Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air water interface which removes material from the air water interface. We present evidence that the NO2 isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO3, and thin organic films as NO2 is usually present in high concentrations in these experimental systems and (2) the effect of NO2 air pollution on the unsaturated fatty acids and lipids found at the air liquid surface of human lung lining fluid.

Fair weather atmospheric electricity

Abstract. Not long after Franklin’s iconic studies, an atmospheric electric field was discovered in “fair weather” regions, well away from thunderstorms. The origin of the fair weather field was sought by Lord Kelvin, through development of electrostatic instrumentation and early data logging techniques, but was ultimately explained through the global circuit model of C.T.R. Wilson. In Wilson’s model, charge exchanged by disturbed weather electrifies the ionosphere, and returns via a small vertical current density in fair weather regions. New insights into the relevance of fair weather atmospheric electricity to terrestrial and planetary atmospheres are now emerging. For example, there is a possible role of the global circuit current density in atmospheric processes, such as cloud formation. Beyond natural atmospheric processes, a novel practical application is the use of early atmospheric electrostatic investigations to provide quantitative information on past urban air pollution.

Multimodel estimates of intercontinental source-receptor relationships for ozone pollution

Understanding the surface O3 response over a “receptor” region to emission changes over a foreign “source” region is key to evaluating the potential gains from an international approach to abate ozone (O3) pollution. We apply an ensemble of 21 global and hemispheric chemical transport models to estimate the spatial average surface O3 response over east Asia (EA), Europe (EU), North America (NA), and south Asia (SA) to 20% decreases in anthropogenic emissions of the O3 precursors, NOx, NMVOC, and CO (individually and combined), from each of these regions. We find that the ensemble mean surface O3 concentrations in the base case (year 2001) simulation matches available observations throughout the year over EU but overestimates them by >10 ppb during summer and early fall over the eastern United States and Japan. The sum of the O3 responses to NOx, CO, and NMVOC decreases separately is approximately equal to that from a simultaneous reduction of all precursors. We define a continental-scale “import sensitivity” as the ratio of the O3 response to the 20% reductions in foreign versus “domestic” (i.e., over the source region itself) emissions. For example, the combined reduction of emissions from the three foreign regions produces an ensemble spatial mean decrease of 0.6 ppb over EU (0.4 ppb from NA), less than the 0.8 ppb from the reduction of EU emissions, leading to an import sensitivity ratio of 0.7. The ensemble mean surface O3 response to foreign emissions is largest in spring and late fall (0.7–0.9 ppb decrease in all regions from the combined precursor reductions in the three foreign regions), with import sensitivities ranging from 0.5 to 1.1 (responses to domestic emission reductions are 0.8–1.6 ppb). High O3 values are much more sensitive to domestic emissions than to foreign emissions, as indicated by lower import sensitivities of 0.2 to 0.3 during July in EA, EU, and NA when O3 levels are typically highest and by the weaker relative response of annual incidences of daily maximum 8-h average O3 above 60 ppb to emission reductions in a foreign region (<10–20% of that to domestic) as compared to the annual mean response (up to 50% of that to domestic). Applying the ensemble annual mean results to changes in anthropogenic emissions from 1996 to 2002, we estimate a Northern Hemispheric increase in background surface O3 of about 0.1 ppb a−1, at the low end of the 0.1–0.5 ppb a−1 derived from observations. From an additional simulation in which global atmospheric methane was reduced, we infer that 20% reductions in anthropogenic methane emissions from a foreign source region would yield an O3 response in a receptor region that roughly equals that produced by combined 20% reductions of anthropogenic NOx, NMVOC, and CO emissions from the foreign source region.

