RESUMO

The Amazon rainforest suffers increasing pressure from anthropogenic activities. A key aspect not fully understood is how anthropogenic atmospheric emissions within the basin interact with biogenic emissions and impact the forest's atmosphere and biosphere. We combine a high-resolution atmospheric chemical transport model with an improved emissions inventory and in-situ measurements to investigate a surprisingly high concentration of ozone (O3) and secondary organic aerosol (SOA) 150-200 km downwind of Manaus city in an otherwise pristine forested region. We show that atmospheric dynamics and photochemistry determine a gross production of secondary pollutants seen in the simulation. After sunrise, the erosion of the nocturnal boundary layer mixes natural forest emissions, rich in biogenic volatile organic compounds, with a lofted pollution layer transported overnight, rich in nitrogen oxides and formaldehyde. As a result, O3 and SOA concentrations greater than ∼47 ppbv and 1.8 µg m-3, respectively, were found, with maximum concentrations occurring at 2 pm LT, 150-200 km downwind of Manaus city. These high concentrations affect a large primary forested area of about 11,250 km2. These oxidative areas are under a NOx-limited regime so that changes in NOx emissions from Manaus have a significant impact on O3 and SOA production.

Assuntos

RESUMO

Great efforts have been made over the years to assess the effectiveness of air pollution controls in place in the metropolitan area of São Paulo (MASP), Brazil. In this work, the community multiscale air quality (CMAQ) model was used to evaluate the efficacy of emission control strategies in MASP, considering the spatial and temporal variability of fine particle concentration. Seven different emission scenarios were modeled to assess the relationship between the emission of precursors and ambient aerosol concentration, including a baseline emission inventory, and six sensitivity scenarios with emission reductions in relation to the baseline inventory: a 50% reduction in SO2 emissions; no SO2 emissions; a 50% reduction in SO2, NOx, and NH3 emissions; no sulfate (PSO4) particle emissions; no PSO4 and nitrate (PNO3) particle emissions; and no PNO3 emissions. Results show that ambient PM2.5 behavior is not linearly dependent on the emission of precursors. Variation levels in PM2.5 concentrations did not correspond to the reduction ratios applied to precursor emissions, mainly due to the contribution of organic and elemental carbon, and other secondary organic aerosol species. Reductions in SO2 emissions are less likely to be effective at reducing PM2.5 concentrations at the expected rate in many locations of the MASP. The largest reduction in ambient PM2.5 was obtained with the scenario that considered a reduction in 50% of SO2, NOx, and NH3 emissions (1 to 2 µg/m3 on average). It highlights the importance of considering the role of secondary organic aerosols and black carbon in the design of effective policies for ambient PM2.5 concentration control.

Assuntos

RESUMO

Atmospheric pollution in cities is due to several human factors, for instance the number of cars in circulation, fuel efficiency and industrial waste, as well as orographic and meteorological conditions that determine air circulation. Ozone contingencies cause health disorders on the population, making it important to understand the factors that trigger such contingencies. Here, we analyze meteorological (wind, temperature, relative humidity) and atmospheric composition (ozone, and NOx) data of five atmospheric monitoring stations on Mexico City, from March 2004 to May 2018, comparing normal days with the extreme days in the 90th percentile of ozone. Moreover, we present the synoptic patterns of the seasonal differences of geopotential height at 500 hPa between extreme and control days. We found that, in the dry-hot season (from March to May) an atmospheric blockage with meteorological conditions of almost no wind, low relative humidity, and small temperature fluctuations occurs. Because the air in the city permanently contains large amounts of ozone precursors like NOx, this meteorological scenario raises ozone levels to those of an environmental contingency. Thus, during the dry-hot season on Mexico City, ozone contingencies are triggered by atmospheric blocking. This scenario will be present in cities surrounded by mountains with high levels of Ozone precursors.

