995 resultados para REACTIVE NITROGEN-OXIDES


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Studies have suggested that diets rich in polyphenols Such as flavonoids may lead to a reduced risk of gastrointestinal cancers. We demonstrate the ability of monomeric and dimeric flavanols to scavenge reactive nitrogen species derived from nitrous acid. Both epicatechin and dimer B2 (epicatechin dimer) inhibited nitrous acid-induced formation of 3-nitrotyrosine and the formation of the carcinogenic N-nitrosamine, N-nitrosodimethylamine. The reaction of monomeric and dimeric epicatechin with nitrous acid led to the formation of mono- and di-nitroso flavanols, whereas the reaction with hesperetin resulted primarily in the formation of nitrated products. Although, epicatechin was transferred across the jejunum of the small intestine yielding metabolites, its nitroso form was not absorbed. Dimer B2 but not epicatechin monomer inhibited the proliferation of, and triggered apoptosis in, Caco-2 cells. The latter was accompanied by caspase-3 activation and reductions in Akt phosphorylation, suggesting activation of apoptosis via inhibition of prosurvival signaling. Furthermore, the dinitroso derivative of dimer B2, and to a lesser extent the dinitroso-epicatechin, also induced significant toxic effects in Caco-2 cells. The inhibitory effects on cellular proliferation were paralleled by early inhibition of ERK 1/2 phosphorylation and later reductions in cyclin D I levels, indicating modulation of cell cycle regulation in Caco-2 cells. These effects highlight multiple routes in which dietary derived flavanols may exert beneficial effects in the gastrointestinal tract. (c) 2005 Elsevier Inc. All rights reserved.

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The roles of nitrogen (N) and phosphorus (P) as key nutrients determining the trophic status of water bodies are examined, and evidence reviewed for trends in concentrations of N and P species which occur in freshwaters, primarily in northern temperate environments. Data are reported for water bodies undergoing eutrophication and acidification, especially water bodies receiving increased nitrogen inputs through the atmospheric deposition of nitrogen oxides (NOx). Nutrient loading on groundwaters and surface freshwaters is assessed with respect to causes and rates of change, relative rates of change for N and P, and implications of change for the future management of lakes, rivers and groundwaters. In particular, the nature and emphasis of studies for N species and P fractions in lakes versus rivers and groundwaters are contrasted. This review paper primarily focuses on results from North America and Europe, particularly for the UK where a wide range of data sets exists. Few nutrient loading data have been published on water bodies in less developed countries; however, some of the available data are presented to provide a global perspective. In general, N and P concentrations have increased dramatically (>20 times background concentrations) in many areas and causes vary considerably, ranging from urbanization to changes in agricultural practices.

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Emissions of exhaust gases and particles from oceangoing ships are a significant and growing contributor to the total emissions from the transportation sector. We present an assessment of the contribution of gaseous and particulate emissions from oceangoing shipping to anthropogenic emissions and air quality. We also assess the degradation in human health and climate change created by these emissions. Regulating ship emissions requires comprehensive knowledge of current fuel consumption and emissions, understanding of their impact on atmospheric composition and climate, and projections of potential future evolutions and mitigation options. Nearly 70% of ship emissions occur within 400 km of coastlines, causing air quality problems through the formation of ground-level ozone, sulphur emissions and particulate matter in coastal areas and harbours with heavy traffic. Furthermore, ozone and aerosol precursor emissions as well as their derivative species from ships may be transported in the atmosphere over several hundreds of kilometres, and thus contribute to air quality problems further inland, even though they are emitted at sea. In addition, ship emissions impact climate. Recent studies indicate that the cooling due to altered clouds far outweighs the warming effects from greenhouse gases such as carbon dioxide (CO2) or ozone from shipping, overall causing a negative present-day radiative forcing (RF). Current efforts to reduce sulphur and other pollutants from shipping may modify this. However, given the short residence time of sulphate compared to CO2, the climate response from sulphate is of the order decades while that of CO2 is centuries. The climatic trade-off between positive and negative radiative forcing is still a topic of scientific research, but from what is currently known, a simple cancellation of global mean forcing components is potentially inappropriate and a more comprehensive assessment metric is required. The CO2 equivalent emissions using the global temperature change potential (GTP) metric indicate that after 50 years the net global mean effect of current emissions is close to zero through cancellation of warming by CO2 and cooling by sulphate and nitrogen oxides.

