Pérola de Castro Vasconcellos

Emission of 2‐methyl‐3‐buten‐2‐ol by pines: A potentially large natural source of reactive carbon to the atmosphere

High rates of emission of 2-methyl-3-buten-2-ol (MBO) were measured from needles of several pine species. Emissions of MBO in the light were 1 to 2 orders of magnitude higher than emissions of monoterpenes and, in contrast to monoterpene emissions from pines, were absent in the dark. MBO emissions were strongly dependent on incident light, behaving similarly to net photosynthesis. Emission rates of MBO increased exponentially with temperature up to approximately 35°C. Above approximately 42°C, emission rates declined rapidly. Emissions could be modeled using existing algorithms for isoprene emission. We propose that emissions of MBO from lodgepole and ponderosa pine are the primary source of high concentrations of this compound, averaging 1–3 ppbv, found in ambient air samples collected in Colorado at an isolated mountain site approximately 3050 m above sea level. Subsequent field studies in a ponderosa pine plantation in California confirmed high MBO emissions, which averaged 25 μg C g−1 h−1 for 1-year-old needles, corrected to 30°C and photon flux of 1000 μmol m−2 s−1. A total of 34 pine species growing at Eddy Arboretum in Placerville, California, were investigated, of which 11 exhibited high emissions of MBO (>5 μg C g−1 h−1), and 6 emitted small but detectable amounts. All the emitting species are of North American origin, and most are restricted to western North America. These results indicate that MBO emissions from pines may constitute a significant source of reactive carbon and a significant source of acetone, to the atmosphere, particularly in the western United States.

Formation and transport of 2‐nitrofluoranthene and 2‐nitropyrene of photochemical origin in the troposphere

The occurrence of 2-nitrofluoranthene and 2-nitropyrene in particulate matter collected in urban, suburban, forest, and remote areas located in Europe, America, Asia, and Antarctica was investigated. The results obtained confirm the photochemical origin of these components by gas phase reactions with OH radicals and their ubiquitous occurrence in the troposphere. An important role in their formation and dispersion seems to be played by carbon particles.

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in São Paulo, Brazil

This study was conducted at three sites of different characteristics in São Paulo State: São Paulo (SPA), Piracicaba (PRB) and Mata Atlântica Forest (MAT). PM(10), n-alkanes, pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site. Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants. Air mass transport from biomass burning regions is likely to impact the sites with specific molecular markers. The concentrations of all species were variable and dependent of seasonal changes. In the most dry and polluted seasons, n-alkane and cation total concentrations were similar between the megacity and the biomass burning site. PAHs and inorganic ion abundances were higher at São Paulo than Piracicaba, yet, the site influenced by biomass burning seems to be the most impacted by the organic anion abundance in the atmosphere. Pristane and phytane confirm the contamination by petroleum residues at urban sites; at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane.

A preliminary characterization of the mutagenicity of atmospheric particulate matter collected during sugar cane harvesting using the Salmonella/microsome microsuspension assay.

During sugar cane harvesting season, which occurs from May to November of each year, the crops are burnt, cut, and transported to the mills. There are reports showing that mutagenic activity and PAH content increase during harvesting season in some areas of São Paulo State in comparison with nonharvesting periods. The objective of this work was to preliminarily characterize the mutagenic activity of the total organic extracts as well as corresponding organic fractions of airborne particulate matter (PM) collected twice from two cities, Araraquara (ARQ) and Piracicaba (PRB), during sugar cane harvesting season using the Salmonella/microsome microssuspension assay. One sample collected in São Paulo metropolitan area was also included. The mutagenicity of the total extracts ranged from 55 to 320 revertants per cubic meter without the addition of S9 and from not detected to 57 revertants per cubic meter in the presence of S9 in areas with sugar cane plantations. Of the three fractions analyzed, the most polar ones (nitro and oxy) were the most potent. A comparison of the response of TA98 with YG1041 and the increased potencies without S9 indicated that nitro compounds are causing the observed effect. More studies are necessary to verify the sources of the mutagenic activity such as burning of vegetal biomass and combustion of heavy duty vehicles used to transport the sugar cane to the mills. The Salmonella/microsome assay can be an important tool to monitor the atmosphere for mutagenicity during sugar cane harvesting season. Environ. Mol. Mutagen. 2008.

