Air pollution in cities

Air quality in cities is the result of a complex interaction between natural and anthropogenic environmental conditions. Air pollution in cities is a serious environmental problem – especially in the developing countries. The air pollution path of the urban atmosphere consists of emission and transmission of air pollutants resulting in the ambient air pollution. Each part of the path is influenced by different factors. Emissions from motor traffic are a very important source group throughout the world. During transmission, air pollutants are dispersed, diluted and subjected to photochemical reactions. Ambient air pollution shows temporal and spatial variability. As an example of the temporal variability of urban air pollutants caused by motor traffic, typical average annual, weekly and diurnal cycles of NO, NO₂, O₃ and O_x are presented for an official urban air-quality station in Stuttgart, southern Germany. They are supplemented by weekly and diurnal cycles of selected percentile values of NO, NO₂, and O₃. Time series of these air pollutants give information on their trends. Results are discussed with regard to air pollution conditions in other cities. Possibilities for the assessment of air pollution in cities are shown. In addition, a qualitative overview of the air quality of the world's megacities is given.     

Comparison of Ozone Temporal Scales for Large Urban,Small Urban,and Rural Areas in Georgia

Abstract

Ground‐level ozone (O₃) time series are characterized by the sum of several distinct temporal scales: long‐term, seasonal, synoptic, diurnal (daily), and intraday variation. In this study, the authors use a Kolmorogov‐Zurbenko filter to separate the 1981–2001 O₃ time‐series from many sites in and around Georgia into these various components. The authors compare the temporal components to examine differences between small and large metropolitan areas and between urban and rural areas. They then focus on the synoptic component to define a predominant transport region or airshed for each site.     

Effects of 10% biofuel substitution on ground level ozone formation in Bangkok,Thailand

The Thai Government's search for alternatives to imported petroleum led to the consideration of mandating 10% biofuel blends (biodiesel and gasohol) by 2012. Concerns over the effects of biofuel combustion on ground level ozone formation in relation to their conventional counterparts need addressing. Ozone formation in Bangkok is explored using a trajectory box model. The model is compared against O₃, NO, and NO₂ time concentration data from air monitoring stations operated by the Thai Pollution Control Department. Four high ozone days in 2006 were selected for modeling. Both the traditional trajectory approach and a citywide average approach were used. The model performs well with both approaches but slightly better with the citywide average. Highly uncertain and missing data are derived within realistic bounds using a genetic algorithm optimization. It was found that 10% biofuel substitution will lead to as much as a 16 ppb peak O₃ increase on these four days compared to a 48 ppb increase due to the predicted vehicle fleet size increase between 2006 and 2012. The approach also suggests that when detailed meteorological data is not available to run three dimensional airshed models, and if the air is stagnant or predominately remains over an urban area during the day, that a simple low cost trajectory analysis of O₃ formation may be applicable.     

Modeling smog chamber measurements of incremental reactivities of volatile organic compounds

A series of experiments performed at the GM chamber facility provided useful data for the evaluation of two current chemical mechanisms used in airshed models (SAPRC97 and SAPRC93 mechanisms) and a test of their predictions of maximum incremental reactivities which describe the change in ozone caused by adding a small amount of a compound to a polluted urban mixture under high-NO_x conditions. In general, the SAPRC97 detailed mechanism performed well in simulating the volatile organic compound (VOC) reactivity experiments for most test species; however, it had a tendency to underpredict incremental reactivities. For base-case runs containing a nine-component urban-surrogate mixture under high-NO_x conditions, where maximum concentrations of either O₃ or the smog produced (SP=the initial NO oxidized plus the ozone produced) were not attained during a 12-h irradiation, the SAPRC97 performed well while the SAPRC93 underestimated SP or O₃ significantly. Under low-NO_x conditions where SP or O₃ maximums were attained, the SAPRC97 as well as the SAPRC93 underpredicted SP or O₃ for runs containing the urban-surrogate mixture. Simulations of incremental reactivity experiments and special chamber runs showed that the SAPRC97 mechanism performed poorly for n-octane and some aromatic isomers such as ethylbenzene and p-xylene, while it performed well for other aromatic isomers such as toluene, m-xylene and 1,3,5-trimethylbenzene. Although, additional chamber data for aromatic isomers is needed to further clarify the parameterized chemical mechanisms for aromatic isomers, the newer SAPRC97 mechanism appears to be much improved over the older SAPRC93 mechanism for simulating aromatic chemistry.     

