Atmospheric Environment (v.44, #15)

Oxygenated polycyclic aromatic hydrocarbons in atmospheric particulate matter: Molecular characterization and occurrence by Christophe Walgraeve; Kristof Demeestere; Jo Dewulf; Ralf Zimmermann; Herman Van Langenhove (1831-1846).
Particulate matter (PM) has become a major research issue receiving increasing attention because of its significant negative impact on human health. There are main indicators that next to the morphological characteristics of the particle, also the chemical composition plays an important role in the adverse health effects of PM. In this context, the rather polar organic fraction of PM is expected to play a major role, and advanced analytical techniques are developed to improve the knowledge on the molecular composition of this fraction. One component class that deserves major attention consists of the oxygenated polycyclic aromatic hydrocarbons (PAHs). Those compounds are considered to be among the key compounds in PM toxicity. This paper presents a comprehensive review focusing on the analysis, fate and behavior of oxygenated PAHs in the atmosphere. The first part of the paper briefly introduces (i) the main sources and atmospheric pathways of oxygenated PAHs, (ii) available physical–chemical properties and (iii) their health effects. The second and main part of this paper gives a thorough discussion on the entire analytical sequence necessary to identify and quantify oxygenated PAHs on atmospheric PM. Special attention is given to critical parameters and innovations related to (i) sampling, (ii) sample preparation including both extraction and clean-up, and (iii) separation and detection. Third, the state-of-the-art knowledge about the atmospheric occurrence of oxygenated PAHs is discussed, including an extended overview of reported concentrations presented as a function of sampling season and geographical location. A clear seasonal effect is observed with the median of the oxygenated PAHs concentrations during winter being a factor of 3–4 higher than during summer. However, the oxygenated PAH/parent PAH ratio is about 20 times higher during summer, indicating the importance of photochemical activity in the atmosphere.
Keywords: Particulate matter; Polycyclic aromatic hydrocarbons; Oxygenated; Oxidized; Oxygenated PAH; Analysis; Concentrations;

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO3 radicals with a series of acrylate esters: ethyl acrylate (k 1), n-butyl acrylate (k 2), methyl methacrylate (k 3) and ethyl methacrylate (k 4) at 298 ± 1 K and 760 Torr. The obtained rate constants are k 1  = (1.8 ± 0.25) × 10−16  cm3  molecule−1  s−1, k 2  = (2.1 ± 0.33) × 10−16  cm3  molecule−1  s−1, k 3  = (3.6 ± 1.2) × 10−15  cm3 molecule−1 s−1, k 4  = (4.9 ± 1.7) × 10−15  cm3  molecule−1  s−1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO3 radicals. In addition, the atmospheric lifetimes of the compound against NO3 attack are estimated and the results show that NO3 reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.
Keywords: Kinetics; Acrylate esters; Rate constant; Atmospheric lifetimes;

Measurement of plutonium isotopes, 239Pu and 240Pu, in air-filter samples from Seville (2001–2002) by E. Chamizo; M. García-León; S.M. Enamorado; M.C. Jiménez-Ramos; L. Wacker (1851-1858).
Since the last nuclear atmospheric test carried out by the People Republic of China in 1980 and since the Chernobyl accident in 1986, the plutonium hasn't been directly released into the atmosphere. However, nowadays, it is still present in the troposphere. This is due to plutonium-bearing soil particles physical resuspension processes. In this work, we study for the first time the temporal variation of plutonium isotopes, 239Pu and 240Pu, baseline concentrations on a monthly basis in surface air from Seville (Spain), and their correlation with some tracers of mineral dust, during 2001 and 2002. The Pu analyses were performed by low-energy Accelerator Mass Spectrometry (AMS). The 239Pu plus 240Pu (239+240Pu) activity levels achieved maximums during the summer period, characterized by the absence of rains, and minimums during the rainy seasons, laying in the range 1–20 nBq m−3. The 240Pu/239Pu two-year average atomic ratio was 0.18 ± 0.03, in agreement with the fallout plutonium. A good correlation with Pu and Al and Ti levels is observed. They are crustal components usually used as tracers of African dust over European countries. The hypothesis of the influence of the Saharan dust intrusions is supported as well through the study of Total Ozone Mass Spectrometer (TOMS) daily images.
Keywords: Plutonium; Pu-239; Pu-240; Accelerator mass spectrometry; AMS; Aerosols; Seville; Saharan dust; Soil resuspension; Spain;

