Indigo adsorption on a silicate surface: a theoretical density functional study.

The applicability of naturally available low-cost and eco-friendly adsorbent materials for the removal of hazardous dyes from aqueous waste is of increasing environmental interest. Among the adsorption treatments available, clays seem to be economically attractive due to their abundance and adsorption capabilities. Indeed, many ancient coloring materials utilized clays mixed with natural dyes (e.g., indigo in Maya Blue). In this work, we performed a quantum-mechanical theoretical study of the adsorption of the indigo molecule onto the (001) surface of a phyllosilicate. Different methods and approaches were applied and compared. We found that the presence of a tetrahedral charge and a sodium counterion significantly increased the adsorption energy of the indigo molecule. The vibrational spectrum of the dye-surface system was also studied, and some interesting shifts in the frequencies of the main vibrational modes of indigo due to its interaction with the surface of the clay mineral were identified.

Molecular description of indigo oxidation mechanisms initiated by OH and OOH radicals.

In this work, we report a quantum chemistry mechanistic study of the hydroxyl (•OH) and hydroperoxyl (•OOH) radicals initiated oxidation of indigo, within the density functional theory framework. All possible hydrogen abstraction and radical addition reaction pathways have been considered. We find that the reaction between a free indigo molecule and an •OH radical occurs mainly through two competing mechanisms: H-abstraction from an NH site and •OH addition to the central C═C double bond. Although the latter is favored, both channels occur, the indigo chromophore group structure is modified, and thus the color is changed. This mechanism adequately accounts for the loss of chromophore in urban air, including indoor air such as in museums and in urban areas. Regarding the reactivity of indigo toward •OOH radicals, only •OOH-addition to the central double bond is thermodynamically feasible. The corresponding transition state free energy value is about 10 kcal/mol larger than the one for the •OH initiated oxidation. Therefore, even considering that the •OOH concentration is considerably larger than the one of •OH, this reaction is not expected to contribute significantly to indigo oxidation under atmospheric conditions.

Instrumental nuclear activation analysis (INAA) characterization of environmental air filter samples.

Nuclear techniques have been used in quantitations of environmental pollutants, and instrumental neutron activation analysis (INAA) has turned out to be particularly useful in the analysis of airborne suspended particles. This work describes the INAA characterization of the particulate material in the environmental samples obtained in a monitoring campaign in Mexico City's Metropolitan Area. As the types of the irradiation facilities and gamma-ray detection system impose some limitations on the possibilities of INAA analysis, the actual experimental conditions at Gamma Spectroscopy Laboratory, where the analysis was performed, had been assessed. The facilities had been found suitable for the analysis of samples from this campaign, in which 22 elements were determined.

Spatial differences in outdoor PM10 mass and aerosol composition in Mexico City.

Twenty-five MiniVol samplers were operated throughout the Mexico City metropolitan region from February 22 through March 22, 1997, to evaluate the variability of PM10 concentrations and composition. The highest PM10 concentrations were found in neighborhoods with unpaved or dirty roads, and elements related to crustal material were the main cause of differences from nearby (<200 m) monitors that were not adjacent to the roadbed. SO4(2-) concentrations were homogeneous across the city. SO4(2-) measured at the city boundaries was about two-thirds of the concentrations measured within the urbanized area, indicating that most SO4(2-) is of regional origin. Elemental carbon (EC) and organic carbon (OC) concentrations were highly variable, with higher concentrations in areas that had high diesel traffic and older vehicles. Spatial correlations among PM10 concentrations were high, even though absolute concentrations were variable, indicating a common effect of meteorology on the concentration or dispersion of local emissions.