Modeling reactive pollutant dispersion in an urban street canyon

Reactive pollutant dispersion in an urban street canyon with a street aspect ratio of one is numerically investigated using a computational fluid dynamics (CFD) model. The CFD model developed is a Reynolds-averaged Navier–Stokes equations (RANS) model with the renormalization group (RNG) k–ε turbulence model and includes transport equations for NO, NO₂, and O₃ with simple photochemistry. An area emission source of NO and NO₂ is considered in the presence of background O₃ and street bottom heating (ΔT=5 °C) with an ambient wind perpendicular to the along-canyon direction. A primary vortex is formed in the street canyon and the line connecting the centers of cross-sectional vortices meanders over time and in the canyon space. The cross-canyon-averaged temperature and reactive pollutant concentrations oscillate with a period of about 15 min. The averaged temperature is found to be in phase with NO and NO₂ concentrations but out of phase with O₃ concentration. The photostationary state defect is small in the street canyon except for near the roof level and the upper downwind region of the canyon and its local minimum is observed near the center of the primary vortex. The budget analysis of NO (NO₂) concentration shows that the magnitude of the advection or turbulent diffusion term is much larger (larger) than that of the chemical reaction term and that the advection term is largely balanced by the turbulent diffusion term. On the other hand, the budget analysis of O₃ concentration shows that the magnitude of the chemical reaction term is comparable to that of the advection or turbulent diffusion term. The inhomogeneous temperature distribution itself affects O₃ concentration to some extent due to the temperature-dependent photolysis rate and reaction rate constant.     

Development of a condensed SAPRC-07 chemical mechanism

The development of a condensed version of the SAPRC-07 mechanism, designated CS07A, is described. It is comparable in size to CB05 and was derived directly from detailed SAPRC-07, which serves as the basis for its predictive capability and evaluation against chamber data. It incorporates the more condensed and approximate peroxy radical lumped operator method employed in SAPRC-99, and condensations involving removing or lumping less reactive compounds, lumping some product species in isoprene or aromatic mechanisms with other species with similar mechanisms using reactivity weighting, removing some compounds and reactions that are rapidly reversed, and using fewer model species to represent emitted alkanes and similar species. It gives predictions of O₃, total PANs and OH radicals that are very close to the standard SAPRC-07 mechanism for airshed models used as the starting point, but predicts about 15% more H₂O₂. Use of CS07A is suitable for models where the priority is O₃ formation, while the less condensed version should be used if more accurate hydroperoxide predictions are a priority.     

Condensed atmospheric photooxidation mechanisms for isoprene

Two condensed mechanisms for the atmospheric reactions of isoprene, which differ in the number of species used to represent isoprene's reactive products, have been developed for use in ambient air quality modehng. They are based on a detailed isoprene mechanism that has recently been developed and extensively evaluated against environmental chamber data. The new condensed mechanisms give very close predictions to those of the detailed mechanism for ozone, OH radicals, nitric acid, H₂O₂, formaldehyde, total PANS, and for incremental effects of isoprene on ozone formation in one day simulations. The effects of the condensations become somewhat greater in multi-day simulations, particularly in cases where NO₃ reactions are important at nighttime, but the ozone predictions are still very close. On the other hand, the SAPRC-90, RADM-2, and Carbon Bond IV isoprene mechanisms give quite different predictions of these quantities. It is recommended that the new mechanisms replace those currently used in airshed simulations where isoprene emissions are important.     

A study of the ozone formation by ensemble back trajectory-process analysis using the Eta–CMAQ forecast model over the northeastern U.S. during the 2004 ICARTT period

The integrated process rates (IPRs) estimated by the Eta–CMAQ model at grid cells along the trajectory of the air mass transport path were analyzed to quantitatively investigate the relative importance of physical and chemical processes for O₃ formation and evolution over the northeastern U.S. during the 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) period. The Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model is used to determine the back trajectory of air masses reaching the northeast by linking a downwind receptor to upwind source areas. The process analysis is applied to a high O₃ episode occurring on July 22, 2004 at three selected sites in the northeastern U.S. The process analysis at the location of the site shows that during the daytime, the O₃ concentrations in the surface layer are mainly enhanced by the vertical diffusion of O₃-rich air from aloft, followed by horizontal advection (HADV) and chemical production (CHEM), whereas dry deposition (DDEP) and vertical advection (ZADV) mainly deplete O₃ concentrations at the sites of Valley Central (VC), NY and Castle Spring (CS), NH. By integrating the effects of each process over the depth of the daytime planetary boundary layer (PBL), it was found that at the VC site, CHEM and HADV contributed about 53% and 41%, respectively, to O₃ levels within the PBL. This confirms the significance of regional transport of O₃ from the industrialized areas into the Northeast. On the other hand, the process analysis results for O₃ formation in moving air masses indicate that on July 22, large chemical production of O₃ along the transport path over the polluted urban regions leads to significant increase in O₃ in the air mass reaching the VC site, whereas the low chemical production of O₃ along the transport path over the low emission regions leads to the low O₃ concentration at the site of Belleayre Mountain (BM), NY. The dramatic buildup of O₃ concentration from 50 ppb to 102 ppb in the air masses before reaching the VC site after 12:00 EST on 7/22 indicates the significant impact of pollution from the northeastern urban corridor at this site. On the basis of the results at the CS site, it was found that high NO_x emissions along the transport path led to large chemical production of O₃ in the air mass reaching the CS site on July 22. In contrast, the low chemical production of O₃ associated with low emission (relatively clean conditions) along the transport path over the northern portions of the domain is responsible for the low O₃ concentration at the CS site on July 26.     