A multi-layer model for pollutant dispersion with dry deposition to the ground by D.M. Moreira; T. Tirabassi; M.T. Vilhena; A.G. Goulart (1859-1865).
This paper presents a semi-analytical solution for the steady advection–diffusion equation that allows simulating the vertical turbulent dispersion of air pollution with deposition to the ground. The performances of the solution, with a proper parameterization of the vertical profiles of wind and eddy diffusivity, were evaluated against Hanford diffusion experiment dataset using two tracers (): a non-depositing gas (SF6) and depositing particles (ZnS). Results show that the dispersion model with the K-parameterization included produces a good fitting of the measured ground-level concentration data and there are no big differences between the parameterizations taken from literature. A comparison with other models was shown and discussed.
Keywords: Dry deposition; Air pollution modeling; Atmospheric boundary layer;

Quantifying trace gas emissions from composite landscapes: A mass-budget approach with aircraft measurements by S. Alfieri; U. Amato; M.F. Carfora; M. Esposito; V. Magliulo (1866-1876).
Quantifying trace gas emissions and the influence of surface exchange processes on the atmosphere is a necessary step towards the control of global greenhouse gas emissions and reliability of air quality models. This paper proposes a procedure based on the mass balance method and implemented on highly resolved aircraft data. It allows one to estimate surface exchanges on areas of several km2 and heterogeneous features exploiting the characteristics of convective boundary layer during steady state conditions that permit the estimation of emission/absorption terms as functions of advective fluxes only. A nonparametric approach is adopted and the fluxes on the surface of a virtual box surrounding the area of interest are reconstructed on the basis of scalar densities and wind vectors using Shepard functions. Two different techniques are also proposed to face lack of data on the top surface of the box. The method has been applied to experimental data coming from measurement campaigns on two different sites. It provides realistic estimates of the CO2 emission/absorption in the considered areas that are in good agreement with CO2 fluxes evaluated by Airborne Eddy Covariance and confirm the suitability of the proposed approach for the assessment of turbulent exchange of trace gases by composite landscapes. Uncertainties on the estimated emissions due to both propagation of the experimental error and interpolation have been quantified by bootstrap analysis as 6%.
Keywords: Mass balance; Airborne fluxes; Sky Arrow ERA; CO2 exchange; Shepard functions;

An assessment of the impact of climate change on air quality at two UK sites by Maria Athanassiadou; Jonathan Baker; David Carruthers; William Collins; Sofia Girnary; David Hassell; Matthew Hort; Colin Johnson; Kate Johnson; Richard Jones; David Thomson; Nicki Trought; Claire Witham (1877-1886).
Possible effects of climate change on air quality are studied for two urban sites in the UK, London and Glasgow. Hourly meteorological data were obtained from climate simulations for two periods representing the current climate and a plausible late 21st century climate. Of the meteorological quantities relevant to air quality, significant changes were found in temperature, specific humidity, wind speed, wind direction, cloud cover, solar radiation, surface sensible heat flux and precipitation. Using these data, dispersion estimates were made for a variety of single sources and some significant changes in environmental impact were found in the future climate. In addition, estimates for future background concentrations of NOx, NO2, ozone and PM10 upwind of London and Glasgow were made using the meteorological data in a statistical model. These showed falls in NOx and increases in ozone for London, while a fall in NO2 was the largest percentage change for Glasgow. Other changes were small. With these background estimates, annual-average concentrations of NOx, NO2, ozone and PM10 were estimated within the two urban areas. For London, results averaged over a number of sites showed a fall in NOx and a rise in ozone, but only small changes in NO2 and PM10. For Glasgow, the changes in all four chemical species were small. Large-scale background ozone values from a global chemical transport model are also presented. These show a decrease in background ozone due to climate change. To assess the net impact of both large scale and local processes will require models which treat all relevant scales.
Keywords: Climate change; Air quality; Urban pollution; Dispersion modelling; Ozone; Nitrogen Oxides; PM10;

