959 resultados para Atmospheric Chemistry|Environmental Sciences|Engineering, Environmental
Resumo:
Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.
Resumo:
Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO(4)(2-) and a large proportion of the precipitation is acidic, with 98% of samples at Amersfoort and 94% at Louis Trichardt having a pH below 5.6 ( average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.
Resumo:
The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H2SO4) and organic acids (18%). Most of the H2SO4 component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS.ha(-1).yr(-1) and 2.8 kgN.ha(-1).yr(-1), respectively. The N deposition was mainly in the form of NH4+. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.
Resumo:
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Resumo:
The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO2; SO2; O3; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatography-ion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO2 varied between 9.5 and 23 μg m-3, whereas SO2 showed an interval from 0.1 to 4.8 μg m-3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5 μg m-3 and 1.2 μg m-3, respectively. © Springer Science + Business Media B.V. 2009.
Resumo:
Sewage sludge may be used as an agricultural fertilizer, but the practice has been criticized because sludge may contain trace elements and pathogens. The aim of this study was to compare the effectiveness of total and pseudototal extractants of Cu, Fe, Mn, and Zn, and to compare the results with the bioavailable concentrations of these elements to maize and sugarcane in a soil that was amended with sewage sludge for 13 consecutive years and in a separate soil that was amended a single time with sewage sludge and composted sewage sludge. The 13-year amendment experiment involved 3 rates of sludge (5, 10, and 20 t ha-1). The one-time amendment experiment involved treatments reflecting 50, 100, and 200 % of values stipulated by current legislation. The metal concentrations extracted by aqua regia (AR) were more similar to those obtained by Environmental Protection Agency (EPA) 3052 than to those obtained by EPA3051, and the strongest correlation was observed between pseudo(total) concentrations extracted by AR and EPA3052 and bioavailable concentrations obtained by Mehlich III. An effect of sewage sludge amendment on the concentrations of heavy metals was only observed in samples from the 13-year experiment. © 2012 Springer Science+Business Media B.V.
Resumo:
Microparticles found in the air may be associated with organic matter that contains several compounds, such as Polycyclic Aromatic Hydrocarbons (PAHs) and nitro-PAHs, and may pose a significant risk to human health, possibly leading to DNA mutations and cancers. This study associated genotoxicity assays for evaluating human exposure with the atmospheric air of two urban areas in southern Brazil, that received different atmospheric contributions. Site 1 was under urban-industrial influence and the other was a non-industrial reference, Site 2. Organic extracts from the airborne particulate matter were tested for mutagenicity via the Salmonella/microsome assay and analyzed for PAH composition. Cells samples of people residing in these two cities were evaluated using the comet and micronucleus assay (MN).Concentrations of the individual PAHs ranged from 0.01ng/m3 (benzo[a]anthracene) to 5.08ng/m3 (benzo[ghi]perylene). As to mutagenicity analysis of airborne, Site 1 presented all the mutagenic responses, which varied from 3.2±1.22rev/m3 (TA98 no S9) to 32.6±2.05rev/m3 (TA98, S9), while Site 2 ranged from negative to minimal responses. Site 1 presented a high quantity of nitro and amino derivatives of PAHs, and peaked at 56.0±3.68rev/μg (YG1024 strain). The two groups presented very low DNA damage levels without intergroup difference. Although Site 1 presented high mutagenic responses in the air samples, high PAH levels, healthy people exposed to this environment did not show significative damage in their genetic material. However, the evaluation of different environmental and genetic damage in such population is necessary to monitor possible damages. © 2013 Elsevier Inc.