RESUMO

Rate coefficients for the gas-phase reactions of OH radicals and Cl atoms with 1-methoxy-2-propanone (1-M-2-PONE), 1-methoxy-2-propanol (1-M-2-POL), and 1-methoxy-2-butanol (1-M-2-BOL) were determined at room temperature and atmospheric pressure using a conventional relative-rate technique. The following absolute rate coefficients were derived: k 1(OH + 1-M-2-PONE) = (0.64 ± 0.13) × 10-11, k 2(OH + 1-M-2-BOL) = (2.19 ± 0.23) × 10-11, k 3(Cl + 1-M-2-PONE = (1.07 ± 0.24) × 10-10, k 4(Cl + 1-M-2-POL) = (2.28 ± 0.21) × 10-10, and k 5 (Cl + 1-M-2-BOL) = (2.79 ± 0.23) × 10-10, in units of cm3 molecule-1 s-1. This is the first experimental determination of k 2-k 5. These rate coefficients were used to discuss the influence of the structure on the reactivity of the studied polyfunctional organic compounds. The atmospheric implications for 1-M-2-PONE, 1-M-2-POL, and 1-M-2-BOL and their reactions were investigated estimating atmospheric parameters such as lifetimes, global warming potentials, and average photochemical ozone production. The approximate nature of these values was stressed considering that the studied oxygenated volatile organic compounds are short-lived compounds for which the calculated parameters may vary depending on chemical composition, location, and season at the emission points.

Assuntos

RESUMO

The rate coefficient for the reaction CH3 OH+OH was determined by means of a relative method in a simulation chamber under quasi-real atmospheric conditions (294 K, 1 atm of air) and variable humidity or water concentration. Under these conditions, a quadratic dependence of the rate coefficient for the reaction CH3 OH+OH on the water concentration was found. Thus the catalytic effect of water is not only important at low temperatures, but also at room temperature. The detailed mechanism responsible of the reaction acceleration is still unknown. However, this dependence should be included in the atmospheric global models since it is expected to be important in humid regions as in the tropics. Additionally, it could explain several differences regarding the global and local atmospheric concentration of methanol in tropical areas, for which many speculations about the sinks and sources of methanol have been reported.

RESUMO

We report a permutationally invariant, ab initio potential energy surface (PES) for the OH + HBr → Br + H2O reaction. The PES is a fit to roughly 26 000 spin-free UCCSD(T)/cc-pVDZ-F12a energies and has no classical barrier to reaction. It is used in quasiclassical trajectory calculations with a focus on the thermal rate constant, k(T), over the temperature range 5 to 500 K. Comparisons with available experimental data over the temperature range 23 to 416 K are made using three approaches to treat the OH rotational and associated electronic partition function. All display an inverse temperature dependence of k(T) below roughly 160 K and a nearly constant temperature dependence above 160 K, in agreement with experiment. The calculated rate constant with no treatment of spin-orbit coupling is overall in the best agreement with experiment, being (probably fortuitously) within 20% of it.

RESUMO

Objetivo: determinar la influencia de contaminantes atmosféricos sobre el agua de lluvia. Métodos: utilización de la deposición húmeda en un estudio de largo plazo, realizado en el Estado de Acre, Amazonia Occidental, 2005-2010. Se monitorearon 185 eventos de lluvia, se determinó en ellos el pH, la conductividad eléctrica y la concentración de carbono orgánico total. Se monitoreó la carga de aerosoles atmosféricos mediante fotometría solar y las condiciones meteorológicas a través de mediciones del vapor de agua, temperatura, vientos y lluvias en su comportamiento estacional. Resultados: la concentración de contaminantes según la profundidad óptica de aerosoles varió desde valores muy altos, entre 3 y 4 durante la seca, hasta valores muy bajos, aproximadamente de 0,08, durante la estación lluviosa. El 25 % de las lluvias fue ácida con pH entre 3 y 4,7 y un promedio de 5,4. Los valores de conductividad eléctrica generalmente fueron inferiores a 10 µS cm-1. El carbono orgánico total alcanzó valores relativamente altos, entre 20 y 30 mg L-1. Conclusiones: durante la seca los incendios forestales responden por la alta contaminación de la atmósfera, que queda limpia durante la estación lluviosa por efecto de la deposición húmeda. Durante la seca la carga de aerosoles atmosféricos aumenta en más de 40 veces, en comparación con el estado de la atmósfera en la estación lluviosa. Son necesarias medidas más eficientes de control de la degradación ambiental en la Amazonia y de monitoreo sistemático de la contaminación de su atmósfera, en beneficio de la salud humana y de otras formas de vida.

