A significant proportion of the solar irradiance that reaches the Earth's surface is normally attenuated by atmospheric properties and overcast conditions related to the rainy season. The Solar Analyst (SA) model, irradiance and long term precipitation data were used to assess this relationship in Guadalajara, Mexico. A spatial analysis based on morphological and statistical criteria increased the model's certainty. The SA model explains 95.4% of the irradiation variability observed on the ground, with average uncertainties of 3.7% during clear sky conditions in the dry season and 4.4% on sunny days in the wet season. The meteorological data analysis shows that total precipitation in 2014 had an atypical temporal distribution and was slightly lower (12.6%) than the average from 1991 to 2012. A deficit of 39% in precipitation compared to the long term average was found in the first half of the season, which was later partially compensated. This deficit was interpreted as a temporary delay in high values of precipitation. Based on the potential average irradiation from the SA model and field observations, it can be concluded that overcast conditions related to rainfall through 2014 attenuated approximately 28.5% of the incoming solar energy. Taking the global energy balance into account, this fraction was higher in comparison to the energy proportion reflected by the cloud's albedo (ca 23%). These results suggest that both the high proportion of energy attenuated and atypical weather conditions may be local effects of large-scale phenomena such as the El Niño-Southern Oscillation.
This study aims to establish the influence of primary emission sources and atmospheric transformation process contributing to the concentrations of quinones associated to particulate matter of less than 2.5 µm (PM 2.5 ) in three sites within the Metropolitan Area of Guadalajara (MAG), namely Centro (CEN), Tlaquepaque (TLA) and Las Águilas (AGU). Environmental levels of quinones extracted from PM 2.5 filters were analyzed using Gas Chromatography coupled to Mass Spectrometry (GC-MS). Overall, primary emissions in combination with photochemical and oxidation reactions contribute to the presence of quinones in the urban atmosphere of MAG. It was found that quinones in PM 2.5 result from the contributions from direct emission sources by incomplete combustion of fossil fuels such as diesel and gasoline that relate mainly to vehicular activity intensity in the three sampling sites selected. However, this also suggests that the occurrence of quinones in MAG can be related to photochemical transformation of the parent Polycyclic Aromatic Hydrocarbons (PAHs), to chemical reactions with oxygenated species, or a combination of both routes. The higher concentration of 1,4-Chrysenequinone during the rainy season compared to the warm-dry season indicates chemical oxidation of chrysene, since the humidity could favor singlet oxygen collision with parent PAH present in the particle phase. On the contrary, 9,10-Anthraquinone/Anthracene and 1,4-Naftoquinone/Naphthalene ratios were higher during the warm-dry season compared to the rainy season, which might indicate a prevalence of the photochemical formation during the warm-dry season favored by the large solar radiation typical of the season. In addition, the estimated percentage of photochemical formation of 9,10-Phenanthrenequinone showed that the occurrence of this compound in Tlaquepaque (TLA) and Las Águilas (AGU) sites is mainly propagated by conditions of high solar radiation such as in the warm-dry season and during long periods of advection of air masses from emission to the reception areas. This was shown by the direct association between the number hourly back trajectories arriving in the TLA and AGU from Centro and other areas in MAG and the highest photochemical formation percentage.
. Spatial variations were found during the dry-warm season, which were attributed mainly to differing intensities of local traffic and less dispersion of air pollutants in Miravalle. Seasonal variations were associated with increases in rainfall (June-September) and differences in temperature (January-May and October-January). The benzo(a)pyrene-equivalent (BaPE) and BaP results suggest that exposure to PM 2.5 -containing carcinogenic PAHs (C-PAHs) in Miravalle during the warm-dry and cold-dry seasons can be seen as representing a serious risk to human health. The contributions from potential sources to PAHs in PM 2.5 were evaluated by the diagnostic ratios between PAHs and principal component analysis (PCA). In the whole sampling period, vehicular emission activity, probably related to light and heavy traffic, was found to be the predominant contributor to PM 2.5 -bound PAHs.
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