Photochemical nitro-nitrite rearrangement in methyl parathion decay under tropical conditions

This work presents a study of the abiotic degradation of commercially available methyl parathion in aqueous solution at two different concentrations (88 mg/L and 200 μg/L). The effects of solar irradiation and the presence of humic acids were evaluated and revealed a synergistic response between them. The half-life of methyl parathion ranged from 4.9 to 37 days, and the experimental data also show that photochemical processes were the most relevant in this case. The only byproduct found in samples submitted to shadowed conditions was 4-nitrophenol. On the other hand, 4-nitrophenol, methyl paraoxon and a new degradation product (O,O-dimethyl O-p-hydroxyphenyl phosphorothioate) were detected when the samples were exposed directly to sunlight. This newly identified compound was prepared in the laboratory by thiophosphorylation of hydroquinone, and coelution experiments with authentic samples provided unambiguous confirmation of the presence of O,O-dimethyl O-p-hydroxy phenylphosphorothioate in samples.     

Intake fraction distributions for benzene from vehicles in the Helsinki metropolitan area

The intake fraction (iF) gives a measure of the portion of a source's emissions that is inhaled by an exposed population over a defined period of time. This study examines spatial and population-based iF distributions of a known human carcinogen, benzene, from a ubiquitous urban source, local vehicular traffic, in the Helsinki Metropolitan Area using three computational methods. The first method uses the EXPAND model (EXPosure to Air pollution, especially to Nitrogen Dioxide and particulate matter), which incorporates spatial and temporal information on population activity patterns as well as urban-scale and street canyon dispersion models to predict spatial population exposure distributions. The second method uses data from the personal monitoring study EXPOLIS (Air Pollution Exposure Distributions of Adult Urban Populations in Europe) to estimate the intake fractions for individuals in the study. The third method, a one-compartment box model provides estimates within an order-of-magnitude or better for non-reactive agents in an urban area. Population intake fractions are higher using the personal monitoring data method (median iF 30 per million, mean iF 39 per million) compared with the spatial model (annual mean iF 10 per million) and the box model (median iF 4 per million, mean iF 7 per million). In particular, this study presents detailed intake fraction distributions on several different levels (spatial, individual, and generic) for the same urban area.     

Modelling the photochemical pollution over the metropolitan area of Porto Alegre,Brazil

The main purpose of this study is to evaluate the photochemical pollution over the Metropolitan Area of Porto Alegre (MAPA), Brazil, where high concentrations of ozone have been registered during the past years. Due to the restricted spatial coverage of the monitoring air quality network, a numerical modelling technique was selected and applied to this assessment exercise. Two different chemistry-transport models – CAMx and CALGRID – were applied for a summer period, driven by the MM5 meteorological model. The meteorological model performance was evaluated comparing its results to available monitoring data measured at the Porto Alegre airport. Validation results point out a good model performance. It was not possible to evaluate the chemistry models performance due to the lack of adequate monitoring data. Nevertheless, the model intercomparison between CAMx and CALGRID shows a similar behaviour in what concerns the simulation of nitrogen dioxide, but some discrepancies concerning ozone. Regarding the fulfilment of the Brazilian air quality targets, the simulated ozone concentrations surpass the legislated value in specific periods, mainly outside the urban area of Porto Alegre. The ozone formation is influenced by the emission of pollutants that act as precursors (like the nitrogen oxides emitted at Porto Alegre urban area and coming from a large refinery complex) and by the meteorological conditions.     

High ozone levels in the northeast of Portugal: Analysis and characterization

Each summer period extremely high ozone levels are registered at the rural background station of Lamas d'Olo, located in the Northeast of Portugal. In average, 30% of the total alert threshold registered in Portugal is detected at this site. The main purpose of this study is to characterize the atmospheric conditions that lead to the ozone-rich episodes at this site. Synoptic patterns anomalies and back trajectories cluster analysis were performed, for the period between 2004 and 2007, considering 76 days when ozone maximum hourly concentrations were above 200 μg m^?3. The obtained atmospheric anomaly fields suggested that a positive temperature anomaly is visible above the Iberian Peninsula. A strong wind flow pattern from NE is observable in the North of Portugal and Galicia, in Spain. These two features may lead to an enhancement of the photochemical production and to the transport of pollutants from Spain to Portugal. In addition, the 3D mean back trajectories associated to the ozone episode days were analysed. A clustering method has been applied to the obtained back trajectories. Four main clusters of ozone-rich episodes were identified, with different frequencies of occurrence: north-westerly flows (11%); north-easterly flows (45%), southern flow (4%) and westerly flows (40%). Both analyses highlight the NE flow as a dominant pattern over the North of Portugal during summer. The analysis of the ozone concentrations for each selected cluster indicates that this northeast circulation pattern, together with the southern flow, are responsible for the highest ozone peak episodes. This also suggests that long-range transport of atmospheric pollutants is the main contributor to the ozone levels registered at Lamas d'Olo. This is also highlighted by the correlation of the ozone time-series with the meteorological parameters analysed in the frequency domain.     