Resumo:
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Resumo:
We present the results of airborne measurements of carbon monoxide (CO) and aerosol particle number concentration (CN) made during the Balan double dagger o Atmosf,rico Regional de Carbono na Amazonia (BARCA) program. The primary goal of BARCA is to address the question of basin-scale sources and sinks of CO2 and other atmospheric carbon species, a central issue of the Large-scale Biosphere-Atmosphere (LBA) program. The experiment consisted of two aircraft campaigns during November-December 2008 (BARCA-A) and May-June 2009 (BARCA-B), which covered the altitude range from the surface up to about 4500 m, and spanned most of the Amazon Basin. Based on meteorological analysis and measurements of the tracer, SF6, we found that airmasses over the Amazon Basin during the late dry season (BARCA-A, November 2008) originated predominantly from the Southern Hemisphere, while during the late wet season (BARCA-B, May 2009) low-level airmasses were dominated by northern-hemispheric inflow and mid-tropospheric airmasses were of mixed origin. In BARCA-A we found strong influence of biomass burning emissions on the composition of the atmosphere over much of the Amazon Basin, with CO enhancements up to 300 ppb and CN concentrations approaching 10 000 cm(-3); the highest values were in the southern part of the Basin at altitudes of 1-3 km. The Delta CN/Delta CO ratios were diagnostic for biomass burning emissions, and were lower in aged than in fresh smoke. Fresh emissions indicated CO/CO2 and CN/CO emission ratios in good agreement with previous work, but our results also highlight the need to consider the residual smoldering combustion that takes place after the active flaming phase of deforestation fires. During the late wet season, in contrast, there was little evidence for a significant presence of biomass smoke. Low CN concentrations (300-500 cm(-3)) prevailed basinwide, and CO mixing ratios were enhanced by only similar to 10 ppb above the mixing line between Northern and Southern Hemisphere air. There was no detectable trend in CO with distance from the coast, but there was a small enhancement of CO in the boundary layer suggesting diffuse biogenic sources from photochemical degradation of biogenic volatile organic compounds or direct biological emission. Simulations of CO distributions during BARCA-A using a range of models yielded general agreement in spatial distribution and confirm the important contribution from biomass burning emissions, but the models evidence some systematic quantitative differences compared to observed CO concentrations. These mismatches appear to be related to problems with the accuracy of the global background fields, the role of vertical transport and biomass smoke injection height, the choice of model resolution, and reliability and temporal resolution of the emissions data base.
Resumo:
As a part of the AMAZE-08 campaign during the wet season in the rainforest of central Amazonia, an ultraviolet aerodynamic particle sizer (UV-APS) was operated for continuous measurements of fluorescent biological aerosol particles (FBAP). In the coarse particle size range (> 1 mu m) the campaign median and quartiles of FBAP number and mass concentration were 7.3x10(4) m(-3) (4.0-13.2x10(4) m(-3)) and 0.72 mu g m(-3) (0.42-1.19 mu g m(-3)), respectively, accounting for 24% (11-41%) of total particle number and 47% (25-65%) of total particle mass. During the five-week campaign in February-March 2008 the concentration of coarse-mode Saharan dust particles was highly variable. In contrast, FBAP concentrations remained fairly constant over the course of weeks and had a consistent daily pattern, peaking several hours before sunrise, suggesting observed FBAP was dominated by nocturnal spore emission. This conclusion was supported by the consistent FBAP number size distribution peaking at 2.3 mu m, also attributed to fungal spores and mixed biological particles by scanning electron microscopy (SEM), light microscopy and biochemical staining. A second primary biological aerosol particle (PBAP) mode between 0.5 and 1.0 mu m was also observed by SEM, but exhibited little fluorescence and no true fungal staining. This mode may have consisted of single bacterial cells, brochosomes, various fragments of biological material, and small Chromalveolata (Chromista) spores. Particles liquid-coated with mixed organic-inorganic material constituted a large fraction of observations, and these coatings contained salts likely from primary biological origin. We provide key support for the suggestion that real-time laser-induce fluorescence (LIF) techniques using 355 nm excitation provide size-resolved concentrations of FBAP as a lower limit for the atmospheric abundance of biological particles in a pristine environment. We also show some limitations of using the instrument for ambient monitoring of weakly fluorescent particles < 2 mu m. Our measurements confirm that primary biological particles, fungal spores in particular, are an important fraction of supermicron aerosol in the Amazon and that may contribute significantly to hydrological cycling, especially when coated by mixed inorganic material.
Resumo:
Large conurbations are a significant source of the anthropogenic pollution and demographic differences between cities that result in a different pollution burden. The metropolitan area of Sao Paulo (MASP, population 20 million) accounts for one fifth of the Brazilian vehicular fleet. A feature of MASP is the amount of ethanol used by the vehicular fleet, known to exacerbate air quality. The study describes the diurnal behaviour of the submicron aerosol and relies on total particle number concentration, particle number size distribution, light scattering and light absorption measurements. Modelled planetary boundary layer (PBL) depth and air mass movement data were used to aid the interpretation. During morning rush-hour, stagnant air and a shallow PBL height favour the accumulation of aerosol pollution. During clear-sky conditions, there was a wind shift towards the edge of the city indicating a heat island effect with implications on particulate pollution levels at the site. The median total particle number concentration for the submicron aerosol typically varied in the range 1.6 x 10(4)-3.2 x 10(4) cm(-3) frequently exceeding 4 x 10(4) cm-3 during the day. During weekdays, nucleation-mode particles are responsible for most of the particles by numbers. The highest concentrations of total particle number concentrations and black carbon (BC) were observed on Fridays. Median diurnal values for light absorption and light scattering (at 637 nm wavelength) varied in the range 12-33 Mm(-1) and 21-64 Mm(-1), respectively. The former one is equal to 1.8-5.0 mu g m(-3) of BC. The growth of the PBL, from the morning rush-hour until noon, is consistent with the diurnal cycle of BC mass concentrations. Weekday hourly median single-scattering albedo (omega(0)) varied in the range 0.59-0.76. Overall, this suggests a top of atmosphere (TOA) warming effect. However, considering the low surface reflectance of urban areas, for the given range of omega(0), the TOA radiative forcing can be either positive or negative for the sources within the MASP. On the average, weekend omega(0) values were 0.074 higher than during weekdays. During 11% of the days, new particle formation (NPF) events occurred. The analysed events growth rates ranged between 9 and 25 nm h(-1). Sulphuric acid proxy concentrations calculated for the site were less than 5% of the concentration needed to explain the observed growth. Thus, other vapours are likely contributors to the observed growth.
