Numerical study of the atmospheric flow over a coastal cliff

This work presents a numerical method suitable for the study of the development of internal boundary layers (IBL) and their characteristics for flows over various types of coastal cliffs. The IBL is an important meteorological occurrence for flows with surface roughness and topographical step changes. A two-dimensional flow program was used for this study. The governing equations were written using the vorticity-velocity formulation. The spatial derivatives were discretized by high-order compact finite differences schemes. The time integration was performed with a low storage fourth-order Runge-Kutta scheme. The coastal cliff (step) was specified through an immersed boundary method. The validation of the code was done by comparison of the results with experimental and observational data. The numerical simulations were carried out for different coastal cliff heights and inclinations. The results show that the predominant factors for the height of the IBL and its characteristics are the upstream velocity, and the height and form (inclination) of the coastal cliff. Copyright (C) 2010 John Wiley & Sons, Ltd.

Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH(-) and F(-) with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO(3)(-) is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH(-) at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (18)OH(-) showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH(2)(-) and SH(-) to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

Desenvolvimento de uma unidade laboratorial para quantificação de BTX como poluentes atmosféricos, usando microextração em fase sólida

This dissertation aims the development of an experimental device to determine quantitatively the content of benzene, toluene and xylenes (BTX) in the atmosphere. BTX are extremely volatile solvents, and therefore play an important role in atmospheric chemistry, being precursors in the tropospheric ozone formation. In this work a BTX new standard gas was produced in nitrogen for stagnant systems. The aim of this dissertation is to develop a new method, simple and cheaper, to quantify and monitor BTX in air using solid phase microextraction/ gas chromatography/mass spectrometry (SPME/CG/MS). The features of the calibration method proposed are presented in this dissertation. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fiber exposed for 10 min standard gas mixtures. It is observed that the main parameters that affect the extraction process are sampling time and concentration. The results of the BTX multicomponent system studied have shown a linear and a nonlinear range. In the non-linear range, it is remarkable the effect of competition by selective adsorption with the following affinity order p-xylene > toluene > benzene. This behavior represents a limitation of the method, however being in accordance with the literature. Furthermore, this behavior does not prevent the application of the technique out of the non-linear region to quantify the BTX contents in the atmosphere.

Observational Characterization of the Downward Atmospheric Longwave Radiation at the Surface in the City of São Paulo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Precipitation chemistry in semi-arid areas of Southern Africa: A case study of a rural and an industrial site

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.

Lightning characteristics observed by a VLF/LF lightning detection network (LINET) in Brazil, Australia, Africa and Germany

This paper describes lightning characteristics as obtained in four sets of lightning measurements during recent field campaigns in different parts of the world from mid-latitudes to the tropics by the novel VLF/LF (very low frequency/low frequency) lightning detection network (LINET). The paper gives a general overview on the approach, and a synopsis of the statistical results for the observation periods as a whole and for one special day in each region. The focus is on the characteristics of lightning which can specifically be observed by this system like intra-cloud and cloud-to-ground stroke statistics, vertical distributions of intra-cloud strokes or peak current distributions. Some conclusions regarding lightning produced NOx are also presented as this was one of the aims of the tropical field campaigns TROCCINOX (Tropical Convection, Cirrus and Nitrogen Oxides Experiment) and TroCCiBras (Tropical Convection and Cirrus Experiment Brazil) in Brazil during January/February 2005, SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) and TWP-ICE (Tropical Warm Pool-International Cloud Experiment) during November/December 2005 and January/February 2006, respectively, in the Darwin area in N-Australia, and of AMMA (African Monsoon Multidisciplinary Analyses) in W-Africa during June-November 2006.