Examination of a subgrid-scale parameterization for the transport of pollutants in a nonprecipitating cumulus cloud ensemble

The mass flux based subgrid-scale parameterization technique of Gidel (1983, J. geophys. Res.88, 6587–6599) is re-examined for use in Eulerian long-range transport models. Specifically, the parameterization scheme is incorporated into the STEM-II Eulerian transport/transformation/removal model and the model is used to investigate pollutant transport in a nonprecipitating cumulus cloud ensemble. The effects of entrainment, detrainment, evaporation and the transport by subsidence, updrafts and turbulent diffusion are included in the analysis. Presented simulation results indicate that the parameterization is able to treat the rapid vertical transport by cloud updrafts, enables the calculation of reaction rates based on subgrid-scale concentrations, and is readily adopted by Eulerian models.     

Characterizations of chemical oxidants in Mexico City: A regional chemical dynamical model (WRF-Chem) study

The formation of chemical oxidants, particularly ozone, in Mexico City were studied using a newly developed regional chemical/dynamical model (WRF-Chem). The magnitude and timing of simulated diurnal cycles of ozone (O₃), carbon monoxide (CO) and nitrogen oxides (NO_x)_, and the maximum and minimum O₃ concentrations are generally consistent with surface measurements. Our analysis shows that the strong diurnal cycle in O₃ is mainly attributable to photochemical variations, while diurnal cycles of CO and NO_x mainly result from variations of emissions and boundary layer height. In a sensitivity study, oxidation reactions of aromatic hydrocarbons (HCs) and alkenes yield highest peak O₃ production rates (20 and 18 ppbv h⁻¹, respectively). Alkene oxidations, which are generally faster, dominate in early morning. By late morning, alkene concentrations drop, and oxidations of aromatics dominate, with lesser contributions from alkanes and CO. The sensitivity of O₃ concentrations to NO_x and HC emissions was assessed. Our results show that daytime O₃ production is HC-limited in the Mexico City metropolitan area, so that increases in HC emissions increase O₃ chemical production, while increases in NO_x emissions decrease O₃ concentrations. However, increases in both NO_x and HC emissions yield even greater O₃ increases than increases in HCs alone. Uncertainties in HC emissions estimates give large uncertainties in calculated daytime O₃, while NO_x emissions uncertainties are less influential. However, NO_x emissions are important in controlling O₃ at night.     

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.     

Ground-level ozone in the Pearl River Delta region: Analysis of data from a recently established regional air quality monitoring network

The ambient air quality monitoring data of 2006 and 2007 from a recently established Pearl River Delta (PRD) regional air quality monitoring network are analyzed to investigate the characteristics of ground-level ozone in the region. Four sites covering urban, suburban, rural and coastal areas are selected as representatives for detailed analysis in this paper. The results show that there are distinct seasonal and diurnal cycles in ground-level ozone across the PRD region. Low ozone concentrations are generally observed in summer, while high O₃ levels are typically found in autumn. The O₃ diurnal variations in the urban areas are larger than those at the rural sites. The O₃ concentrations showed no statistically significant difference between weekend and weekdays in contrast to the findings in many other urban areas in the world. The average ozone concentrations are lower in urban areas compared to the sites outside urban centers. Back trajectories are used to show the major air-mass transport patterns and to examine the changes in ozone from the respective upwind sites to a site in the center of the PRD (Wanqingsha). The results show higher average ozone concentrations at the upwind sites in the continental and coastal air masses, but higher 1 h-max O₃ concentrations (by 8–16 ppbv) at the center PRD site under each of air-mass category, suggesting that the ozone pollution in the PRD region exhibits both regional and super-regional characteristics.     