Objective: to determine the influence of air pollutants on the rainwater. Methods: use of wet deposition in a long-term study conducted in the state of Acre, in Western Amazon, from 2005 to 2010. One hundred and eightyfive rainy events were monitored to determine the pH value, the electrical conductivity and the concentration of total organic carbon. The atmospheric aerosol load was measured by solar photometry whereas the water vapors, temperature, winds and rains were monitored to observe weather conditions. Results: the pollutant concentration, depending on the aerosol optical depth, varied from very high values of 3 and 4 during the dry season, to very low values of about 0.08 during the rainy season. Twenty five percent of rainfalls were acidic with pH ranging 3 to 4.7, being 5.4 the average value. The electrical conductivity values were generally lower than 10 µS cm-1. The total organic carbon reached relatively high values of 20 to 30 mg L-1. Conclusions: in the dry season, the forest fires are responsible for high degree of air pollution, but the situation changes in the rainy season when the environment is clean because of the wet deposition. During the dry season, the air aerosol load increases 40 times if compared to the environmental conditions in the dry season. Therefore, more efficient control measures are needed to stop environmental degradation in the Amazon as well as a systematic monitoring of the air pollution for the benefit of human health and other forms of life.

RESUMO

The understanding of the natural processes that regulate atmospheric composition in Amazonia is critical to the establishment of a sustainable development strategy in the region. The large emissions of trace gases and aerosols during the dry season, as a result of biomass burning, profoundly change the composition of the atmosphere in most of its area. The concentration of trace gases and aerosols increases by a factor of 2 to 8 over large areas, affecting the natural mechanisms of several key atmospheric processes in the region. Cloud formation mechanisms, for instance, are strongly affected when the concentration of cloud condensation nuclei (CCN) changes from 200-300 CCN/cc in the wet season to 5,000-10,000 CCN/cc in the dry season. The cloud droplet radius is reduced from values of 18 to 25 micrometers in the wet season to 5 to 10 micrometers in the dry season, suppressing cloud formation and the occurrence of precipitation under some conditions. Ozone is a key trace gas for changes in the forest health, with concentrations increasing from 12 parts per billion (ppb), at the wet season, to values as high as 100 ppb (in the dry season in areas strongly affected by biomass burning emissions). At this level, ozone could be damaging the vegetation in regions far from the emissions. The atmospheric radiation balance is also strongly affected, with a net loss of up to 70% of photosynthetic active radiation at the surface.

Entender os processos naturais que regulam a composição da atmosfera é crítico para que se possa desenvolver uma estratégia de desenvolvimento sustentável na região. As grandes emissões de gases e partículas durante a estação seca provenientes das queimadas alteram profundamente a composição da atmosfera amazônica na maior parte de sua área. As concentrações de partículas de aerossóis e gases traço aumentam por fatores de 2 a 8 em grandes áreas, afetando os mecanismos naturais de uma série de processos atmosféricos na região amazônica. Os mecanismos de formação de nuvens, por exemplo, são profundamente alterados quando a concentração de núcleos de condensação de nuvens (NCN) passa de 200 a 300 NCN/cm³ na estação chuvosa para 5.000-10.000 NCN/centímetro cúbico na estação seca. As gotas de nuvens sofrem uma redução de tamanho de 18 a 25 micrômetros para 5 a 10 micrômetros, diminuindo a eficiência do processo de precipitação e suprimindo a formação de nuvens. A concentração de ozônio, um gás importante para a saúde da floresta amazônica passa de cerca de 12 partes por bilhão em volume (ppb) (concentração típica ao meio do dia na estação chuvosa) para valores em regiões fortemente impactadas por queimadas de até 100 ppb, nível que pode ser fitotóxico para a vegetação. O balanço de radiação é fortemente afetado, com uma perda líquida de até 70% da radiação fotossinteticamente ativa na superfície.