Resumo:
We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).
Resumo:
In dieser Arbeit wird ein neu entwickeltes Spektralradiometer zur Messung des solaren aktinischen Strahlungsflusses, speziell bei bewölkter Atmosphäre, vorgestellt. Das Meßsystem benutzt ein spezielles neu entwickeltes optisches Empfangssystem mit winkelunabhängiger Empfindlichkeit über den gesamten Raum (4pisr). Das Spektrometer besteht aus einem Gitterspektrographen und einer CCD-Kamera als Detektor, wodurch die schnelle simultane Messung eines Wellenlängenbereiches von 300nm bis 660nm ermöglicht wird. Zudem können Spektren von drei Empfangssystemen gleichzeitig aufgenommen werden, was zur höhenaufgelösten Messung des aktinischen Flusses verwendet wird. Photolysefrequenzen von Ozon, Stickstoffdioxid, und anderen für die troposphärische Chemie interessanten Molekülen werden mit Literaturdaten des molekularen Absorptionsquerschnitts und der Quantenausbeute und dem gemessenen aktinischen Strahlungsfluß berechnet. Zudem werden anhand von Spektren des aktinischen Flusses, die bei der Feldmeßkampagne BERLIOZ (BERLIn OZonexperiment) und bei Feldmessungen an einem 107m hohen Turm auf einem Berg (753m NN, Hunsrück) aufgenommen wurden, die Effekte unterschiedlicher Bewölkungssituationen untersucht. Als Ergebnis dieser Arbeit wurden verschiedene wellenlängenabhängige Effekte deutlich: bei partieller Bewölkung ist der aktinische Fluß am Erdboden gegenüber dem wolkenfreien Fall teilweise reduziert, aber auch erhöht, wobei diese Effekte mit zunehmender Wellenlänge größer werden. Oberhalb von Wolken ist der aktinische Fluß gegenüber dem wolkenfreien Fall erhöht. Dieser Effekt nimmt mit abnehmender Wellenlänge zu.
Resumo:
It has been demonstrated that iodine does have an important influence on atmospheric chemistry, especially the formation of new particles and the enrichment of iodine in marine aerosols. It was pointed out that the most probable chemical species involved in the production or growth of these particles are iodine oxides, produced photochemically from biogenic halocarbon emissions and/or iodine emission from the sea surface. However, the iodine chemistry from gaseous to particulate phase in the coastal atmosphere and the chemical nature of the condensing iodine species are still not understood. A Tenax / Carbotrap adsorption sampling technique and a thermo-desorption / cryo-trap / GC-MS system has been further developed and improved for the volatile organic iodine species in the gas phase. Several iodo-hydrocarbons such as CH3I, C2H5I, CH2ICl, CH2IBr and CH2I2 etc., have been measured in samples from a calibration test gas source (standards), real air samples and samples from seaweeds / macro-algae emission experiments. A denuder sampling technique has been developed to characterise potential precursor compounds of coastal particle formation processes, such as molecular iodine in the gas phase. Starch, TMAH (TetraMethylAmmonium Hydroxide) and TBAH (TetraButylAmmonium Hydroxide) coated denuders were tested for their efficiencies to collect I2 at the inner surface, followed by a TMAH extraction and ICP/MS determination, adding tellurium as an internal standard. The developed method has been proved to be an effective, accurate and suitable process for I2 measurement in the field, with the estimated detection limit of ~0.10 ng∙L-1 for a sampling volume of 15 L. An H2O/TMAH-Extraction-ICP/MS method has been developed for the accurate and sensitive determination of iodine species in tropospheric aerosol particles. The particle samples were collected on cellulose-nitrate filters using conventional filter holders or on cellulose nitrate/tedlar-foils using a 5-stage Berner impactor for size-segregated particle analysis. The water soluble species as IO3- and I- were separated by anion exchanging process after water extraction. Non-water soluble species including iodine oxide and organic iodine were digested and extracted by TMAH. Afterwards the triple samples were analysed by ICP/MS. The detection limit for particulate iodine was determined to be 0.10~0.20 ng•m-3 for sampling volumes of 40~100 m3. The developed methods have been used in two field measurements in May 2002 and September 2003, at and around the Mace Head Atmospheric Research Station (MHARS) located at the west coast of Ireland. Elemental iodine as a precursor of the iodine chemistry in the coastal atmosphere, was determined in the gas phase at a seaweed hot-spot around the MHARS, showing I2 concentrations were in the range of 0~1.6 ng∙L-1 and indicating a positive correlation with the ozone