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Atmospheric Environment (v.41, #1)
Characterisation of local and external contributions of atmospheric particulate matter at a background coastal site
by Pedro Salvador; B. ArtÃñano Begoña ArtÃñano; Xavier Querol; A. Andrés Alastuey; Miguel Costoya (pp. 1-17).
This study applies a methodology for discriminating local and external contributions of atmospheric particulate matter (PM) at a rural background station in the North-western coast of Spain. The main inputs at the nearest scale have come from soil dust, marine aerosol and road traffic. At a larger scale, the highest contributions have come from fossil-fuel combustion sources, giving rise to relatively high ammonium sulphate background levels, mainly in summer. External contributions from long-range transport processes of African dust and nitrate have been detected. Morocco and Western Sahara have been identified as the main potential source regions of African dust, with a higher content of Al and Ti than other crustal components. Geographical areas from central and Eastern Europe have been identified as potential sources of particulate nitrate. The discrimination of the PM contribution from natural and anthropogenic sources at different geographical scales is a necessary information for establishing PM reduction strategies in specific areas.
Keywords: Source apportionment; Trajectory statistics; Regional transport; Long-range transport
Assessment of ensemble-based chemical data assimilation in an idealized setting
by Emil M. Constantinescu; Adrian Sandu; Tianfeng Chai; Gregory R. Carmichael (pp. 18-36).
Data assimilation is the process of integrating observational data and model predictions to obtain an optimal representation of the state of the atmosphere. As more chemical observations in the troposphere are becoming available, chemical data assimilation is expected to play an essential role in air quality forecasting, similar to the role it has in numerical weather prediction (NWP). Considerable progress has been made recently in the development of variational tools for chemical data assimilation. In this paper, we assess the performance of the ensemble Kalman filter (EnKF). Results in an idealized setting show that EnKF is promising for chemical data assimilation.
Keywords: Data assimilation; Ensemble Kalman filter; Chemical and transport models; Atmospheric models
Assessing the importance of heterogeneous reactions of polycyclic aromatic hydrocarbons in the urban atmosphere using the Multimedia Urban Model
by Nana-Owusua A. Kwamena; John P. Clarke; Tara F. Kahan; Miriam L. Diamond; D.J. Donaldson (pp. 37-50).
The Multimedia Urban Model (MUM-Fate) of Diamond, M.L., Priemer, D.A., Law, N.L., 2001. Developing a multimedia model of chemical dynamics in an urban area. Chemosphere 44, 1655–1667 was used to evaluate the contribution of heterogeneous reactions of polycyclic aromatic hydrocarbons (PAHs) with gas-phase ozone to the total loss of these compounds in an illustrative urban environment. Recent laboratory studies by Kahan, T.F., Kwamena, N.-O.A., Donaldson, D.J., 2006. Heterogeneous ozonation kinetics of polycyclic aromatic hydrocarbons on organic films. Atmospheric Environment 40, 3448–3459 and Kwamena, N.-O.A., Thornton, J.A., Abbatt, J.P.D., 2004. Kinetics of surface-bound benzo[ a] pyrene and ozone on solid organic and salt aerosols. Journal of Physical Chemistry A 108, 11626–11634 provided half-lives for these heterogeneous reactions on surface films and atmospheric particulate matter, respectively. Two model scenarios were studied, representing urban environments with varying amounts of impervious surface coverage. We investigated six PAHs spanning a wide range of physical and chemical properties; results for anthracene, pyrene and benzo[ a]pyrene are presented here. Advection from air was the dominant loss process for all PAHs investigated. Heterogeneous reactions primarily on surface films but also on atmospheric particulate matter accounted for up to 75% of the reactive losses of lower volatility PAHs, which accumulate in condensed phases. The results suggest that surface films can be efficient reactive sinks for lower volatility PAHs.
Keywords: Surface film; Particulate matter; Heterogeneous reactions; Urban air pollution; Mass balance model
Characteristics influencing the variability of urban CO2 fluxes in Melbourne, Australia
by Andrew M. Coutts; Jason Beringer; Nigel J. Tapper (pp. 51-62).