Using Phylogenetic Diversity Measures to Set Priorities in Conservation: an Example from Southern South America

Abstract: Phylogenetic diversity measures rank areas for biodiversity conservation priorities based on information encoded in phylogenies (cladograms). The goal of these ranks for conservation is to consider as many factors as possible that provide additional taxic information, such as taxa richness, taxa distributional patterns, area endemicity, and complementarity between areas. At present there are many measures that consider phylogenetic information, including node-based, genetic-distance, and feature-based measures. We devised a modified phylogenetic node-based index that we call "taxonomic endemicity standardized weight," which considers not only the taxonomic distinctness of the taxa that inhabit a given area but their endemicity as well. Once the standardized weight of the taxonomic endemicity identifies the area of highest priority, complementarity can be used to identify the second area and so on. We used this node-based index to rank priority areas for conservation in southern South America, and we compared the results of our rankings to results based on other node-based indexes. Our index identified Santiago district, in Central Chile province, as the highest priority area for conservation, followed by Maule, Malvinas, and districts of Subantarctic province. Malvinas exhibits greater complementarity relative to Santiago than Maule does, however, so Malvinas is ranked second in priority. Indexes based on phylogenetic information measure the evolutionary component of biodiversity and allow one to identify areas that will ensure the preservation of evolutionary potential and phylogenetically rare taxa. The modified index we propose is sensitive to taxic distinctness and endemicity as well and allows information from diverse taxa to be combined (i.e., different cladograms). The use of complementarity allows for preservation of the maximum quantity of taxa in a minimal number of protected areas.     

Assessment of indoor airborne contamination in a wastewater treatment plant

The main objective of this work was to quantify and characterize the major indoor air contaminants present in different stages of a municipal WWTP, including microorganisms (bacteria and fungi), carbon dioxide, carbon monoxide, hydrogen sulfide ammonia, formaldehyde, and volatile organic compounds (VOCs). In general, the total bacteria concentration was found to vary from 60 to >52,560 colony-forming units (CFU)/m³, and the total fungi concentration ranged from 369 to 14,068 CFU/m³. Generally, Gram-positive bacteria were observed in higher number than Gram-negative bacteria. CO₂ concentration ranged from 251 to 9,710 ppm, and CO concentration was either not detected or presented a level of 1 ppm. H₂S concentration ranged from 0.1 to 6.0 ppm. NH₃ concentration was <2 ppm in most samples. Formaldehyde was <0.01 ppm at all sampling sites. The total VOC concentration ranged from 36 to 1,724 μg/m³. Among the VOCs, toluene presented the highest concentration. Results point to indoor/outdoor ratios higher than one. In general, the highest levels of airborne contaminants were detected at the primary treatment (SEDIPAC 3D), secondary sedimentation, and sludge dehydration. At most sampling sites, the concentrations of airborne contaminants were below the occupational exposure limits (OELs) for all the campaigns. However, a few contaminants were above OELs in some sampling sites.     

Differences in metal concentration by particle size in house dust and soil

The majority of particles that adhere to hands are <63 μm in diameter yet risk assessments for soil remediation are typically based on soil samples sieved to <250 μm. The objective of our study was to determine if there is a significant difference in metal concentration by particle size in both house dust and soil. We obtained indoor dust and yard soil samples from 10 houses in Tucson, Arizona. All samples were sieved to <63 μm and 63 to <150 μm and analyzed for 30 elements via ICP-MS following nitric acid digestion. We conducted t-tests of the log-transformed data to assess for significant differences that were adjusted with a Bonferroni correction to account for multiple comparisons. In house dust, significant differences in concentration were observed for Be, Al, and Mo between particles sizes, with a higher concentration observed in the smaller particle sizes. Significant differences were also determined for Mg, Ca, Cr, Co, Cu, Ge, Zr, Ag, Ba, and Pb concentration in yard soil samples, with the higher concentration observed in the smaller particles size for each element. The results of this exploratory study indicate that current risk assessment practices for soil remediation may under estimate non-dietary ingestion exposure. This is of particular concern for young children who are more vulnerable to this exposure route due to their high hand mouthing frequencies. Additional studies with a greater number of samples and wider geographic distribution with different climates and soil types should be completed to determine the most relevant sampling practices for risk assessment.     

Pesticide residues in river sediments from the Pantanal Wetland, Brazil

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included lambda -cyhalothrin (1.0 to 5.0 micro g kg(- 1)), p,p'-DDT (3.6 micro g kg(- 1)), deltamethrin (20.0 micro g kg(- 1)) and permethrin (1.0 to 7.0 micro g kg(- 1)).