Galactic outflows and the pollution of the galactic environment by supernovae

We here explore the effects of the SN explosions into the halo of star-forming galaxies like the Milky Way. Successive randomly distributed and clustered SNe explosions cause the formation of hot superbubbles that drive either fountains or galactic winds above the galactic disk, depending on the amount and concentration of energy that is injected by the SNe. In a galactic fountain, the ejected gas is re-captured by the gravitational potential and falls back onto the disk. From 3D non-equilibrium radiative cooling hydrodynamical simulations of these fountains, we find that they may reach altitudes up to about 5 kpc in the halo and thus allow for the formation of the so called intermediate-velocity-clouds (IVCs) which are often observed in the halos of disk galaxies. The high-velocity-clouds that are also observed but at higher altitudes (of up to 12 kpc) require another mechanism to explain their production. We argue that they could be formed either by the capture of gas from the intergalactic medium and/or by the action of magnetic fields that are carried to the halo with the gas in the fountains. Due to angular momentum losses to the halo, we find that the fountain material falls back to smaller radii and is not largely spread over the galactic disk. Instead, the SNe ejecta fall nearby the region where the fountain was produced, a result which is consistent with recent chemical models of the galaxy. The fall back material leads to the formation of new generations of molecular clouds and to supersonic turbulence feedback in the disk. (C) 2009 COSPAR. Published by Elsevier Ltd. All rights reserved.

On the development of summer thunderstorms in the city of Sao Paulo: Mean meteorological characteristics and pollution effect

This study investigates how the summer thunderstorms developed over the city of Sao Paulo and if the pollution might affect its development or characteristics during the austral summer (December-January-February-March, DJFM months). A total of 605 days from December 1999 to March 2004 was separated as 241 thunderstorms days (TDs) and 364 non-thunderstorm days (NTDs). The analyses are performed by using hourly measurements of air temperature (T), web-bulb temperature (Tw), surface atmospheric pressure (P), wind velocity and direction, rainfall and thunder and lightning observations collected at the Meteorological Station of the University of Sao Paulo in conjunction with aerosol measurements obtained by AERONET (Aerosol Robotic Network), and the NCEP-DOE (National Centers for Environmental Prediction Department of Energy) reanalysis and radiosondes. The wind diurnal cycle shows that for TDs the morning flow is from the northwest rotating to the southeast after 16: 00 local time (LT) and it remains from the east until the night. For the NTDs, the wind is well characterized by the sea-breeze circulation that in the morning has the wind blowing from the northeast and in the afternoon from the southeast. The TDs show that the air temperature diurnal cycle presents higher amplitude and the maximum temperature of the day is 3.2 degrees C higher than in NTDs. Another important factor found is the difference between moisture that is higher during TDs. In terms of precipitation, the TDs represent 40% of total of days analyzed and those days are responsible for more than 60% of the total rain accumulation during the summer, for instance 50% of the TDs had more than 15.5mm day(-1) while the NTDs had 4 mm day(-1). Moreover, the rainfall distribution shows that TDs have higher rainfall rate intensities and an afternoon precipitation maximum; while in the NTDs there isn`t a defined precipitation diurnal cycle. The wind and temperature fields from NCEP reanalysis concur with the local weather station and radiosonde observations. The NCEP composites show that TDs are controlled by synoptic circulation characterized by a pre-frontal situation, with a baroclinic zone situated at southern part of Sao Paulo. In terms of pollution, this study employed the AERONET data to obtain the main aerosol characteristics in the atmospheric column for both TDs and NTDs. The particle size distribution and particle volume size distribution have similar concentrations for both TDs and NTDs and present a similar fine and coarse mode mean radius. In respect to the atmospheric loading, the aerosol optical depth (AOD) at different frequencies presented closed mean values for both TDs and NTDs that were statistically significant at 95% level. The spectral dependency of those values in conjunction with the Angstrom parameter reveal the higher concentration of the fine mode particles that are more likely to be hygroscopic and from urban areas. In summary, no significant aerosol effect could be found on the development of summer thunderstorms, suggesting the strong synoptic control by the baroclinic forcing for deep convective development. (C) 2010 Published by Elsevier B. V.