NDACC/SAOZ UV-visible total ozone measurements: improved retrieval and comparison with correlative ground-based and satellite observations

Accurate long-term monitoring of total ozone is one of the most important requirements for identifying possible natural or anthropogenic changes in the composition of the stratosphere. For this purpose, the NDACC (Network for the Detection of Atmospheric Composition Change) UV-visible Working Group has made recommendations for improving and homogenizing the retrieval of total ozone columns from twilight zenith-sky visible spectrometers. These instruments, deployed all over the world in about 35 stations, allow measuring total ozone twice daily with limited sensitivity to stratospheric temperature and cloud cover. The NDACC recommendations address both the DOAS spectral parameters and the calculation of air mass factors (AMF) needed for the conversion of O-3 slant column densities into vertical column amounts. The most important improvement is the use of O-3 AMF look-up tables calculated using the TOMS V8 (TV8) O-3 profile climatology, that allows accounting for the dependence of the O-3 AMF on the seasonal and latitudinal variations of the O-3 vertical distribution. To investigate their impact on the retrieved ozone columns, the recommendations have been applied to measurements from the NDACC/SAOZ (Systeme d'Analyse par Observation Zenithale) network. The revised SAOZ ozone data from eight stations deployed at all latitudes have been compared to TOMS, GOMEGDP4, SCIAMACHY-TOSOMI, SCIAMACHY-OL3, OMI-TOMS, and OMI-DOAS satellite overpass observations, as well as to those of collocated Dobson and Brewer instruments at Observatoire de Haute Provence (44 degrees N, 5.5 degrees E) and Sodankyla (67 degrees N, 27 degrees E), respectively. A significantly better agreement is obtained between SAOZ and correlative reference ground-based measurements after applying the new O-3 AMFs. However, systematic seasonal differences between SAOZ and satellite instruments remain. These are shown to mainly originate from (i) a possible problem in the satellite retrieval algorithms in dealing with the temperature dependence of the ozone cross-sections in the UV and the solar zenith angle (SZA) dependence, (ii) zonal modulations and seasonal variations of tropospheric ozone columns not accounted for in the TV8 profile climatology, and (iii) uncertainty on the stratospheric ozone profiles at high latitude in the winter in the TV8 climatology. For those measurements mostly sensitive to stratospheric temperature like TOMS, OMI-TOMS, Dobson and Brewer, or to SZA like SCIAMACHY-TOSOMI, the application of temperature and SZA corrections results in the almost complete removal of the seasonal difference with SAOZ, improving significantly the consistency between all ground-based and satellite total ozone observations.

End-to-end validation of EPS / MetOp GOME-2 trace gas data

Within the next decade, the improved version 2 of Global Ozone Monitoring Experiment (GOME-2), a ultraviolet-visible spectrometer dedicated to the observation of key atmospheric trace species from space, will be launched successively on board three EUMETSAT Polar System (EPS) MetOp satellites. Starting with the launch of MetOp-1 scheduled for summer 2006, the GOME-2 series will extend till 2020 the global monitoring of atmospheric composition pioneered with ERS-2 GOME-1 since 1995 and enhanced with Envisat SCIAMACHY since 2002 and EOS-Aura OMI since 2004. For more than a decade, an international pool of scientific teams active in ground-and space-based ultraviolet-visible remote sensing have contributed to the successful post-launch validation of trace gas data products and the associated maturation of retrieval algorithms for the latter satellites, ensuring that geophysical data products are/become reliable and accurate enough for intended research and applications. Building on this experience, this consortium plans now to develop and carry out appropriate validation of a list of GOME-2 trace gas column data of both tropospheric and stratospheric relevance: nitrogen dioxide (NO 2), ozone (O 3), bromine monoxide (BrO), chlorine dioxide (OClO), formaldehyde (HCHO), and sulphur dioxide (SO 2). The proposed investigation will combine four complementary approaches resulting in an end-to-end validation of expected column data products.

Including the sub-grid scale plume rise of vegetation fires in low resolution atmospheric transport models

We describe and begin to evaluate a parameterization to include the vertical transport of hot gases and particles emitted from biomass burning in low resolution atmospheric-chemistry transport models. This sub-grid transport mechanism is simulated by embedding a 1-D cloud-resolving model with appropriate lower boundary conditions in each column of the 3-D host model. Through assimilation of remote sensing fire products, we recognize which columns have fires. Using a land use dataset appropriate fire properties are selected. The host model provides the environmental conditions, allowing the plume rise to be simulated explicitly. The derived height of the plume is then used in the source emission field of the host model to determine the effective injection height, releasing the material emitted during the flaming phase at this height. Model results are compared with CO aircraft profiles from an Amazon basin field campaign and with satellite data, showing the huge impact that this mechanism has on model performance. We also show the relative role of each main vertical transport mechanisms, shallow and deep moist convection and the pyro-convection (dry or moist) induced by vegetation fires, on the distribution of biomass burning CO emissions in the troposphere.

