Analytical investigation of the atmospheric radiation limits in semigray atmospheres in radiative equilibrium

We model the wavelength-dependent absorption of atmospheric gases by assuming constant mass absorption coefficients in finite-width spectral bands. Such a semigray atmosphere is analytically solved by a discrete ordinate method. The general solution is analyzed for a water vapor saturated atmosphere that also contains a carbon dioxide-like absorbing gas in the infrared. A multiple stable equilibrium with a relative upper limit in the outgoing long-wave radiation is found. Differing from previous radiative–convective models, we find that the amount of carbon dioxide strongly modifies the value of this relative upper limit. This result is also obtained in a gray (i.e., equal absorption of radiation at all infrared wavelengths) water vapor saturated atmosphere. The destabilizing effect of carbon dioxide implies that massive carbon dioxide atmospheres are more likely to reach a runaway greenhouse state than thin carbon dioxide ones

Size distribution of atmospheric particulate ionic species at a coastal site in Portugal

A Berner impactor was used to collect size-differentiated aerosol samples from March to August 2003 in the city of Aveiro, on the Portuguese west coast. The samples were analysed for the main water-soluble ion species. The average concentration of sulphate, nitrate, chloride and ammonium was 6.38, 3.09, 1.67 and 1.27 µg m-3, respectively. The results show that SO4(2-) and NH4+ were consistently present in the fine fraction < 1 µm, which represents, on average, 72 and 89% of their total atmospheric concentrations, respectively. The NO3-particles were concentrated in the coarse size. Chloride presented the characteristic coarse mode for marine aerosols. During some spring/summer events, an ammonium surplus was observed (NH4+/SO4(2-) molar ratios > 2), possibly due to greater availability of ammonia coming from agricultural activities or from the neighbouring chemical industrial complex. During the remaining periods, the aerosol was found to be somewhat acidic and predominantly in the form of ammonium bisulphate (NH4+/SO4(2-) molar ratios = 0.5-1.25). Samples collected under a major or exclusive influence of maritime air masses were essentially constituted by coarse particles with enrichment in sea salt, while for air masses of continental origin the contribution of water-soluble ionic species in the fine mode was more pronounced.

Solution thermodynamics of methocarbamol in some ethanol + water mixtures

Apparent thermodynamic functions, Gibbs energy, enthalpy and entropy of solution and mixing, for methocarbamol in ethanol + water mixtures, were evaluated from solubility data determined at temperatures from 293.15 K to 313.15 K and from calorimetric values of drug fusion. The drug solubility was greatest in the mixtures with 0.70 or 0.80 mass fraction of ethanol and lowest in neat water across all temperatures studied. Non-linear enthalpy-entropy compensation was found for the dissolution processes. Accordingly, solution enthalpy drives the respective processes in almost all the solvent systems analyzed.

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Evaluation of the dioxin and furan formation thermodynamics in combustion processes of urban solid wastes

Specific combustion programs (Gaseq, Chemical equilibria in perfect gases, Chris Morley) are used to model dioxin and formation in the incineration processes of urban solid wastes. Thanks to these programs, it is possible to establish correlations with the formation mechanisms postulated in literature on the subject. It was found that minimum oxygen quantities are required to obtain a significant formation of these compounds and that more furans than dioxins are formed. Likewise, dioxin and furan formation is related to the presence of carbon monoxide, and dioxin and furan distribution among its different compounds depends on the chlorine and hydrogen relative composition. This is due to the fact that an increased chlorine availability leads to the formation of compounds bearing a higher chlorine concentration (penta-, hexa-, hepta-, and octachlorides), whereas an increased hydrogen availability leads to the formation of compounds bearing a lower chlorine number (mono, di-, tri-, and tetrachlorides).

Application of a non isotropic turbulence model to stable atmospheric flows and dispersion over 3D topography

A non isotropic turbulence model is extended and applied to three dimensional stably stratified flows and dispersion calculations. The model is derived from the algebraic stress model (including wall proximity effects), but it retains the simplicity of the "eddy viscosity" concept of first order models. The "modified k-epsilon" is implemented in a three dimensional numerical code. Once the flow is resolved, the predicted velocity and turbulence fields are interpolated into a second grid and used to solve the concentration equation. To evaluate the model, various steady state numerical solutions are compared with small scale dispersion experiments which were conducted at the wind tunnel of Mitsubishi Heavy Industries, in Japan. Stably stratified flows and plume dispersion over three distinct idealized complex topographies (flat and hilly terrain) are studied. Vertical profiles of velocity and pollutant concentration are shown and discussed. Also, comparisons are made against the results obtained with the standard k-epsilon model.

