Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX?=?O₃?+?NO₂), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO₂ and OX cycles. The variation of OX concentrations with NO _x is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO _x was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO₂]/[OX] and [NO₂]/[NO _x ] vs. [NO _x ] were analysed to find the fraction of OX in the form of NO₂, and the possible source of the local NO _x -dependent contribution, respectively. The progressive increase of the ratio [NO₂]/[OX] with [NO _x ] observed shows a greater proportion of OX in the form of NO₂ as the level of NO _x increases. The higher measured values in the ratio [NO₂]/[NO _x ] should not be attributed to NO _x emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO₂ photolysis, J _NO2?=?0.18–0.64 min^?1, a key atmospheric reaction that influence O₃ production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.     

Ultraviolet Irradiance over Mexico City

Abstract

This article compiles and analyzes information on the interaction of both ground-level ultraviolet radiation and anthropogenic ozone in the extremely polluted atmosphere of Mexico City. Simultaneous anthropogenic ozone and global flux (sun and sky) measurements were recorded in near ultraviolet radiation (295-385 nm) for a 30-month period (March 1990 to August 1992). Results reveal that under clear sky conditions, high concentrations of ozone (and presumably of other pollutants) impede UV-fluxes from reaching their maximum values. Furthermore, heavy cloud cover causes ozone concentrations to reach their minimum values together with UV-minimum fluxes. Seasonal variation in UV-irradiance is also discussed. Findings indicate that maximum UV-fluxes occur in spring and summer and that minimum values occur in autumn and winter. Significant daily local reductions in UV-fluxes (up to 50%) during afternoon hours in Mexico City can be attributed to air pollution. Finally, the growing incidence of rickets in children residing in the Mexico City metropolitan area may be related both to dietary deficiencies and to the UV-flux depletion on the ground.     

Cytological study and immunohistochemical location of PSP toxins in foot skin of the ormer, Haliotis tuberculata, from the Galician coast (NW Spain)

The ormer, Haliotis tuberculata Linnaeus, 1758, is able to accumulate paralytic shellfish toxins (PST) in the foot side skin. Epidermal and secretory cells are described separately for the pedal side and sole epithelia, as notable differences have been observed. Melanin and photosynthetic pigment granules in the epidermal cells of the foot side epithelium give this skin its appearance and characteristic color. This epidermis also has abundant secretory cells containing at least three kinds of secretory granules. Conversely, the epidermal cells of foot sole epithelium do not have pigment granules, and the secretory cells are mostly subepithelial. Immunohistochemical reaction against PST (saxitoxin and its derivatives) showed that the toxins are located in specific cells of the foot side epithelium, which are distinct from the epidermal cells. Immunofluorescence also reveals toxins throughout many areas of the mucilage covering the epithelium, suggesting the secretory nature of the cells containing the toxins. These results do not show any apparent relationship between melanin or photosynthetic pigment granules and PST content. PST were not detected in the foot sole epithelium either immunohistochemically or by HPLC. Considering the toxic characteristics of ormers described in previous studies and the results presented here, the authors discuss the role of toxins retained or produced by the foot side epithelium Received: 25 July 2000 / Accepted: 7 November 2000     

Relationships between trace elements in <Emphasis Type="Italic">Posidonia oceanica</Emphasis> shoots and in sediment fractions along Latium coasts (northwestern Mediterranean Sea)

The Mediterranean endemic seagrass Posidonia oceanica is widely used as a sensitive bioindicator of trace elements (TEs) in the coastal environment. Therefore, a bulk of data exist on TE levels from impacted versus unpolluted sites while only recent studies started comparing TE accumulation in plant compartments versus both water column and sediment characteristics. In this study, six TEs (As, Cd, Cr, Cu, Ni, Pb) were analyzed in P. oceanica shoots related to depth (?10 and ?20 m) and to TE concentrations in the different grain size fractions of the sediment, from two Sites of Community interest (SIC) in the central Tyrrhenian Sea. TE concentrations in both shoots and sediment were generally low, except for Cr. Cu was the only element showing significantly different concentrations at the two sites while As differed significantly between samples taken at different depths. TE concentrations in the unsieved sediment were found uncorrelated to TEs in shoots except for the important nutrient Cu (positive correlation). The finest sediment fractions were enriched in TEs and significantly correlated to Cd, Cr, Cu, and Ni concentrations in the shoots.     