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A state-of-the-art chemistry climate model coupled to a three-dimensional ocean model is used to produce three experiments, all seamlessly covering the period 1950–2100, forced by different combinations of long-lived Greenhouse Gases (GHGs) and Ozone Depleting Substances (ODSs). The experiments are designed to quantify the separate effects of GHGs and ODSs on the evolution of ozone, as well as the extent to which these effects are independent of each other, by alternately holding one set of these two forcings constant in combination with a third experiment where both ODSs and GHGs vary. We estimate that up to the year 2000 the net decrease in the column amount of ozone above 20 hPa is approximately 75% of the decrease that can be attributed to ODSs due to the offsetting effects of cooling by increased CO2. Over the 21st century, as ODSs decrease, continued cooling from CO2 is projected to account for more than 50% of the projected increase in ozone above 20 hPa. Changes in ozone below 20 hPa show a redistribution of ozone from tropical to extra-tropical latitudes with an increase in the Brewer-Dobson circulation. In addition to a latitudinal redistribution of ozone, we find that the globally averaged column amount of ozone below 20 hPa decreases over the 21st century, which significantly mitigates the effect of upper stratospheric cooling on total column ozone. Analysis by linear regression shows that the recovery of ozone from the effects of ODSs generally follows the decline in reactive chlorine and bromine levels, with the exception of the lower polar stratosphere where recovery of ozone in the second half of the 21st century is slower than would be indicated by the decline in reactive chlorine and bromine concentrations. These results also reveal the degree to which GHGrelated effects mute the chemical effects of N2O on ozone in the standard future scenario used for the WMO Ozone Assessment. Increases in the residual circulation of the atmosphere and chemical effects from CO2 cooling more than halve the increase in reactive nitrogen in the mid to upper stratosphere that results from the specified increase in N2O between 1950 and 2100.

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Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.

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In addition to CO2, the climate impact of aviation is strongly influenced by non-CO2 emissions, such as nitrogen oxides, influencing ozone and methane, and water vapour, which can lead to the formation of persistent contrails in ice-supersaturated regions. Because these non-CO2 emission effects are characterised by a short lifetime, their climate impact largely depends on emission location and time; that is to say, emissions in certain locations (or times) can lead to a greater climate impact (even on the global average) than the same emission in other locations (or times). Avoiding these climate-sensitive regions might thus be beneficial to climate. Here, we describe a modelling chain for investigating this climate impact mitigation option. This modelling chain forms a multi-step modelling approach, starting with the simulation of the fate of emissions released at a certain location and time (time-region grid points). This is performed with the chemistry–climate model EMAC, extended via the two submodels AIRTRAC (V1.0) and CONTRAIL (V1.0), which describe the contribution of emissions to the composition of the atmosphere and to contrail formation, respectively. The impact of emissions from the large number of time-region grid points is efficiently calculated by applying a Lagrangian scheme. EMAC also includes the calculation of radiative impacts, which are, in a second step, the input to climate metric formulas describing the global climate impact of the emission at each time-region grid point. The result of the modelling chain comprises a four-dimensional data set in space and time, which we call climate cost functions and which describes the global climate impact of an emission at each grid point and each point in time. In a third step, these climate cost functions are used in an air traffic simulator (SAAM) coupled to an emission tool (AEM) to optimise aircraft trajectories for the North Atlantic region. Here, we describe the details of this new modelling approach and show some example results. A number of sensitivity analyses are performed to motivate the settings of individual parameters. A stepwise sanity check of the results of the modelling chain is undertaken to demonstrate the plausibility of the climate cost functions.