Insights into the dynamics and sources of atmospheric lead and particulate matter in Sao Paulo, Brazil, from high temporal resolution sampling

We present the first results of a study investigating the processes that control concentrations and sources of Pb and particulate matter in the atmosphere of Sao Paulo City Brazil Aerosols were collected with high temporal resolution (3 hours) during a four-day period in July 2005 The highest Pb concentrations measured coincided with large fireworks during celebration events and associated to high traffic occurrence Our high-resolution data highlights the impact that a singular transient event can have on air quality even in a megacity Under meteorological conditions non-conducive to pollutant dispersion Pb and particulate matter concentrations accumulated during the night leading to the highest concentrations in aerosols collected early in the morning of the following day The stable isotopes of Pb suggest that emissions from traffic remain an Important source of Pb in Sao Paulo City due to the large traffic fleet despite low Pb concentrations in fuels (C) 2010 Elsevier BV All rights reserved

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

This study was conducted at three sites of different characteristics in Sao Paulo State Sao Paulo (SPA), Piracicaba (PRB) and Mate Atlantica 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 front 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 canon total concentrations were similar between the megacity and the biomass burning site PAHs and inorganic ion abundances were higher at Sao Paulo than Piracicaba, yet, the site influenced by biomass burning seems lobe 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 (C) 2010 Elsevier B V All rights reserved

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 Sao 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 Sao 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.

Mutagenicity and DNA adduct formation of PAH, nitro-PAH, and oxy-PAH fractions of atmospheric particulate matter from Sao Paulo, Brazil

Urban particulate matter (UPM) contributes to lung cancer incidence. Here, we have studied the mutagenic activity and DNA adduct-forming ability of fractionated UPM extractable organic matter (EOM). UPM was collected with a high-volume sampler in June 2004 at two sites, one at street level adjacent to a roadway and the other inside a park within the urban area of the city of Sao Paulo, Brazil. UPM was extracted using dichloromethane, and the resulting EOM was separated by HPLC to obtain PAH, nitro-PAH, and oxy-PAH fractions which were tested for mutagenicity with the Salmonella strains TA98 and YG1041 with and without S9 metabolic activation. The PAH fraction from both sites showed negligible mutagenic activity in both strains. The highest mutagenic activity was found for the nitro-PAH fraction using YG1041 without metabolic activation; however, results were comparable for both sites. The nitro-PAH and oxy-PAH fractions were incubated with calf thymus DNA under reductive conditions appropriate for the activation of nitro aromatic compounds, then DNA adduct patterns and levels were determined with thin-layer chromatography (TLC) (32)p-postlabeling method using two enrichment procedures-nuclease PI digestion and butanol extraction. Reductively activated fractions from both sites produced diagonal radioactive zones (DRZ) of putative aromatic DNA adducts on thin layer plates with both enrichment procedures. No such DRZ were observed in control experiments using fractions from unexposed filters or from incubations without activating system. Total adduct levels produced by the nitro-PAH fractions were similar for both sites ranging from 30 to 45 adducts per 10(8) normal nucleotides. In contrast, the DNA binding of reductively activated oxy-PAH fractions was three times higher and the adduct pattern consisted of multiple discrete spots along the diagonal line on the thin layer plates. However, DNA adduct levels were not significantly different between the sampling sites. Both samples presented the same levels of mutagenic activity. The response in the Salmonella assay was typical of nitroaromatics. Although, more mutagenic activity was related to the nitro-PAH fraction in the Salmonella assay, the oxy-PAH fractions showed the highest DNA adduct levels. More studies are needed to elucidate the nature of the genotoxicants occurring in Sao Paulo atmospheric samples. (C) 2008 Elsevier B.V. All rights reserved.