A study of the effect of overshooting deep convection on the water content of the TTL and lower stratosphere from Cloud Resolving Model simulations

Simulations of overshooting, tropical deep convection using a Cloud Resolving Model with bulk microphysics are presented in order to examine the effect on the water content of the TTL (Tropical Tropopause Layer) and lower stratosphere. This case study is a subproject of the HIBISCUS (Impact of tropical convection on the upper troposphere and lower stratosphere at global scale) campaign, which took place in Bauru, Brazil (22° S, 49° W), from the end of January to early March 2004. Comparisons between 2-D and 3-D simulations suggest that the use of 3-D dynamics is vital in order to capture the mixing between the overshoot and the stratospheric air, which caused evaporation of ice and resulted in an overall moistening of the lower stratosphere. In contrast, a dehydrating effect was predicted by the 2-D simulation due to the extra time, allowed by the lack of mixing, for the ice transported to the region to precipitate out of the overshoot air. Three different strengths of convection are simulated in 3-D by applying successively lower heating rates (used to initiate the convection) in the boundary layer. Moistening is produced in all cases, indicating that convective vigour is not a factor in whether moistening or dehydration is produced by clouds that penetrate the tropopause, since the weakest case only just did so. An estimate of the moistening effect of these clouds on an air parcel traversing a convective region is made based on the domain mean simulated moistening and the frequency of convective events observed by the IPMet (Instituto de Pesquisas Meteorológicas, Universidade Estadual Paulista) radar (S-band type at 2.8 Ghz) to have the same 10 dBZ echo top height as those simulated. These suggest a fairly significant mean moistening of 0.26, 0.13 and 0.05 ppmv in the strongest, medium and weakest cases, respectively, for heights between 16 and 17 km. Since the cold point and WMO (World Meteorological Organization) tropopause in this region lies at ∼ 15.9 km, this is likely to represent direct stratospheric moistening. Much more moistening is predicted for the 15-16 km height range with increases of 0.85-2.8 ppmv predicted. However, it would be required that this air is lofted through the tropopause via the Brewer Dobson circulation in order for it to have a stratospheric effect. Whether this is likely is uncertain and, in addition, the dehydration of air as it passes through the cold trap and the number of times that trajectories sample convective regions needs to be taken into account to gauge the overall stratospheric effect. Nevertheless, the results suggest a potentially significant role for convection in determining the stratospheric water content. Sensitivity tests exploring the impact of increased aerosol numbers in the boundary layer suggest that a corresponding rise in cloud droplet numbers at cloud base would increase the number concentrations of the ice crystals transported to the TTL, which had the effect of reducing the fall speeds of the ice and causing a ∼13% rise in the mean vapour increase in both the 15-16 and 16-17 km height ranges, respectively, when compared to the control case. Increases in the total water were much larger, being 34% and 132% higher for the same height ranges, but it is unclear whether the extra ice will be able to evaporate before precipitating from the region. These results suggest a possible impact of natural and anthropogenic aerosols on how convective clouds affect stratospheric moisture levels.

Efeito de um revestimento com processamento rápido para fundição de titânio na camada de reação, porosidade interna, fluidez, rugosidade superficial e adaptação marginal de Copings

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Measurements and modeling of reactive nitrogen deposition in southeast Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atmospheric pollutants in São Paulo state, Brazil and effects on human health – a review

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ozone and nitrogen dioxide gas sensor based on a nanostructured SrTi0.85Fe0.15O3 thin film

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Carbon monoxide and related trace gases and aerosols over the Amazon Basin during the wet and dry seasons

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.