Aerosol organic nitrogen over the remote Atlantic Ocean by Timothy Lesworth; Alex R. Baker; Timothy Jickells (1887-1893).
Water soluble organic nitrogen (WSON) has been measured in aerosols collected on three research cruises on the Atlantic Ocean from approximately 55°N to 45°S. Results are interpreted using air mass back trajectories and results for other aerosol components. WSON concentrations range from <1 to ∼40 (median 5.6) nmol m−3 with significant WSON concentrations in both fine (<1 μm) and coarse mode (>1 μm) aerosol. Concentrations of WSON were highest in samples containing Saharan dust, suggesting a locally significant source associated with soil dust. More generally WSON concentrations were highest in air which had recently crossed continental areas. In the whole data set, WSON is well correlated to total soluble nitrogen and represents approximately 25% of total nitrogen. This correlation implies a significant anthropogenic contribution to the organic nitrogen.
Keywords: Organic nitrogen; Size-segregated aerosols; Nitrate; Ammonium; Atlantic Ocean;

City breathability and its link to pollutant concentration distribution within urban-like geometries by Riccardo Buccolieri; Mats Sandberg; Silvana Di Sabatino (1894-1903).
This paper is devoted to the study of pollutant concentration distribution within urban-like geometries. By applying efficiency concepts originally developed for indoor environments, the term ventilation is used as a measure of city “breathability”. It can be applied to analyse pollutant removal within a city in operational contexts. This implies the evaluation of the bulk flow balance over the city and of the mean age of air. The influence of building packing density on flow and pollutant removal is, therefore, evaluated using those quantities. Idealized cities of regular cubical buildings were created with packing density ranging from 6.25% to 69% to represent configurations from urban sprawl to compact cities. The relative simplicity of these arrangements allowed us to apply the Computational Fluid Dynamics (CFD) flow and dispersion simulations using the standard kɛ turbulence model. Results show that city breathability within the urban canopy layer is strongly dependent from the building packing density. At the lower packing densities, the city responds to the wind as an agglomeration of obstacles, at larger densities (from about 44%) the city itself responds as a single obstacle. With the exception of the lowest packing density, airflow enters the array through lateral sides and leaves throughout the street top and flow out downstream. The air entering through lateral sides increases with increasing packing density.At the street top of the windward side of compact building configurations, a large upward flow is observed. This vertical transport reduces over short distance to turn into a downward flow further downstream of the building array. These findings suggest a practical way of identifying city breathability. Even though the application of these results to real scenarios require further analyses the paper illustrates a practical framework to be adopted in the assessment of the optimum neighbourhood building layout to minimize pollution levels.
Keywords: City breathability; Mean age of air; Street canyons and building packing density; Steady-state CFD simulations; Urban air quality;

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m−3 whereas the ammonium sulfate concentrations are about 5 μg m−3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m−3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH3 emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH3 emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.
Keywords: Ammonia; Ammonium sulfate; Ammonium nitrate; Secondary inorganic aerosol; COSMO-MUSCAT;

Intake fraction of nonreactive motor vehicle exhaust in Hong Kong by Zhiwen Luo; Yuguo Li; William W. Nazaroff (1913-1918).
The intake fraction (iF) of nonreactive constituents of exhaust from mobile vehicles in the urban area of Hong Kong is investigated using available monitoring data for carbon monoxide (CO) as a tracer of opportunity. Correcting for regional transport of carbon monoxide into Hong Kong, the annual-average iF for nonreactive motor vehicle emissions within the city is estimated to be around 270 per million. This estimated iF is much higher than values previously reported for vehicle emissions in US urban areas, Helsinki and Beijing, and somewhat lower than those reported for a densely populated street canyon in downtown Manhattan, New York City, or for emissions into indoor environments. The reported differences in intake fractions in various cities mainly result from the differences in local population densities. Our analysis highlights the importance of accounting for the influence of upwind transport of pollutants when using ambient data to estimate iF for an urban area. For vehicle exhaust in Hong Kong, it is found that the in/near vehicle microenvironment contributes similarly to the indoor home environment when accounting for the overall iF for children and adults.
Keywords: Intake fraction; Vehicle emission; Regional pollutant transport; Carbon monoxide; Exposure;