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The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

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Forensic taphonomy involves the use of decomposition to estimate postmortem interval (PMI) or locate clandestine graves. Yet, cadaver decomposition remains poorly understood, particularly following burial in soil. Presently, we do not know how most edaphic and environmental parameters, including soil moisture, influence the breakdown of cadavers following burial and alter the processes that are used to estimate PMI and locate clandestine graves. To address this, we buried juvenile rat (Rattus rattus) cadavers (∼18 g wet weight) in three contrasting soils from tropical savanna ecosystems located in Pallarenda (sand), Wambiana (medium clay), or Yabulu (loamy sand), Queensland, Australia. These soils were sieved (2 mm), weighed (500 g dry weight), calibrated to a matric potential of -0.01 megapascals (MPa), -0.05 MPa, or -0.3 MPa (wettest to driest) and incubated at 22 °C. Measurements of cadaver decomposition included cadaver mass loss, carbon dioxide-carbon (CO2-C) evolution, microbial biomass carbon (MBC), protease activity, phosphodiesterase activity, ninhydrin-reactive nitrogen (NRN) and soil pH. Cadaver burial resulted in a significant increase in CO2-C evolution, MBC, enzyme activities, NRN and soil pH. Cadaver decomposition in loamy sand and sandy soil was greater at lower matric potentials (wetter soil). However, optimal matric potential for cadaver decomposition in medium clay was exceeded, which resulted in a slower rate of cadaver decomposition in the wettest soil. Slower cadaver decomposition was also observed at high matric potential (-0.3 MPa). Furthermore, wet sandy soil was associated with greater cadaver decomposition than wet fine-textured soil. We conclude that gravesoil moisture content can modify the relationship between temperature and cadaver decomposition and that soil microorganisms can play a significant role in cadaver breakdown. We also conclude that soil NRN is a more reliable indicator of gravesoil than soil pH.

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Some death scene investigations commence without knowledge of the location of the body and/or decomposition site. In these cases, it is necessary to locate the remains or the site where the body decomposed prior to movement. We hypothesized that the burial of a mammalian cadaver will result in the release of ninhydrin reactive nitrogen (NRN) into associated soil and that this reaction might have potential as a tool for the identification of clandestine graves. Juvenile rat (Rattus rattus) cadavers were buried in three contrasting soil types in Australian tropical savanna ecosystems and allowed to decompose over a period of 28 days. Soils were sequentially harvested and analyzed for NRN. Cadaver burial resulted in an approximate doubling (mean = 1.7 ± 0.1) in the concentration of soil NRN. This reaction has great potential to be used as a presumptive test for gravesoil and this use might be greatly enhanced following more detailed research.

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In the metropolitan area of Sao Paulo, Brazil, ozone and particulate matter ( PM) are the air pollutants that pose the greatest threat to air quality, since the PM and the ozone precursors ( nitrogen oxides and volatile organic compounds) are the main source of air pollution from vehicular emissions. Vehicular emissions can be measured inside road tunnels, and those measurements can provide information about emission factors of in-use vehicles. Emission factors are used to estimate vehicular emissions and are described as the amount of species emitted per vehicle distance driven or per volume of fuel consumed. This study presents emission factor data for fine particles, coarse particles, inhalable particulate matter and black carbon, as well as size distribution data for inhalable particulate matter, as measured in March and May of 2004, respectively, in the Janio Quadros and Maria Maluf road tunnels, both located in Sao Paulo. The Janio Quadros tunnel carries mainly light-duty vehicles, whereas the Maria Maluf tunnel carries light-duty and heavy-duty vehicles. In the Janio Quadros tunnel, the estimated light-duty vehicle emission factors for the trace elements copper and bromine were 261 and 220 mu g km(-1), respectively, and 16, 197, 127 and 92 mg km(-1), respectively, for black carbon, inhalable particulate matter, coarse particles and fine particles. The mean contribution of heavy-duty vehicles to the emissions of black carbon, inhalable particulate matter, coarse particles and fine particles was, respectively 29, 4, 6 and 6 times higher than that of light-duty vehicles. The inhalable particulate matter emission factor for heavy-duty vehicles was 1.2 times higher than that found during dynamometer testing. In general, the particle emissions in Sao Paulo tunnels are higher than those found in other cities of the world.