Wind tunnel simulation of atmospheric boundary layer flows

The present work shows how thick boundary layers can be produced in a short wind tunnel with a view to simulate atmospheric flows. Several types of thickening devices are analysed. The experimental assessment of the devices was conducted by considering integral properties of the flow and the spectra: skin-friction, mean velocity profiles in inner and outer co-ordinates and longitudinal turbulence. Designs based on screens, elliptic wedge generators, and cylindrical rod generators are analysed. The paper describes in detail the experimental arrangement, including the features of the wind tunnel and of the instrumentation. The results are compared with experimental data published by other authors and with naturally developed flows.

Effects of different ammoniacal nitrogen sources on N-metabolism of the atmospheric bromeliad Tillandsia pohliana Mez

Increasing levels of atmospheric ammonia from anthropogenic sources have become a serious problem for natural vegetation. Short-term effects of different ammoniacal sources on the N metabolism of Tillandsia pohliana, an atmospheric bromeliad, were investigated. One-year-old, aseptically grown plants were transferred to a modified Knudson medium lacking N for three weeks. Plants were subsequently transferred to Knudson media supplemented with 0.5, 1.0, or 1.5 mM of N in the forms of NH3 or NH4+ as the sole N source. The activities of glutamine synthetase (GS) and glutamate dehydrogenase (GDH-NADH) were determined after 40 h. The GS activity was stimulated significantly by increasing the levels of the gaseous form. The GDH-NADH activity increased significantly under increasing N concentrations with NH3, while no significant differences were observed with NH4+ as a N source. These results may reflect a faster NH3 absorption by T. pohliana compared to NH4+ uptake. The increased activity of GDH-NADH in NH3 treatment may play a role in protecting the cells from the toxic effects of increased endogenous level of free ammonium. A raise in the concentration of N, especially in the form of NH3, greatly increased the content of free amino acids and soluble proteins. A possible utilisation of T. pohliana to evaluate the changes of atmospheric gaseous ammonia is proposed.

In situ variation of cervical mucus pH during exposure to atmospheric air

The objective of the present study was to determine if exposure of cervical mucus to air during specular examination could modify mucus pH. Detection of changes is justified because of their possible interference with sperm-mucus interaction, since an acidic pH is unfavorable to sperm penetration and is associated with infertility due to the cervical factor. Twenty women with good quality mucus were evaluated. pH measurements of ecto- and endocervical mucus were made in situ using a glass electrode after 0-, 5- and 10-min exposure to air. There was a progressive alkalinization of mucus pH. Mean values of ectocervical mucus pH were 6.91, 7.16 and 7.27, while mean values of endocervical mucus pH were 7.09, 7.34 and 7.46 at 0, 5 and 10 min, respectively. Significant differences were found between the mean values obtained at 0 and 5 min, and at 0 and 10 min (P<0.05), whereas the differences in mean values at 5 and 10 min were not significant at either site. We conclude that 5 to 10 min of exposure to atmospheric air affects cervical mucus pH in a significant way. Since tests used to evaluate sperm-mucus interaction generally have not considered this possibility, we suggest that they should be performed immediately after mucus collection in order to avoid misinterpretation of the results.

Dynamic characteristics of Atmospheric boundary Layer during different phases of Monsoon

Atmospheric Boundary layer (ABL) is the layer just above the earth surface and is influenced by the surface forcing within a short period of an hour or less. In this thesis, characteristics of the boundary layer over ocean, coastal and inland areas of the atmosphere, especially over the monsoon regime are thoroughly studied. The study of the coastal zone is important due to its high vulnerability mainly due to sea breeze circulation and associated changes in the atmospheric boundary layer. The major scientific problems addressed in this thesis are diurnal and seasonal variation of coastal meteorological properties, the characteristic difference in the ABL during active and weak monsoons, features of ABL over marine environment and the variation of the boundary layer structure over an inland station. The thesis describes the various features in the ABL associated with the active and weak monsoons and, the surface boundary layer properties associated with the active and weak epochs. The study provides knowledge on MABL and can be used as the estimated values of boundary layer parameters over the marine atmosphere and to know the values and variabilities of the ABL parameters such as surface wind, surface friction, drag coefficient, wind stress and wind stress curl.

Thermodynamics of transfer of polar nonelectrolytes from water to aqueous salt solutions

The Setschenow parameter and thermodynamic parameters of transfer of a number of monosubstituted benzoic acids from water to different salt solutions have been reported. The data have been rationalized by considering the structure breaking effects of the ions of the salts, the localised hydrolysis model, the internal pressure theory and Symons' theory of water structure.

Thermodynamics of Transfer of Aminobenzoic Acids from Water to Aqueous Salt Solutions

The Setschenow parameter and thermodynamic parameters of transfer of 2- and 4-aminobenzoic acids from water to salt solutions have been reported. The results are discussed in terms of the structure- breaking effects of the ions of the salts, the localized hydrolysis model, and the internal pressure theory.