Urban areas are significant contributors to global carbon dioxide emissions. Vehicle emissions and other anthropogenic related activities are a frequent source of CO2 to the atmosphere, contributing to global warming. Micrometeorological techniques used for observations in Northern Hemisphere cities have found that urban CO2 fluxes are consistently a source. This study investigates CO2 fluxes in an Australian city, adding to the global database of CO2 fluxes in a bid to aid in future development of planning policies concerning reductions in CO2 emissions. Using the eddy covariance approach, fluxes of CO2 were measured at a suburban site (Preston) in Melbourne, Australia from February 2004 to June 2005 to investigate temporal variability. A second site (Surrey Hills) with differing surface characteristics (in particular, greater vegetation cover) was also established in Melbourne and ran simultaneously for 6 months (February 2004–July 2004). Results showed that both sites were a net source of CO2 to the atmosphere. Diurnal patterns of fluxes were largely influenced by traffic volumes, with two distinct peaks occurring at the morning and evening traffic peak hours, with the winter morning peak averaging 10.9μmolm−2s−1 at Preston. Summer time fluxes were lower than during winter due to greater vegetative influence and reduced natural gas combustion. Vegetation limited the source of CO2 in the afternoon, yet was not enough to combat the strong local anthropogenic emissions. Surrey Hills showed higher fluxes of CO2 despite greater vegetation cover because of higher local traffic volumes. Annual emissions from Preston were estimated at 84.9tCO2ha−1yr−1. Magnitudes and patterns of suburban CO2 fluxes in Melbourne were similar to those observed in Northern Hemisphere suburban areas.
Keywords: Carbon dioxide fluxes; Urban area; Vegetation cover; Melbourne; Eddy covariance
Diurnal and seasonal trends in carbonyl levels in a semi-urban coastal site in the Gulf of Campeche, Mexico
by Ceron R.M. Cerón; Ceron J.G. Cerón; M. Muriel (pp. 63-71).
Concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde were measured in a semi-urban coastal site in the Gulf of Campeche, Mexico, during the winter, summer and autumn seasons. Measurements were carried out from 10 February 2004 to 16 November 2004. Carbonyl compound levels showed pronounced diurnal and seasonal variations. Maximum concentrations occurred between 13:00h and 16:00h, when vehicular traffic and photochemical activity were intense, and during the summer (when there was greater solar radiation). Only acetone during the first campaign (winter) did not correlate with temperature; it showed an inverse diurnal pattern, with higher concentrations during the night, probably due to a local and temporal source. The low concentrations of the main carbonyls found in this study, compared with the values reported for other urban areas, seem to indicate that air quality is still satisfactory in Carmen City.
Keywords: Carbonyls; Air quality; Coastal site; Mexico
Multi-element composition of historical lichen collections and bark samples, indicators of changing atmospheric conditions
by O.W. Purvis; P.D.J. Chimonides; T.E. Jeffries; G.C. Jones; A.-M. Rusu; H. Read (pp. 72-80).
Thirty six element signatures were compared in historical Parmelia sulcata samples from the Natural History Museum herbarium collected over the period 1797–1967 with those recorded in the same species and tree bark sampled in 2000 from Burnham Beeches, lying 40km west of London. Nineteen elements reached highest concentrations in herbarium samples, consistent with a pollution legacy and dust contamination in the herbarium. Healthy Parmelia sampled east and down-wind of London at a farm during peak SO2 emissions in 1967 contained highest V, Ni, Zn, Cd, Se, Ge contents, supporting derivation from fuel combustion; the same sample was previously determined as having a low δ34S and high S and N contents. Lowest V, Co, Ni, Cu, Zn, Sn, Ba, Pb, Mo, Sb, Li, B, Cs, U, Th, Ga contents were recorded in a sample with a high δ34S and low S content collected in 1887 from a remote region from Ross-shire, Scotland. Se and Cd enrichment, never-the-less suggest a transboundary pollution influence. Lichen Pb concentrations from Burnham Beeches were amongst the lowest recorded in spite of lichens being collected close to roads. Herbarium samples help interpret changes in element deposition where few data exist, in spite of dust contamination.
Keywords: Parmelia; Climate change; Pollution; Herbarium
Size-resolved sulfate and ammonium measurements in marine boundary layer over the North and South Pacific
by Atsushi Ooki; Mitsuo Uematsu; Shinichiro Noriki (pp. 81-91).
Marine background levels of non-sea-salt- (nss-) SO42− (5.0–9.7neqm−3), NH4+ (2.1–4.4neqm−3) and elemental carbon (EC) (40–80ngCm−3) in aerosol samples were measured over the equatorial and South Pacific during a cruise by the R/V Hakuho-maru from November 2001 to March 2002. High concentrations of nss-SO42− (47–94neqm−3), NH4+ (35–94neqm−3) and EC (130–460ngCm−3) were found in the western North Pacific near the coast of the Asian continent under the influence of the Asian winter monsoon. Particle size distributions of ionic components showed that the equivalent concentrations of nss-SO42− were balanced with those of NH4+ in the size range of 0.06< D<0.22μm, whereas the concentration ratios of NH4+ to nss-SO42− in the size range of D>0.22μm were decreased with increase in particle size. We estimated the source contributions of those aerosol components in the marine background air over the equatorial and South Pacific. Biomass burning accounted for the large fraction (80–98% in weight) of EC and the minor fraction (2–4% in weight) of nss-SO42−. Marine biogenic source accounted for several tens percents of NH4+ and nss-SO42−. In the accumulation mode, 70% of particle number existed in the size range of 0.1< D<0.2μm. In the size rage of 0.06< D<0.22μm, the dominant aerosol component of (NH4)2SO4 would be mainly derived from the marine biogenic sources.
Keywords: Size distribution; Anthropogenic aerosol; Biogenic sulfate; Ammonium sulfate; Elemental carbon
Modeling of dispersion near roadways based on the vehicle-induced turbulence concept
by Ali M. Sahlodin; Rahmat Sotudeh-Gharebagh; Yifang Zhu (pp. 92-102).
A mathematical model is developed for dispersion near roadways by incorporating vehicle-induced turbulence (VIT) into Gaussian dispersion modeling using computational fluid dynamics (CFD). The model is based on the Gaussian plume equation in which roadway is regarded as a series of point sources. The Gaussian dispersion parameters are modified by simulation of the roadway using CFD in order to evaluate turbulent kinetic energy (TKE) as a measure of VIT. The model was evaluated against experimental carbon monoxide concentrations downwind of two major freeways reported in the literature. Good agreements were achieved between model results and the literature data. A significant difference was observed between the model results with and without considering VIT. The difference is rather high for data very close to the freeways. This model, after evaluation with additional data, may be used as a framework for predicting dispersion and deposition from any roadway for different traffic (vehicle type and speed) conditions.
Keywords: Vehicle-induced turbulence; CFD; Eddy diffusivity; Freeway; Dispersion modeling; Gaussian plume equation
The impact of NO x, CO and VOC emissions on the air quality of Zurich airport
by Schurmann Gregor Schürmann; Schafer Klaus Schäfer; Carsten Jahn; Herbert Hoffmann; Martina Bauerfeind; Emanuel Fleuti; Rappengluck Bernhard Rappenglück (pp. 103-118).
To study the impact of emissions at an airport on local air quality, a measurement campaign at the Zurich airport was performed from 30 June 2004 to 15 July 2004. Measurements of NO, NO2, CO and CO2 were conducted with open path devices to determine real in-use emission indices of aircraft during idling. Additionally, air samples were taken to analyse the mixing ratios of volatile organic compounds (VOC). Temporal variations of VOC mixing ratios on the airport were investigated, while other air samples were taken in the plume of an aircraft during engine ignition. CO concentrations in the vicinity of the terminals were found to be highly dependent on aircraft movement, whereas NO concentrations were dominated by emissions from ground support vehicles. The measured emission indices for aircraft showed a strong dependence upon engine type. Our work also revealed differences from emission indices published in the emission data base of the International Civil Aviation Organisation. Among the VOC, reactive C2–C3 alkenes were found in significant amounts in the exhaust of an engine compared to ambient levels. Also, isoprene, a VOC commonly associated with biogenic emissions, was found in the exhaust, however it was not detected in refuelling emissions. The benzene to toluene ratio was used to discriminate exhaust from refuelling emission. In refuelling emissions, a ratio well below 1 was found, while for exhaust this ratio was usually about 1.7.
Keywords: Airport air quality; Aircraft engine emissions; DOAS; FTIR; VOC distribution
Investigation of the motor vehicle exhaust contribution to primary fine particle organic carbon in urban air
by J.R. Brook; L. Graham; J.P. Charland; Y. Cheng; X. Fan; G. Lu; S.M. Li; C. Lillyman; P. MacDonald; G. Caravaggio; J.A. MacPhee (pp. 119-135).
Motor vehicle (MV) emissions and ambient particle concentrations under a variety of situations were studied in Toronto and Vancouver, Canada. Petroleum biomarkers (i.e., hopanes and steranes) were used to determine the fraction of fine particle organic carbon (OC) attributed to primary particles in MV exhaust. Source profiles obtained from a tunnel and from direct tailpipe emissions were applied to ambient measurements at locations ranging from rush hour traffic to a regional background site. The greatest amount of MV OC, 4.0μgCm−3 out of 9.1μgCm−3 or 43%, was observed 75m south of a commuter highway during a period that included morning rush hour. Monthly estimates of MV-OC were determined for a downtown Toronto monitoring site for 2 years. Total OC concentrations were greater in the summer, due to secondary OC, but the amount of MV-OC did not exhibit a strong seasonal pattern. However, on a per cent basis, MV contributions from primary OC emissions were greatest in the winter (15–20%) and smallest in the summer (10–15%) with a two-year average of 14% of the OC or about 5% of the PM2.5.
Keywords: Particulate matter; Motor vehicle emissions; Source apportionment; Hopanes and steranes; Organic carbon
The dry-deposition of speciated mercury to the Florida Everglades: Measurements and modeling
by Frank J. Marsik; Gerald J. Keeler; Matthew S. Landis (pp. 136-149).
The Florida Everglades Dry-Deposition Study (FEDDS) was designed to test the viability of using new and existing measurement techniques in the estimation of the dry-depositional loading of speciated mercury (elemental gaseous, reactive gaseous and particulate) to a mixed sawgrass (Cladium jamaicense) and cattail (Typha domingensis) stand within the Florida Everglades. Measurement intensives were performed during 24 February–04 March 1999 and 05–21 June 2000, which corresponded to the climatological dry and wet seasons in South Florida, respectively. During these intensives, direct measurements of mercury dry-deposition were made using a newly developed surrogate water surface technique. These direct measurements were compared with modeled estimates of mercury dry-deposition to the site that were obtained through the use of an inferential or “bigleaf� model that was modified for use with speciated mercury. On-site measurements of ambient speciated mercury concentrations and numerous micrometeorological variables were used as input to the model.The average mercury dry-deposition measured during the 1999 FEDDS measurement intensive was 13.3±4.0ngm−2day−1, while the modeled deposition for this period was 3.4±2.3ngm−2day−1. The average mercury dry-deposition measured during the 2000 FEDDS measurement intensive was lower, 5.9±2.8ngm−2day−1, while the average modeled deposition for this period was 1.8±0.6ngm−2day−1. A least-squares linear regression suggests that the model was able to explain 74% and 73% of the variability in the datasets for the 1999 and 2000 FEDDS intensives, respectively. While reported reductions in total mercury emissions across South Florida between study periods could explain the reductions in both the measured and predicted mercury dry-deposition estimates, the increased presence of cumulus convection during the summer-intensive could have also resulted in a removal of reactive and particulate mercury species within the atmosphere of South Florida.
Keywords: Mercury; Dry-deposition; Modeling; Florida Everglades
Influence of fuel composition on polycyclic aromatic hydrocarbon emissions from a fleet of in-service passenger cars
by McKenzie C.H. Lim; Godwin A. Ayoko; Lidia. Morawska; Zoran D. Ristovski; E. Rohan Jayaratne (pp. 150-160).
The composition of exhaust emissions from eight in-service passenger cars powered by liquefied petroleum gas (LPG) and unleaded petrol (ULP) were measured on a chassis dynamometer at two driving speeds (60 and 80kmh−1) with the aims of evaluating their polycyclic aromatic hydrocarbon (PAH) contents and investigating the effects of the type of fuel on vehicle performance, ambient air quality and associated health risks. Naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene were the most prominent PAHs emitted by both ULP and LPG powered cars. The total emission factors of PAHs from LPG cars were generally lower than (but statistically comparable with) those of ULP cars. Similarly, the total BAPeq of the PAHs emitted by LPG cars were lower than those from ULP cars. Multi-criteria decision making (MCDM) methods showed that cars powered by LPG fuel performed better than those powered by ULP fuel in term of PAH levels. The implications of these observations on the advantages and disadvantages of using ULP and LPG fuels are discussed.
Keywords: Liquefied petroleum gas; Unleaded petrol; Exhaust emission; Polycyclic aromatic hydrocarbons; Toxicity evaluation and multivariate analysis
A consistent method for modelling PM10 and PM2.5 concentrations across the United Kingdom in 2004 for air quality assessment
by John R. Stedman; Andrew J. Kent; Susannah Grice; Tony J. Bush; Richard G. Derwent (pp. 161-172).
A modelling method has been developed to map PM10 and PM2.5 concentrations across the UK at background and roadside locations. Separate models have been calibrated using gravimetric measurements and Tapered Element Oscillating Microbalance instruments (TEOM) using source apportionments appropriate to the size fractions and sampling methods. Maps have been prepared for a base year of 2004 and predictions have been calculated for 2010 and 2020 on the basis of current policies. Comparisons of the modelling results with air quality regulations suggest that exceedences of the EU Daughter Directive stage 1 24-h limit value for PM10 at the roadside in 2004 will be largely eliminated by 2020. The concentration cap of 25μgm−3 for PM2.5 proposed within the CAFÉ Directive is expected to be met at all locations. Projections for 2010 and 2020 suggest that the proposed exposure reduction (ER) target is likely to be considerably more stringent and require additional measures beyond current policies. Thus the model results suggest that the balance between the stringency of the concentration cap and the ER target in the proposed directive is appropriate. Measures to achieve greater reductions should therefore have the maximum public health benefit and air quality policy is not driven by the need to reduce concentrations at isolated ‘hotspots’.
Keywords: Particulate matter; Source apportionment; Dispersion model; EU limit value; Exposure reduction target
Evaluation and intercomparison of Ozone and PM10 simulations by several chemistry transport models over four European cities within the CityDelta project
by R. Vautard; P.H.J. Builtjes; P. Thunis; C. Cuvelier; M. Bedogni; B. Bessagnet; Honore C. Honoré; N. Moussiopoulos; G. Pirovano; M. Schaap; R. Stern; L. Tarrason; P. Wind (pp. 173-188).
The CityDelta project Cuvelier et al. [2006. CityDelta: a model intercomparison study to explore the impact of emission reductions in European cities in 2010. Atmospheric Environment] is designed to evaluate the air quality response of several emission abatement scenarios for 2010 at the scale of the European continent, and specifically in the areas where most people live: the cities. Before evaluating this response, the model simulations in a control case must be evaluated against observations in order to understand their main strengths and weaknesses. In this article six different models are used to simulate a full year (1999) of air quality pollutant concentrations over domains encompassing a large area around four major European cities: Berlin, Milan, Paris and Prague. Three models are used both at large-scale (typically 50km) and small-scale resolution (5km). The intercomparison of the simulation results for ozone and particles smaller than 10 microns (PM10) leads to the following conclusions:(i)Models capture fairly well the mean, daily maxima and variability of ozone concentrations, as well as the time and intercity variability. However, a significant overestimation of ozone in city centres is found especially for large-scale models.(ii)PM10 simulation skill is generally poor, and large-scale models underestimate their mass. The difference between Milan (highly polluted) and the other cities is not reproduced. All models have difficulties in capturing the observed seasonal variations.(iii)The fine scale models show higher PM10 and lower ozone concentrations in urban areas, which are closer to the observations than are the large-scale models.
Keywords: Air quality; Ozone; PM; Model intercomparison; Emission–reduction scenarios
CityDelta: A model intercomparison study to explore the impact of emission reductions in European cities in 2010
by C. Cuvelier; P. Thunis; R. Vautard; M. Amann; B. Bessagnet; M. Bedogni; R. Berkowicz; J. Brandt; F. Brocheton; P. Builtjes; C. Carnavale; A. Coppalle; B. Denby; J. Douros; A. Graf; O. Hellmuth; A. Hodzic; Honore C. Honoré; J. Jonson; A. Kerschbaumer; F. de Leeuw; E. Minguzzi; N. Moussiopoulos; C. Pertot; V.H. Peuch; G. Pirovano; L. Rouil; F. Sauter; M. Schaap; R. Stern; L. Tarrason; E. Vignati; M. Volta; L. White; P. Wind; A. Zuber (pp. 189-207).
This paper gives an overview of the set up, methodology and the obtained results of the CityDelta (phase 1 and 2) project. In the context of the Clean Air For Europe programme of the European Commission, the CityDelta project was designed to evaluate the impact of emission-reduction strategies on air quality at the European continental scale and in European cities. Ozone and particulate matter (PM) are the main components that have been studied. To achieve this goal, a model intercomparison study was organized with the participation of more than 20 modelling groups with a large number of modelling configurations. Two following main topics can be identified in the project. First, in order to evaluate their strengths and weaknesses, the participating models were evaluated against observations in a control year (1999). An accompanying paper will discuss in detail this evaluation aspect for four European cities. The second topic is the actual evaluation of the impact of emission reductions on levels of ozone and PM, with particular attention to the differences between large-scale and fine-scale models. An accompanying paper will discuss this point in detail. In this overview paper the main input to the intercomparison is described as well as the use of the ensemble approach. Finally, attention is given to the policy relevant issue on how to implement the urban air quality signal into large-scale air quality models through the use of functional relationships.
Keywords: Air quality; Ozone; Particulate matter; Model intercomparison; Emission-reduction scenarios
Analysis of model responses to emission-reduction scenarios within the CityDelta project
by P. Thunis; L. Rouil; C. Cuvelier; R. Stern; A. Kerschbaumer; B. Bessagnet; M. Schaap; P. Builtjes; L. Tarrason; J. Douros; N. Moussiopoulos; G. Pirovano; M. Bedogni (pp. 208-220).
This paper investigates how air quality models applied at different scales (50 and 5km horizontal resolutions) can predict pollution levels in response to emission control strategies in various cities in Europe. This study, involving five modelling teams and focused on four European cities, has been conducted within the CityDelta project (http://aqm.jrc.it/citydelta). The CityDelta models generally agree, on the O3 changes expected from scenarios representative of the current legislation on air pollution in 2010, named CLE. They also agree about less scope for further improvements from emission controls beyond CLE. For PM10, more significant differences between the models are observed, especially between models with different spatial resolutions. However, these differences are city-dependent and are larger in complex geographical areas such as Milan in the Pô Valley than in the Paris area.Fine scale models generally capture important urban scale effects, which are not represented by regional scale models. For instance, they improve the simulation of potential O3 increase caused by NO x emissions reduction in NMVOC-limited regime situations. Large scale models generally underpredict PM mean concentrations in city areas. A series of emission scenarios to address the question of the efficiency of local emission controls designed independently from regional measures is analyzed. The analysis of the CityDelta results contributes to the quantification of the impact of grid resolution in air quality modelling, and its application to emission control scenarios.
Keywords: Air quality; Ozone; PM; Model intercomparison; Emission-reduction scenarios
Description of pollutant dispersion in an urban street canyon using a two-dimensional lattice model
by Jimenez-Horrnero F.J. Jiménez-Horrnero; Giraldez J.V. Giráldez; Gutierrez de Rave E. Gutiérrez de Ravé; F.J. Moral (pp. 221-226).
The pollutant dispersion in a street canyon has been described in this work by using an isothermal two-dimensional lattice model coupled to the Smagorinsky sub-grid scale model. The influence of the ratio between the height of the upstream and downstream canyon walls, as well as the gap distance between them on the flow pattern, was analyzed considering the situations of ‘open country’ or isolated street canyon and ‘urban roughness’ in which the influence of an urban fabric was considered. The model determined the trajectories of a large number of passive tracer particles released in the computational domain, making it easy to visualize the flow regimes established in each case. The results agreed with the observations reported from the experiments showing a strong influence on the flow inside the canyon exerted by the upstream landscape configuration.
Keywords: Lattice model; Pollutant dispersion; Turbulence; Street canyon
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