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Drug resistance and virulence of Mycobacterium tuberculosis are partially related to the pathogen`s antioxidant systems. Peroxide detoxification in this bacterium is achieved by the heme-containing catalase peroxidase and different two-cysteine peroxiredoxins. M. tuberculosis genome also codifies for a putative one-cysteine peroxiredoxin, alkyl hydroperoxide reductase E (MtAhpE). Its expression was previously demonstrated at a transcriptional level, and the crystallographic structure of the recombinant protein was resolved under reduced and oxidized states. Herein, we report that the conformation of MtAhpE changed depending on its single cysteine redox state, as reflected by different tryptophan fluorescence properties and changes in quaternary structure. Dynamics of fluorescence changes, complemented by competition kinetic assays, were used to perform protein functional studies. MtAhE reduced peroxynitrite 2 orders of magnitude faster than hydrogen peroxide (1.9 x 10(7) M(-1) s(-1) vs 8.2 x 10(4) M(-1) s(-1) at pH 7.4 and 25 degrees C, respectively). The latter also caused cysteine overoxidation to sulfinic acid, but at much slower rate constant (40 M(-1) s(-1)). The pK(a) of the thiol in the reduced enzyme was 5.2, more than one unit lower than that of the sulfenic acid in the oxidized enzyme. The pH profile of hydrogen peroxide-mediated thiol and sulfenic acid oxidations indicated thiolate and sulfenate as the reacting species. The formation of sulfenic acid as well as the catalytic peroxidase activity of MtAhpE was demonstrated using the artificial reducing substrate thionitrobenzoate. Taken together, our results indicate that MtAhpE is a relevant component in the antioxidant repertoire of M. tuberculosis probably involved in peroxide and specially peroxynitrite detoxification.

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Tempol (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) has long been known to protect experimental animals from the injury associated with oxidative and inflammatory conditions. In the latter case, a parallel decrease in tissue protein nitration levels has been observed. Protein nitration represents a shift in nitric oxide actions from physiological to pathophysiological and potentially damaging pathways involving its derived oxidants such as nitrogen dioxide and peroxynitrite. In infectious diseases, protein tyrosine nitration of tissues and cells has been taken as evidence for the involvement of nitric oxide-derived oxidants in microbicidal mechanisms. To examine whether tempol inhibits the microbicidal action of macrophages, we investigated its effects on Leishmania amazonensis infection in vitro (RAW 264.7 murine macrophages) and in vivo (C57B1/6 mice). Tempol was administered in the drinking water at 2 mM throughout the experiments and shown to reach infected footpads as the nitroxide plus the hydroxylamine derivative by EPR analysis. At the time of maximum infection (6 weeks), tempol increased footpad lesion size (120%) and parasite burden (150%). In lesion extracts, tempol decreased overall nitric oxide products and expression of inducible nitric oxide synthase to about 80% of the levels in control animals. Nitric oxide-derived products produced by radical mechanisms, such as 3-nitrotyrosine and nitrosothiol, decreased to about 40% of the levels in control mice. The results indicate that tempol worsened L. amazonensis infection by a dual mechanism involving down-regulation of iNOS expression and scavenging of nitric oxide-derived oxidants. Thus, the development of therapeutic strategies based on nitroxides should take into account the potential risk of altering host resistance to parasite infection. (c) 2008 Elsevier Inc. All rights reserved.