Hidrocarbonetos policíclicos aromáticos como traçadores da queima de cana-de-açúcar: uma abordagem estatística

In this study atmospheric particulates of PAHs were measured in Araraquara, Piracicaba and Sao Paulo in July 2003 (sugarcane harvest season in Araraquara and Piracicaba) and in Araraquara in March of 2003. The results were normalized to the total PAH concentrations. Comparison among the sites and principal component analysis (PCA) were used to investigate possible tracers of emission. Fluoranthene and pyrene concentrations were higher in Piracicaba and Araraquara samples. These PAH were also responsible for the largest negative loadings on the second principal component and account for the negative scores and for the formation of the Araraquara and Piracicaba group.

Genotoxicity and composition of particulate matter from biomass burning in the eastern Brazilian Amazon region

In the present study Tradescantia pallida micronucleus (Trad-MCN) bioassay was used to assess the genotoxicity of particulate matter with a mass median aerodynamic diameter less than 10 μm (PM₁₀) in Tangara da Serra (MT), a Brazilian Amazon region that suffers the impact of biomass burning. The levels of PM (coarse and fine size fractions) and black carbon (BC) collected were also measured. Furthermore, the alkanes and polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in the samples taken during the burning period by gas chromatography with flame ionization detection (GC-FID). The PM and BC results for both fractions indicate a strong correlation (p < 0.001). The analysis of alkanes indicates an anthropic influence. Retene was the most abundant PAH found, an indicator of biomass burning, and 12 other PAHs considered to be potentially mutagenic and/or carcinogenic were identified in this sample. The Trad-MCN bioassay showed a significant increase in micronucleus frequency during the period of most intense burning, possibly related to the mutagenic PAHs that were found in such extracts. This study demonstrated that Trad-MCN was sensitive and efficient in evaluating the genotoxicity of organic compounds from biomass burning. It further emphasizes the importance of performing chemical analysis, because changes in chemical composition generally have a negative effect on many living organisms. This bioassay (ex situ), using T. pallida with chemical analysis, is thus recommended for characterizing the genotoxicity of air pollution.

Quantification and source identification of atmospheric particulate polycyclic aromatic hydrocarbons and their dry deposition fluxes at three sites in Salvador Basin, Brazil, impacted by mobile and stationary sources

The present work has aimed to determine the 16 US EPA priority PAH atmospheric particulate matter levels present in three sites around Salvador, Bahia: (i) Lapa bus station, strongly impacted by heavy-duty diesel vehicles; (ii) Aratu harbor, impacted by an intense movement of goods, and (iii) Bananeira village on Mare Island, a non vehicle-influenced site with activities such as handcraft work and fisheries. Results indicated that BbF (0.130-6.85 ng m-3) is the PAH with highest concentration in samples from Aratu harbor and Bananeira and CRY (0.075-6.85 ng m-3) presented higher concentrations at Lapa station. PAH sources from studied sites were mainly of anthropogenic origin such as gasoline-fueled light-duty vehicles and diesel-fueled heavy-duty vehicles, discharges in the port, diesel burning from ships, dust ressuspension, indoor soot from cooking, and coal and wood combustion for energy production.

