Polycyclic aromatic compounds (PACs) are known due to their mutagenic activity. Among them, 2-nitrobenzanthrone (2-NBA) and 3-nitrobenzanthrone (3-NBA) are considered as two of the most potent mutagens found in atmospheric particles. In the present study 2-NBA, 3-NBA and selected PAHs and Nitro-PAHs were determined in fine particle samples (PM 2.5) collected in a bus station and an outdoor site. The fuel used by buses was a diesel-biodiesel (96:4) blend and light-duty vehicles run with any ethanol-to-gasoline proportion. The concentrations of 2-NBA and 3-NBA were, on average, under 14.8 µg g−1 and 4.39 µg g−1, respectively. In order to access the main sources and formation routes of these compounds, we performed ternary correlations and multivariate statistical analyses. The main sources for the studied compounds in the bus station were diesel/biodiesel exhaust followed by floor resuspension. In the coastal site, vehicular emission, photochemical formation and wood combustion were the main sources for 2-NBA and 3-NBA as well as the other PACs. Incremental lifetime cancer risk (ILCR) were calculated for both places, which presented low values, showing low cancer risk incidence although the ILCR values for the bus station were around 2.5 times higher than the ILCR from the coastal site.

Occurrence of the potent mutagens 2- nitrobenzanthrone and 3-nitrobenzanthrone in fine airborne particles

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5° × 0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.

/pdf/a-global-model-of-natural-volatile-organic-compound-546vyk3ww5.pdf

A global model of natural volatile organic compound emissions

http://joenschem.com/yahoo_site_admin/assets/docs/atkinson2000r.93190106.pdf

Atmospheric chemistry of VOCs and NOx

Atmospheric degradation of volatile organic compounds

. The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1) is a modeling framework for estimating fluxes of biogenic compounds between terrestrial ecosystems and the atmosphere using simple mechanistic algorithms to account for the major known processes controlling biogenic emissions. It is available as an offline code and has also been coupled into land surface and atmospheric chemistry models. MEGAN2.1 is an update from the previous versions including MEGAN2.0, which was described for isoprene emissions by Guenther et al. (2006) and MEGAN2.02, which was described for monoterpene and sesquiterpene emissions by Sakulyanontvittaya et al. (2008). Isoprene comprises about half of the total global biogenic volatile organic compound (BVOC) emission of 1 Pg (1000 Tg or 1015 g) estimated using MEGAN2.1. Methanol, ethanol, acetaldehyde, acetone, α-pinene, β-pinene, t-β-ocimene, limonene, ethene, and propene together contribute another 30% of the MEGAN2.1 estimated emission. An additional 20 compounds (mostly terpenoids) are associated with the MEGAN2.1 estimates of another 17% of the total emission with the remaining 3% distributed among >100 compounds. Emissions of 41 monoterpenes and 32 sesquiterpenes together comprise about 15% and 3%, respectively, of the estimated total global BVOC emission. Tropical trees cover about 18% of the global land surface and are estimated to be responsible for ~80% of terpenoid emissions and ~50% of other VOC emissions. Other trees cover about the same area but are estimated to contribute only about 10% of total emissions. The magnitude of the emissions estimated with MEGAN2.1 are within the range of estimates reported using other approaches and much of the differences between reported values can be attributed to land cover and meteorological driving variables. The offline version of MEGAN2.1 source code and driving variables is available from http://bai.acd.ucar.edu/MEGAN/ and the version integrated into the Community Land Model version 4 (CLM4) can be downloaded from http://www.cesm.ucar.edu/ .

/pdf/the-model-of-emissions-of-gases-and-aerosols-from-nature-4abxgaax5t.pdf

The model of emissions of gases and aerosols from nature version 2.1 (MEGAN2.1): An extended and updated framework for modeling biogenic emissions

The formation of nitro-PAH from the gas-phase reactions of fluoranthene and pyrene with the OH radical in the presence of NOx

The nitrate radical, NO3, has been identified and measured for the first time in the polluted troposphere using long path (970 and 750 m) differential optical absorption spectroscopy at two sites in the Los Angeles basin. NO3 concentrations of up to 355 ppt were measured using the strong NO3 absorption bands at 623 and 662 nm. During pollution episodes from September 11 to September 19, 1979 concentrations increased sharply after sunset and peaked about one hour later at ∼ 20:00 (PDT). In many other cases peak concentrations were much lower and sometimes below the detection limit of several ppt. Possible sinks for the NO3 radical under polluted conditions are considered, including reaction with NO, reaction with organic species, and the hydrolysis of N2O5 for which a new upper limit rate constant is derived.

Detection of NO3 in the polluted troposphere by differential optical absorption

In the past decade, increasing attention has been paid to the role of nitrous acid (HONO) in the polluted troposphere, primarily as an initiator of photochemical air pollution1 through its photodissociation by solar UV radiation into hydroxyl radicals and NO. The OH radical may subsequently attack organics starting a chain photoxidation which leads to the production of O3, peroxyacetyl nitrate and many other secondary pollutants. Measurements of the concentration of HONO, especially in the early morning, are needed to establish the initial conditions to be used in computer kinetic models of photochemical oxidant formation2–4. From laboratory studies, it has been suggested that nitrous acid may also be a precursor to the possible formation of nitrosamines by reaction with simple secondary and tertiary amines in urban air5, or in vivo following inhalation. We report here a series of observations, at Riverside and Claremont, California, of the gradual buildup of HONO during the night and its rapid decay after sunrise. These, we believe, represent the first unequivocal measurements of HONO reported for a major urban air basin impacted by photochemical air pollution.

Observations of nitrous acid in an urban atmosphere by differential optical absorption

Emission rates of organics from vegetation in California's Central Valley

The formation of nitrous acid (HONO) in the dark from initial concentrations of NO2 of 0.1–20 ppm in air, and the concurrent disappearance of NO2, were monitored quantitatively by UV differential optical absorption spectroscopy in two different environmental chambers of ca.4300- and 5800-L volume (both with surface/volume ratios of 3.4 m−1). In these environmental chambers the initial HONO formation rate was first order in the NO2 concentration and increased with the water vapor concentration. However, the HONO formation rate was independent of the NO concentration and relatively insensitive to temperature. The initial pseudo-first-order consumption rate of NO2 was (2.8 ± 1.2) × 10−4 min−1 in the 5800-L Teflon-coated evacuable chamber and (1.6 ± 0.5) × 10−4 min−1 in a 4300-L all-Teflon reaction chamber at ca.300 K and ca.50% RH. The initial HONO yields were ca.40–50% of the NO2 reacted in the evacuable chamber and ca.10–30% in the all-Teflon chamber. Nitric oxide formation was observed during the later stages of the reaction in the evacuable chamber, but ca.50% of the nitrogen could not be accounted for, and gas phase HNO3 was not detected. The implications of these data concerning radical sources in environmental chamber irradiations of NOx− organic-air mixtures, and of HONO formation in polluted atmospheres, are discussed.

/pdf/an-investigation-of-the-dark-formation-of-nitrous-acid-in-rm9a9p264a.pdf

Arthur M. Winer

Papers

The formation of nitro-PAH from the gas-phase reactions of fluoranthene and pyrene with the OH radical in the presence of NOx

Detection of NO3 in the polluted troposphere by differential optical absorption

Observations of nitrous acid in an urban atmosphere by differential optical absorption

Emission rates of organics from vegetation in California's Central Valley

An Investigation of the Dark Formation of Nitrous Acid in Environmental Chambers