Distribution of mercury and organic matter in particle-size classes in sediments contaminated by a waste water treatment plant: Vidy Bay, Lake Geneva, Switzerland

In Lake Geneva, Switzerland, the most Hg-contaminated sediments have been found in the Vidy Bay where high Hg contents largely exceeds the background levels of Lake Geneva sediments. This contamination has been attributed to the discharge of a waste water treatment plant (WWTP). Total Hg (THg) and monomethylmercury (MMHg) were determined in bulk sediment and in three different grain size fractions (i: clay and silt, ii: fine-coarse sand, iii: and very coarse sand and gravel) collected close to the outlet pipe of a WWTP in order to verify whether the standardized procedures of sediment treatment is adequate for this setting and, by extension, for similar contaminated sites. THg was homogeneously distributed in the different grain size fractions and was correlated to organic matter content (R(2) = 0.6). MMHg was homogeneously distributed in the two finer grain fractions (Φ < 0.063 mm; 0.063 mm < Φ <1 mm). The results of this study suggested that the analysis of the bulk sediment seems to be more appropriate for the assessment of the content and spatial distribution of Hg in freshwater sediments contaminated by WWTPs.     

Effect of acid rain on building material of the El Tajín archaeological zone in Veracruz, Mexico

Three limestone slabs (approx. 20 cm2 each) were extracted from the El Tajin archaeological zone in Veracruz, Mexico. X-ray diffraction analysis revealed three components: calcite (81.2%), quartz (17.9%) and feldspar (0.9%). Calcite content by x-ray diffraction analysis was slightly higher than that determined by chemical reaction between the limestone sample and nitric acid. The latter analysis, carried out in triplicate, yielded a calcite content of 77.1%. Mean water absorption, density and porosity of the limestone samples were also determined. Dissolution of limestone samples was investigated using an experimental rainfall simulation chamber, in which the stone samples were irrigated with artificial rain matching the pH and the ionic composition with 40 rainfall samples collected at El Tajin from August 18, 2002, to April 9, 2003. According to calcium and bicarbonate net concentrations found in the effluent of the chamber, a chemical mechanism by which limestone at El Tajin is dissolved by acid rain is proposed. A model used to investigate the air transport pathways corresponding to precipitation events at El Tajin shows that air parcels come mainly from the Gulf of Mexico, although no directional preference is evident for acidic vs. non-acidic events.     

Spatial heterogeneity of PM10 and O3 in São Paulo, Brazil, and implications for human health studies

Developing exposure estimates is a challenging aspect of investigating the health effects of air pollution. Pollutant levels recorded at centrally located ambient air quality monitors in a community are commonly used as proxies for population exposures. However, if ample intraurban spatial variation in pollutants exists, city-wide averages of concentrations may introduce exposure misclassification. We assessed spatial heterogeneity of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) and ozone (O3) and evaluated implications for epidemiological studies in S?o Paulo, Brazil, using daily (24-hr) and daytime (12-hr) averages and 1-hr daily maximums of pollutant levels recorded at the regulatory monitoring network. Monitor locations were also analyzed with respect to a socioeconomic status index developed by the municipal government. Hourly PM10 and O3 data for the Sāo Paulo Municipality and Metropolitan Region (1999-2006) were used to evaluate heterogeneity by comparing distance between monitors with pollutants' correlations and coefficients of divergence (CODs). Both pollutants showed high correlations across monitoring sites (median = 0.8 for daily averages). CODs across sites averaged 0.20. Distance was a good predictor of CODs for PM10 (p < 0.01) but not O3, whereas distance was a good predictor of correlations for O3 (p < 0.01) but not PM10. High COD values and low temporal correlation indicate a spatially heterogeneous distribution of PM10. Ozone levels were highly correlated (r > or = 0.75), but high CODs suggest that averaging over O3 levels may obscure important spatial variations. Of municipal districts in the highest of five socioeconomic groups, 40% have > or = 1 monitor, whereas districts in the lowest two groups, representing half the population, have no monitors. Results suggest that there is a potential for exposure misclassification based on the available monitoring network and that spatial heterogeneity depends on pollutant metric (e.g., daily average vs. daily 1-hr maximum). A denser monitoring network or alternative exposure methods may be needed for epidemiological research. Findings demonstrate the importance of considering spatial heterogeneity and differential exposure misclassification by subpopulation.     

Impact of wildfires on the air quality of Mexico City, 1992-1999

Wildfires in Mexico increased in 1998, compared to information for the last 6 years. The average number of wildfires in the Mexico City Metropolitan Area (MCMA) for this year (1998) were 58% (1916 events) more events than the 1992-1997 (average cases 1217 events). Mexico City affected area corresponds to 1.3% of the national affected area. The purpose of this paper is to evaluate the impact on the particles air quality due to the wildfire emissions at the MCMA and surrounding areas. Using the corresponding US EPA emission factors for wildfires, the tons of particulate matter, nitrogen oxides, carbon monoxide, and total hydrocarbons emitted by this source for the MCMA case were obtained. The calculated emissions during wildfires were correlated with the levels of particles present in the atmosphere. A comparison of the concentration levels of particles, both as PM10 as well as TSP, were made for the years 1992-1998, during wet and dry season, being March, April, and May the critical months due to the presence of wildfires. A good correlation is observed between particulate wildfire emissions and particulate air quality, being stronger for TSP. A clear impact on the particles air quality due to the increase of wildfires in 1998, is observed when this year is compared with 1997, presenting an increment of 200-300% for some monitoring stations.