Influence of sugarcane burning on indoor/outdoor PAH air pollution in Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Contribution of sugar-cane harvesting season to atmospheric contamination by polycyclic aromatic hydrocarbons (PAHs) in Araraquara city, Southeast Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Intercontinental transport of nitrogen oxide pollution plumes

We describe the first satellite observation of intercontinental transport of nitrogen oxides emitted by power plants, verified by simulations with a particle tracer model. The analysis of such episodes shows that anthropogenic NOx plumes may influence the atmospheric chemistry thousands of kilometers away from its origin, as well as the ocean they traverse due to nitrogen fertilization. This kind of monitoring became possible by applying an improved algorithm to extract the tropospheric fraction of NO2 from the spectral data coming from the GOME instrument.As an example we show the observation of NO2 in the time period 4-14 May, 1998, from the South African Plateau to Australia which was possible due to favourable weather conditions during that time period which availed the satellite measurement. This episode was also simulated with the Lagrangian particle dispersion model FLEXPART which uses NOx emissions taken from an inventory for industrial emissions in South Africa and is driven with analyses from the European Centre for Medium-RangeWeather Forecasts. Additionally lightning emissions were taken into account by utilizing Lightning Imaging Sensor data. Lightning was found to contribute probably not more than 25% of the resulting concentrations. Both, the measured and simulated emission plume show matching patterns while traversing the Indian Ocean to Australia and show great resemblance to the aerosol and CO2 transport observed by Piketh et al. (2000).

Remote Sensing Detection of atmospheric pollutants using Lidar, Sodar and correlation with air quality data in an industrial area

Optical remote sensing techniques have obvious advantages for monitoring gas and aerosol emissions, since they enable the operation over large distances, far from hostile environments, and fast processing of the measured signal. In this study two remote sensing devices, namely a Lidar (Light Detection and Ranging) for monitoring the vertical profile of backscattered light intensity, and a Sodar (Acoustic Radar, Sound Detection and Ranging) for monitoring the vertical profile of the wind vector were operated during specific periods. The acquired data were processed and compared with data of air quality obtained from ground level monitoring stations, in order to verify the possibility of using the remote sensing techniques to monitor industrial emissions. The campaigns were carried out in the area of the Environmental Research Center (Cepema) of the University of São Paulo, in the city of Cubatão, Brazil, a large industrial site, where numerous different industries are located, including an oil refinery, a steel plant, as well as fertilizer, cement and chemical/petrochemical plants. The local environmental problems caused by the industrial activities are aggravated by the climate and topography of the site, unfavorable to pollutant dispersion. Results of a campaign are presented for a 24- hour period, showing data of a Lidar, an air quality monitoring station and a Sodar. © 2011 SPIE.

Atmospheric pollutants in São Paulo state, Brazil and effects on human health – a review

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mutagenicity profile of atmospheric particulate matter in a small urban center subjected to airborne emission from vehicle traffic and sugar cane burning

Atmospheric particulate matter (PM) is genotoxic and recently was classified as carcinogenic to humans by the International Agency for Research on Cancer. PM chemical composition varies depending on source and atmospheric conditions. The Salmonella/microsome assay is the most used mutagenicity test and can identify the major chemical classes responsible for observed mutagenicity. The objective of this work was to characterize the mutagenicity of PM samples from a countryside city, Limeira, Brazil, which is influenced by heavy traffic and sugar cane biomass burning. Six samples of total PM were collected. Air mass backward trajectories were calculated. Organic extracts were assayed using the Salmonella/microsome microsuspension mutagenicity assay using TA98, YG1041, and TA1538, with and without metabolic activation (S9). YG1041 was the most sensitive strain and mutagenicity reached 9,700 revertants per m(3) without metabolic activation. Potency for TA1538 was higher than TA98, indicating that this strain should be considered in air mutagenicity studies. The increased response to YG1041 relative to TA98, and the decreased response with S9, suggests that nitroaromatics are the major contributors. Limeira is among the most mutagenic cities in the world. High mutagenicity in Limeira seems to occur when the air mass from the area of sugarcane production is mixed with air from the region impacted by anthropogenic activities such as traffic. An increase in the formation of nitro-polycyclic aromatic hydrocarbons may result from longer contact time between the aromatic compounds and the atmosphere with high NOx and ozone concentration, although more studies are required to confirm this hypothesis. Environ. Mol. Mutagen., 2015. © 2015 Wiley Periodicals, Inc.