A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.     

Does intensity of change matter? Factors affecting adoption of agri-environmental schemes in Spain

Agri-environmental schemes (AES) are the main policy instrument currently available in the EU to promote environmentally-friendly farming practices. However, the rate of adoption of these measures is still relatively low in southern Europe, and understanding how these rates can be increased is still an open issue. The goal of this paper is to increase that understanding by testing whether the factors which determine AES sign-up decisions are influenced by the intensity of change in farming practices that are brought about by adopting the scheme. A micro-economic model reflecting farmer AES sign-up decisions is proposed and applied to two schemes in Spain respectively requiring major or minor intensity of change in practices by surveying farmers eligible for both schemes. The results show that farm structural factors play a role when major practice change is required by the scheme, yet when dealing with minor change, individual farmer characteristics play a more determining role. Social capital and farmer attitude are important factors in both the AES surveyed. Therefore, it may be concluded that improving agronomic design would be an important tool to improve farmer participation in AES where major change is involved, whereas improved targeting and extension would help uptake for AES involving a lesser degree of change.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs).     

Ecotoxicity assessment of lipid regulators in water and biologically treated wastewater using three aquatic organisms

Background, aim, and scope  

The high consumption of blood lipid regulators is leading to frequent reports of the occurrence of fibrates in natural streams and wastewater effluents. This paper describes a study undertaken to evaluate the acute toxicity of bezafibrate, clofibric acid, gemfibrozil, and fenofibric acid, a metabolite of fenofibrate whose ecotoxicity has not been previously reported.     

Evaluation of airborne particulate matter and metals data in personal,indoor and outdoor environments using ED-XRF and ICP-MS and co-located duplicate samples

Factors and sources affecting measurement uncertainty associated with monitoring metals in airborne particulate matter (PM) were investigated as part of the Windsor, Ontario Exposure Assessment Study (WOEAS). The assessment was made using co-located duplicate samples and a comparison of two analytical approaches: ED-XRF and ICP-MS. Sampling variability was estimated using relative percent difference (RPD) of co-located duplicate samples. The comparison of ICP-MS and ED-XRF results yields very good correlations (R² ≥ 0.7) for elements present at concentrations that pass both ICP-MS and ED-XRF detection limits (e.g. Fe, Mn, Zn, Pb and Cu). PM concentration ranges (median, sample number) of 24-h indoor PM₁₀ and personal PM₁₀ filters, and outdoor PM_2.5 filters were determined to be 2.2–40.7 (11.0, n = 48) μg m^?3, 8.0–48.3 (11.9, n = 48) μg m^?3, and 17.1–42.3 (21.6, n = 18) μg m^?3, respectively. The gravimetric analytical results reveal that the variations in PM mass measurements for same-day sampling are insignificant compared to temporal or spatial variations: 92%, 100% and 96% of indoor, outdoor and personal duplicate samples, respectively, pass the quality criteria (RPD ≤ 20%). Uncertainties associated with ED-XRF elemental measurements of S, Ca, Mn, Fe and Zn for 24-h filter samples are low: 78%–100% of the duplicate samples passed the quality criteria. In the case of 24-h filter samples using ICP-MS, more elements passed the quality criteria due to the lower detection limits. These were: Li, Na, K, Ca, Si, Al, V, Fe, Mn, Co, Cu, Mo, Ag, Zn, Pb, As, Mg, Sb, Sn, Sr, Th, Ti, Tl, and U. Low air concentrations of metals (near or below instrumental detection limits) and/or inadvertent introduction of metal contamination are the main causes for excluding elements based on the pass/fail criteria. Uncertainty associated with elemental measurements must be assessed on an element-by-element basis.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.     

Discriminating the regional and urban contributions in the North-Western Mediterranean: PM levels and composition

Simultaneous measurements of the PM concentration levels and chemical composition of atmospheric aerosols at a regional background (RB) and an urban background (UB) site, located in the same geographic region, allowed for the determination of their urban and regional contributions. In the specific case of the North-Western region of the Mediterranean the RB amount has been quantified in 18, 13 and 12 μg m^?3 for PM₁₀, PM_2.5 and PM₁, respectively, whereas the UB contribution reached 22, 13 and 8 μg m^?3, respectively. The UB contributions in the Western Mediterranean are much higher than those observed in other European regions; especially concerning the coarse fraction. The high loads of road dust in the urban areas across the Mediterranean may account for these large differences.The urban contributions are extremely enriched in Ca, Fe, Sb, Sn, Cu, Zn, being the main tracers of the road dust, with concentrations up to 6–8 times higher than those at the RB. Elemental carbon and nitrate are mainly derived from direct vehicular emissions. Some industrial tracers (Mn, Pb, Bi) are also enriched in the urban area. The evaluation of the Cu/Sb, Cu/Zn, Cu/Cd and Cu/Pb ratios and the high enrichment of these trace elements versus the Upper Crustal Composition average values corroborates the importance of the road-traffic emissions in the study area, also influencing the RB.The supplementary results from a suburban site in the Balearic Islands and the evaluation of the V/Ni ratios evidence the strong signature of fuel-oil combustion processes, which is a general characteristic of the Mediterranean aerosols.     

Airborne molds and mycotoxins associated with handling of corn silage and oilseed cakes in agricultural environment

In agricultural areas, the contamination of feedstuffs with molds and mycotoxins presents major environmental and health concerns. During cattle feeding, fungi and mycotoxins were monitored in corn silage, oilseed cakes and bioaerosols collected in Normandy. Most of the corn silages were found to be contaminated by deoxynivalenol (mean concentration: 1883 μg kg^?1) while a few of oilseed cakes were contaminated by alternariol, fumonisin B₁ or gliotoxin. In ambient bioaerosols, the values for fungi per cubic meter of air varied from 4.3 × 10² to 6.2 × 10⁵ cfu m^?3. Seasonal variations were observed with some species like Aspergillus fumigatus which significantly decreased between the 2 seasons (P = 0.0186) while the Penicillium roqueforti group significantly increased during the second season (P = 0.0156). In the personal bioaerosols, the values for fungi per cubic meter of air varied from 3.3 10³ to 1.7 10⁶ cfu m^?3 and the number of A. fumigatus spores significantly decreased between the 2 seasons (P = 0.0488). Gliotoxin, an immunosuppressive mycotoxin, was quantified in 3 personal filters at 3.73 μg m^?3, 1.09 μg m^?3 and 2.97 μg m^?3.