Volatile organic compounds inside urban tunnels of São Paulo City, Brazil

Volatile organic compounds, such as oxygenated hydrocarbons, aliphatic and aromatic hydrocarbons were measured in ambient air from two distinct urban tunnels in Sao Paulo City, Brazil, in special, at rush hours. In these tunnels, traffic jams with significant numbers of vehicles with inadequate emission controls are frequent. Sao Paulo, a highly polluted city, has an unconventional mix of vehicle types in that a variety of gasoline blends, including oxygenated ones are used. Inside and outside tunnel measurements were performed to evaluate pollutant levels originated from direct vehicular emissions and formed by atmospheric photochemistry. Formaldehyde/acetaldehyde ratios of tunnel (A) circulating only light-duty vehicles fueled mainly with gasohol, a mixture containing 78-80% (v/v) gasoline and 20-25% ethanol, were < 1; ratios of tunnel (B) circulating light-duty vehicles fueled mainly with gasohol and heavy diesel vehicles, were approximately equal to 1. Formic acid/acetic acid ratios of both tunnels were much lower than 1. Benzaldehyde was suggested as a possible tracer of light-duty gasohol vehicular emissions. n-alkanes were the most abundant compound class (similar levels in both tunnels) followed by carbonyl compounds (higher levels in B), and aromatics compounds (higher levels in A). Organic acids, the minor species, were found at similar levels in both tunnels. Results of this survey show that toxic pollutants are present at significant levels in both tunnels. Formaldehyde and benzene, human carcinogenic agents, presented maximum mixing ratios of 39.2 and 24.8 ppbv, respectively, inside tunnel A; acetaldehyde, a probable human carcinogenic, reached a maximum of 34.5 ppbv inside tunnel B. Since vehicle occupants that spend a significant time in urban tunnels are commonly exposed to toxic pollutant emissions, future extensive studies should be done in order to estimate exposure levels of toxic ambient air pollutants for these people.

Genetic damage of organic matter in the Brazilian Amazon: A comparative study between intense and moderate biomass burning

BACKGROUND The biomass burning that occurs in the Amazon region has an adverse effect on environmental and human health. However, in this region, there are limited studies linking atmospheric pollution and genetic damage. OBJECTIVE We conducted a comparative study during intense and moderate biomass burning periods focusing on the genetic damage and physicochemical analyses of the particulate matter (PM). METHOD PM and black carbon (BC) were determined; organic compounds were identified and quantified using gas chromatography with flame ionization detection, the cyto-genotoxicity test was performed using two bioassays: cytokinesis-block micronucleus (CBMN) in A549 cells and Tradescantia pallida micronucleus (Trad-MCN) assay. RESULTS The PM10 concentrations were lower than the World Health Organization air quality standard for 24h. The n-alkanes analyses indicate anthropogenic and biogenic influences during intense and moderate biomass burning periods, respectively. Retene was identified as the most abundant polycyclic aromatic hydrocarbon during both sampling periods. Carcinogenic and mutagenic compounds were identified. The genotoxic analysis through CBMN and Trad-MCN tests showed that the frequency MCN from the intense burning period is significantly higher compared to moderate burning period. CONCLUSIONS This is the first study using human alveolar cells to show the genotoxic effects of organic PM from biomass burning samples collected in Amazon region. The genotoxicity of PM can be associated with the presence of several mutagenic and carcinogenic compounds, mainly benzo[a]pyrene. These findings have potential implications for the development of pollution abatement strategies and can minimize negative impact on health.

Determinação dos hidrocarbonetos saturados e policíclicos aromáticos presentes no material particulado da atmosfera amazônica

It was identified and quantified several organic compounds in the atmosphere of a site into Amazon Basin with high impact of biomass burning emission. It was important to know the particulate matter composition with respect to n-alkanes and PAH associated with the particulate matter because they provided indication on the main sources contributing to airborne particles, the contribution of natural vs. man-made emission and the aging of the particles. The main classes of compounds observed were n-alkanes, PAH and nitro-PAH. It was observed the formation of nitro-PAH from photochemical reactions. The aerosol mass concentration is mainly associated with fluoranthene, pyrene and benzo(ghi)perylene. Environmental and direct emissions samples (flaming and smoldering) were collected and analysed.