concentration. A seaweed-chamber experiment performed at the field measurement station showed that the I2 emission rate from macro-algae was in the range of 0.019~0.022 ng•min-1•kg-1. During these experiments, nanometer-particle concentrations were obtained from the Scanning Mobility Particle Sizer (SMPS) measurements. Particle number concentrations were found to have a linear correlation with elemental iodine in the gas phase of the seaweeds chamber, showing that gaseous I2 is one of the important precursors of the new particle formation in the coastal atmosphere. Iodine contents in the particle phase were measured in both field campaigns at and around the field measurement station. Total iodine concentrations were found to be in the range of 1.0 ~ 21.0 ng∙m-3 in the PM2.5 samples. A significant correlation between the total iodine concentrations and the nanometer-particle number concentrations was observed. The particulate iodine species analysis indicated that iodide contents are usually higher than those of iodate in all samples, with ratios in the range of 2~5:1. It is possible that those water soluble iodine species are transferred through the sea-air interface into the particle phase. The ratio of water soluble (iodate + iodide) and non-water soluble species (probably iodine oxide and organic iodine compounds) was observed to be in the range of 1:1 to 1:2. It appears that higher concentrated non-water soluble species, as the products of the photolysis from the gas phase into the particle phase, can be obtained in those samples while the nucleation events occur. That supports the idea that iodine chemistry in the coastal boundary layer is linked with new particle formation events. Furthermore, artificial aerosol particles were formed from gaseous iodine sources (e.g. CH2I2) using a laboratory reaction-chamber experiment, in which the reaction constant of the CH2I2 photolysis was calculated to be based upon the first order reaction kinetic. The end products of iodine chemistry in the particle phase were identified and quantified.
Resumo:
Since conjugated polymers, i.e. polymers with spatially extended pi-bonding system have offered unique physical properties, unobtainable for conventional polymers, significant research efforts directed to better understanding of their chemistry, physics and engineering have been undertaken in the past two and half decades. In this thesis we discuss the synthesis, characterisation and investigation of conjugated semiconducting organic materials for electronic applications. Owing to the versatile properties of metal-organic hybrid materials, there is significant promise that these materials can find use in optical or electronic devices in the future. In addressing this issue, the synthesis of bisthiazol-2-yl-amine (BTA) based polymers is attempted and their metallation is investigated. The focus of this work has been to examine whether the introduction of coordinating metal ions onto the polymer backbone can enhance the conductivity of the material. These studies can provide a basis for understanding the photophysical properties of metal-organic polymers based on BTA. In their neutral (undoped) form conjugated polymers are semiconductors and can be used as active components of plastics electronics such as polymer light-emitting diodes, polymer lasers, photovoltaic cells, field-effect transistors, etc. Toward this goal, it is an objective of the study to synthesize and characterize new classes of luminescent polymeric materials based on anthracene and phenanthrene moieties. A series of materials based on polyphenylenes and poly(phenyleneethynylene)s with 9,10-anthrylene subunits are not only presented but the synthesis and characterization of step-ladder and ladder poly(p-phenylene-alt-anthrylene)s containing 9,10-anthrylene building groups within the main chain are also explored. In a separate work, a series of soluble poly-2,7- and 3,6-phenanthrylenes are synthesized. This can enable us to do a systematic investigation into the optical and electronic properties of PPP-like versus PPV-like. Besides, the self-organization of 3,6-linked macrocyclic triphenanthrylene has been investigated by 2D wide-angle X-ray scattering experiments performed on extruded filaments in solution and in the bulk. Additionally, from the concept that donor-acceptor materials can induce efficient electron transfer, the covalent incorporation of perylene tetracarboxydiimide (PDI) into one block of a poly(2,7-carbazole) (PCz)-based diblock copolymer and 2,5-pyrrole based on push-pull type material are achieved respectively.