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Emissions from residential combustion appliances vary significantly depending on the firing behaviours and combustion conditions, in addition to combustion technologies and fuel quality. Although wood pellet combustion in residential heating boilers is efficient, the combustion conditions during start-up and stop phases are not optimal and produce significantly high emissions such as carbon monoxide and hydrocarbon from incomplete combustion. The emissions from the start-up and stop phases of the pellet boilers are not fully taken into account in test methods for ecolabels which primarily focus on emissions during operation on full load and part load. The objective of the thesis is to investigate the emission characteristics during realistic operation of residential wood pellet boilers in order to identify when the major part of the annual emissions occur. Emissions from four residential wood pellet boilers were measured and characterized for three operating phases (start-up, steady and stop). Emissions from realistic operation of combined solar and wood pellet heating systems was continuously measured to investigate the influence of start-up and stop phases on total annual emissions. Measured emission data from the pellet devices were used to build an emission model to predict the annual emission factors from the dynamic operation of the heating system using the simulation software TRNSYS. Start-up emissions are found to vary with ignition type, supply of air and fuel, and time to complete the phase. Stop emissions are influenced by fan operation characteristics and the cleaning routine. Start-up and stop phases under realistic operation conditions contribute 80 – 95% of annual carbon monoxide (CO) emission, 60 – 90% total hydrocarbon (TOC), 10 – 20% of nitrogen oxides (NO), and 30 – 40% particles emissions. Annual emission factors from realistic operation of tested residential heating system with a top fed wood pelt boiler can be between 190 and 400 mg/MJ for the CO emissions, between 60 and 95 mg/MJ for the NO, between 6 and 25 mg/MJ for the TOC, between 30 and 116 mg/MJ for the particulate matter and between 2x10-13 /MJ and 4x10-13 /MJ for the number of particles. If the boiler has the cleaning sequence with compressed air such as in boiler B2, annual CO emission factor can be up to 550 mg/MJ. Average CO, TOC and particles emissions under realistic annual condition were greater than the limits values of two eco labels. These results highlight the importance of start-up and stop phases in annual emission factors (especially CO and TOC). Since a large or dominating part of the annual emissions in real operation arise from the start-up and stop sequences, test methods required by the ecolabels should take these emissions into account. In this way it will encourage the boiler manufacturers to minimize annual emissions. The annual emissions of residential pellet heating system can be reduced by optimizing the number of start-ups of the pellet boiler. It is possible to reduce up to 85% of the number of start-ups by optimizing the system design and its controller such as switching of the boiler pump after it stops, using two temperature sensors for boiler ON/OFF control, optimizing of the positions of the connections to the storage tank, increasing the mixing valve temperature in the boiler circuit and decreasing the pump flow rate. For 85 % reduction of start-ups, 75 % of CO and TOC emission factors were reduced while 13% increase in NO and 15 % increase in particle emissions was observed.

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Existe um número crescente de componentes químicos lançados ao meio ambiente, muitos dos quais são capazes de induzir efeitos danosos adversos à saúde de animais e humanos, representando uma causa importante de preocupação por seus possíveis efeitos a longo prazo. O impacto ecológico e os riscos a saúde dos organismos associados com a exposição a poluentes ambientais são extremamente difíceis de se avaliar devido a muitos desses componentes serem parte de misturas complexas. Os gases produzidos pelos motores dos veículos à combustão contém diversos poluentes sabidamente genotóxicos, como óxidos de nitrogênio (NOX), monóxido de carbono (CO), óxidos de enxofre (SOx), hidrocarbonetos (HC) e seus derivados, bem como particulados, e metais (cádmio, cromo, cobre, níquel, vanádio, zinco e chumbo). Todos esses compostos isolados ou associados a outros elementos são tóxicos ou de efeito danoso aos organismos, de forma não totalmente esclarecida. Este estudo teve como objetivo verificar o possível efeito genotóxico das emissões dos automóveis em roedor nativo Ctenomys minutus cronicamente exposto, através do Ensaio Cometa (EC), comparando os resultados com o Teste de Micronúcleos (MN), ambos em sangue periférico. Levando em consideração alguns fatores que pudessem influenciar os resultados dos testes de genotoxicidade, este trabalho ainda teve como objetivos: identificar a presença de alguns agentes envolvidos na poluição gerada pelos veículos; verificar possíveis diferenças sazonais, como temperatura e ventos; e se existe influência da idade e sexo dos roedores. Os C. minutus (Octodontidae-Rodentia), foram capturados em dois campos diferentes, ambos ao lado da estrada RS/030, na cidade de Osório, Estado do Rio Grande do Sul (RS): (a) Amaral, e (b) Weber. Animais para controle externo foram capturados no Campo Maribo à cerca de 3 km de distância de outra estrada (RS/389-Osório/RS), conseqüentemente afastada das emissões dos veículos. No final do período desse estudo, foram capturados 123 animais (73 fêmeas e 50 machos).

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The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides