygen (O2), sulphur dioxide (SO2), nitrogen dioxide (NO2), nitrogen oxide (NO), suspended particulate matter (SPM) and noise level using air pollutants measurement methods approved by ASTM for each specific parameter. All equipments and meters were all properly pre-calibrated before each usage for quality assurance. Findings of the study showed that measured levels of noise (61.4 - 101.4 dBA), NO (0.0 - 3.0 ppm), NO2 (0.0 - 3.0 ppm), CO (1.0 – 42.0 ppm) and SPM (0.14 – 4.82 ppm) in all sampling areas were quite high and above regulatory limits however there was no significant difference except in SPM (at all the sampling points), and noise, NO2 and NO (only in major traffic intersection). Air quality index (AQI) indicates that the ambient air can be described as poor for SPM, varied from good to very poor for CO, while NO and NO2 are very good except at major traffic intersection where they were both poor and very poor (D-E). The results suggest that strict and appropriate vehicle emission management, industrial air pollution control coupled with close burning management of wastes should be considered in the study area to reduce the risks associated with these pollutants.

Nitrogen fertilizer rate management as a nitrous oxide mitigation strategy: Development of a nitrous oxide emission reduction protocol (NERP)

Nitrous oxide (N2O) is a potent agricultural greenhouse gas (GHG). More than 50% of the global anthropogenic N2O flux is attributable to emissions from soil, primarily due to large fertilizer nitrogen (N) applications to corn and other non-leguminous crops. Quantification of the trade–offs between N2O emissions, fertilizer N rate, and crop yield is an essential requirement for informing management strategies aiming to reduce the agricultural sector GHG burden, without compromising productivity and producer livelihood. There is currently great interest in developing and implementing agricultural GHG reduction offset projects for inclusion within carbon offset markets. Nitrous oxide, with a global warming potential (GWP) of 298, is a major target for these endeavours due to the high payback associated with its emission prevention. In this paper we use robust quantitative relationships between fertilizer N rate and N2O emissions, along with a recently developed approach for determining economically profitable N rates for optimized crop yield, to propose a simple, transparent, and robust N2O emission reduction protocol (NERP) for generating agricultural GHG emission reduction credits. This NERP has the advantage of providing an economic and environmental incentive for producers and other stakeholders, necessary requirements in the implementation of agricultural offset projects.

Nitrogen fertilizer management for nitrous oxide (N2O) mitigation in intensive corn (Maize) production: an emissions reduction protocol for US Midwest agriculture

Nitrous oxide (N2O) is a major greenhouse gas (GHG) product of intensive agriculture. Fertilizer nitrogen (N) rate is the best single predictor of N2O emissions in row-crop agriculture in the US Midwest. We use this relationship to propose a transparent, scientifically robust protocol that can be utilized by developers of agricultural offset projects for generating fungible GHG emission reduction credits for the emerging US carbon cap and trade market. By coupling predicted N2O flux with the recently developed maximum return to N (MRTN) approach for determining economically profitable N input rates for optimized crop yield, we provide the basis for incentivizing N2O reductions without affecting yields. The protocol, if widely adopted, could reduce N2O from fertilized row-crop agriculture by more than 50%. Although other management and environmental factors can influence N2O emissions, fertilizer N rate can be viewed as a single unambiguous proxy—a transparent, tangible, and readily manageable commodity. Our protocol addresses baseline establishment, additionality, permanence, variability, and leakage, and provides for producers and other stakeholders the economic and environmental incentives necessary for adoption of agricultural N2O reduction offset projects.

Nitrous oxide emissions from fertilized, irrigated cotton (Gossypium hirsutum L.) in the Aral Sea Basin, Uzbekistan : influence of nitrogen applications and irrigation practices

Nitrous oxide emissions were monitored at three sites over a 2-year period in irrigated cotton fields in Khorezm, Uzbekistan, a region located in the arid deserts of the Aral Sea Basin. The fields were managed using different fertilizer management strategies and irrigation water regimes. N2O emissions varied widely between years, within 1 year throughout the vegetation season, and between the sites. The amount of irrigation water applied, the amount and type of N fertilizer used, and topsoil temperature had the greatest effect on these emissions. Very high N2O emissions of up to 3000 μg N2O-N m−2 h−1 were measured in periods following N-fertilizer application in combination with irrigation events. These “emission pulses” accounted for 80–95% of the total N2O emissions between April and September and varied from 0.9 to 6.5 kg N2O-N ha−1.. Emission factors (EF), uncorrected for background emission, ranged from 0.4% to 2.6% of total N applied, corresponding to an average EF of 1.48% of applied N fertilizer lost as N2O-N. This is in line with the default global average value of 1.25% of applied N used in calculations of N2O emissions by the Intergovernmental Panel on Climate Change. During the emission pulses, which were triggered by high soil moisture and high availability of mineral N, a clear diurnal pattern of N2O emissions was observed, driven by daily changes in topsoil temperature. For these periods, air sampling from 8:00 to 10:00 and from 18:00 to 20:00 was found to best represent the mean daily N2O flux rates. The wet topsoil conditions caused by irrigation favored the production of N2O from NO3− fertilizers, but not from NH4+ fertilizers, thus indicating that denitrification was the main process causing N2O emissions. It is therefore argued that there is scope for reducing N2O emission from irrigated cotton production; i.e. through the exclusive use of NH4+ fertilizers. Advanced application and irrigation techniques such as subsurface fertilizer application, drip irrigation and fertigation may also minimize N2O emission from this regionally dominant agro-ecosystem.

Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides

Nitrogen-doped reduced giaphene oxide (RGO) samples with different nitrogen content, prepared by two different methods, as well as nitrogen-doped few-layer graphene have been investigated as supercapacitor electrodes. Two electrode measurements have been carried out both in aqueous (6 M KOH) and in ionic liquid media. Nitrogen-doped reduced graphene oxides exhibit satisfactory specific capacitance, the values reaching 126 F/g at a scan rate of 10 mV/s in aqueous medium. Besides providing supercapacitor characteristics, the study has shown the nitrogen content and surface area to be important factors. High surface-area borocarbonitrides, BxCyNz, prepared by the urea route appear to be excellent supercapacitor electrode materials. Thus, BC4.5N exhibits a specific capacitance of 169 F/g at a scan rate of 10 mV/s in aqueous medium. In an ionic liquid medium, nitrogen-doped RGO and BC4.5N exhibit specific capacitance values of 258 F/g and 240 F/g at a scan rate of 5 mV/s. The ionic liquid enables a larger operating voltage range of 0.0-2.5 V compared to 0.0-1 V in aqueous medium. (C) 2013 Elsevier Ltd. All rights reserved.

Hexamethylenetetramine mediated simultaneous nitrogen doping and reduction of graphene oxide for a metal-free SERS substrate

We report a one-pot hydrothermal synthesis of nitrogen doped reduced graphene oxide (N-rGO) and Ag nanoparticle decorated N-rGO hybrid nanostructures from graphene oxide (GO), metal ions and hexamethylenetetramine (HMT). HMT not only reduces GO and metal ions simultaneously but also acts as the source for the nitrogen (N) dopant. We show that the N-rGO can be used as a metal-free surface enhanced Raman spectroscopy (SERS) substrate, while the Ag nano-particles decorated N-rGO can be used as an effective SERS substrate as well as a template for decorating various other nanostructures on N-rGO.

Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski

I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.