Compositions of volatile organic compound (VOC) emissions from painting applications and printing processes were sampled and measured by gas chromatography–mass spectrometry/flame ionization detection (GC–MS/FID) in Beijing. Toluene and C8 aromatics were the most abundant species, accounting for 76% of the total VOCs emitted from paint applications. The major species in printing emissions included heavier alkanes and aromatics, such as n-nonane, n-decane, n-undecane, toluene, and m/p-xylene. Measurements of VOCs obtained from furniture paint emissions in 2003 and 2007 suggest a quick decline in benzene levels associated with formulation changes in furniture paints during these years. A comparison of VOC source profiles for painting and printing between Beijing and other parts of the world showed significant region-specific discrepancies, probably because of different market demands and environmental standards. We conducted the evaluation of the source reactivities for various VOC emission sources. The ozone formation potential (OFP) for unit mass of VOCs source emissions is the highest for paint applications. Substituting solvent-based paints by water-based in Beijing will lead to an OFP reduction of 152,000 tons per year, which is more than 1/4 of the OFPs for VOCs emissions from vehicle exhaust in the city.
Keywords: VOCs; Solvent use; Paint; Printing; Source profile;

Total Ozone Concentration (TOC) data over nineteen stations around India (fifteen stations) and its adjoining regions (three stations in Pakistan and one station in Bangladesh) are investigated in the present analysis. The overpass satellite data for these nineteen stations, distributed in the latitude range from 8.48°N to 35.83°N and altitude range from 6 m to 2718 m are available from FTP Site. TOC data pertaining to the last twelve years from 1997 to 2008 were obtained from two different instruments: Total Ozone Mapping Spectrometer (TOMS) and Ozone Monitoring Instrument (OMI) on Earth Probe and AURA satellites respectively. The analysis is divided into two phases, each of six years duration; from 1997 to 2002 and from 2003 to 2008. Seasonal average values of TOC are calculated for the two phases and compared to study the spatial distribution (latitude, longitude and station altitude) and the trends of TOC variation. In general a decreasing tendency in ozone concentration was found everywhere. The average yearly rate of the TOC decrease was −0.363 DU over the entire region during the period 1997–2008. The trends in the TOC distribution and its decrease with latitude were found parabolic, with a deep near 14.7°N and 12.1°N for the two phases respectively. The decrease was maximum at lower latitude (−1.87%) and minimum (−0.25%) at higher latitude. Weak oscillatory trends in the TOC distribution and its decrease with longitude were found. A deep in the longitudinal variation was observed in each phase, at 77.4°E during 1997–2002 and at 78.2°E during 2003–2008. The minimum centre of the ozone distribution is therefore shifted from 14.7°N, 77.4°E to 12.1°N, 78.2°E over the last twelve years, and in general a meridional line near 78°E appears to divide symmetrically the TOC distribution over this region. Strong oscillatory trends in the seasonal average of TOC distribution and its decrease with station altitude are observed during the two phases. The inversion of high correlation coefficients between the seasonal average TOC and station altitude in the range 6 m to 2718 m indicate the existence of four transition layers aloft, near 200, 740, 1670, and 2400 m in the lower troposphere. Emission of precursor pollutants together with complex wind pattern around the marine boundary appears to have strong potentials to modulate tropospheric ozone and the observed spatial distribution of TOC may be expected.
Keywords: Tropospheric ozone; Stratospheric ozone; Free radical; Aerosol; Ozone precursor; Photolysis; Photo smog;

Aerosol indirect effect (AIE) was estimated over six Indian regions, which have been identified as main source regions of absorbing aerosol emissions, for four successive contrasting monsoon years, 2001 (normal monsoon rainfall year), 2002 (drought year), 2003 (excess monsoon rainfall year) and 2004 (below normal rainfall year). The AIE has been estimated both for fixed cloud liquid water path (CLWP) and for fixed cloud ice path (CIP) bins, ranging from 1 to 350 gm−2 at 25 gm−2 intervals obtained from Moderate resolution imaging spectroradiometer (MODIS). In 2002 and 2004, AIE found to be of positive (Twomey effect) in majority of the fixed CLWP and CIP bins, while in 2001 and 2003 majority of the bins were found to be showing negative indirect effect (Anti-Twomey effect). Changes in circulation patterns during contrasting monsoon seasons, bringing up air mass containing aerosols of different source origins may be the main reason for this positive and negative AIE. The study suggests that AIE could be one of the factors in modulating Indian summer monsoon. However, further research on this topic is to be carried out to establish the relationship between AIE and Indian monsoon rainfall and also AIE values may be parameterized in climate models for better prediction of monsoon.
Keywords: Aerosol optical depth; Cloud effective radius; Aerosol indirect effect;