Overestimation of urban nitrogen dioxide by passive diffusion tubes: a comparative exposure and model study

A detailed comparative trial of passive diffusion tubes (PDT) for measurement of NO₂ in urban air has been undertaken in Edinburgh, UK. Acrylic, foil-wrapped and quartz tubes were exposed in parallel for 1-week and 4-week periods at three urban sites equipped with continuous analysers for NO, NO_x and O₃. Standard acrylic PDTs significantly overestimated NO₂ concentrations relative to chemiluminescence analysers, by an average of 27% over all sites for 1-week exposures. No significant difference was observed between standard and foil-wrapped acrylic tubes (both UV blocking). The mean ratio between quartz (UV transmitting) tubes and chemiluminescence analysers was 1.06. Quartz PDT data suggest a tendency for in situ photolysis to offset (but in a non-quantifiable way) the effect of chemical overestimation. The 4-week exposures yielded systematically lower NO₂ concentration than average NO₂ from four sequential 1-week exposures over the same period. The reduction in the apparent NO₂ sampling rate with time mostlikely arises from in situ photolysis of trapped NO₂. Hourly NO₂, NO and O₃ data for 20 1-week exposures were used as input to a numerical model of diffusion tube operation incorporating chemical reaction between co-diffusing NO and O₃ within the tube. The mean calculated overestimation of 22% for NO₂ from the PDT model simulations is close to the average difference between acrylic PDT and analyser NO₂ concentrations (24% for the same exposure periods), showing that within-tube chemistry can account for observed discrepancies in NO₂ measurement between the two techniques. Overestimation by PDT generally increased as average NO₂/NO_x ratios decreased. Accurate quantitative correction of PDT measurements is not possible. Nevertheless, PDT NO₂ concentrations were correlated with both analyser NO₂ and NO_x suggesting that acrylic PDTs retain a qualitative measure of NO₂ and NO_x variation at a particular urban location.     

Application of the k–ε turbulence model to the high Reynolds number skimming flow field of an urban street canyon

A two-dimensional, steady, k–ε turbulence model was used to investigate the high Reynolds number skimming flow field of an urban street canyon. We describe the critical canyon width-to-height ratios that distinguish a cascade of vortex patterns that form in an urban street canyon. Details of the flow field are reported that includes the structure of the mean flow field, turbulent kinetic energy, turbulent length scale, turbulent eddy viscosity, and Reynolds stress for three typical different aspect ratios, W/H, of a street canyon. The consequences of vortex layering on vertical transport are explored.     

The use of wind fields in a land use regression model to predict air pollution concentrations for health exposure studies

A methodology is developed to include wind flow effects in land use regression (LUR) models for predicting nitrogen dioxide (NO₂) concentrations for health exposure studies. NO₂ is widely used in health studies as an indicator of traffic-generated air pollution in urban areas. Incorporation of high-resolution interpolated observed wind direction from a network of 38 weather stations in a LUR model improved NO₂ concentration estimates in densely populated, high traffic and industrial/business areas in Toronto-Hamilton urban airshed (THUA) of Ontario, Canada. These small-area variations in air pollution concentrations that are probably more important for health exposure studies may not be detected by sparse continuous air pollution monitoring network or conventional interpolation methods. Observed wind fields were also compared with wind fields generated by Global Environmental Multiscale-High resolution Model Application Project (GEM-HiMAP) to explore the feasibility of using regional weather forecasting model simulated wind fields in LUR models when observed data are either sparse or not available. While GEM-HiMAP predicted wind fields well at large scales, it was unable to resolve wind flow patterns at smaller scales. These results suggest caution and careful evaluation of regional weather forecasting model simulated wind fields before incorporating into human exposure models for health studies. This study has demonstrated that wind fields may be integrated into the land use regression framework. Such integration has a discernable influence on both the overall model prediction and perhaps more importantly for health effects assessment on the relative spatial distribution of traffic pollution throughout the THUA. Methodology developed in this study may be applied in other large urban areas across the world.     

Aircraft observations of aerosols,O3 and NOy in a nighttime urban plume

Nighttime measurements of aerosol surface area, O₃, NO_y and moisture were made downwind of Portland, Oregon, as part of a study to characterize the chemistry in a nocturnal urban plume. Air parcels sampled within the urban plume soon after sunset had positive correlations between O₃, relative humidity, NO_y and aerosol number density. However, the air parcels sampled within the urban plume just before dawn had O₃ mixing ratios that were highly anti-correlated with aerosol number density, NO_y and relative humidity. Back-trajectories from a mesoscale model show that both the post-sunset and pre-dawn parcels came from a common maritime source to the northwest of Portland. The pre-dawn parcels with strong anti-correlations passed directly over Portland in contrast to the other parcels that were found to pass west of Portland. Several gas-phase mechanisms and a heterogeneous mechanism involving the loss of O₃ to the aerosol surface, are examined to explain the observed depletion in O₃ within the pre-dawn parcels that had passed over Portland.     

Measurements and analyses of nitrogen oxides and ozone in the yard and on the roof of a street-canyon in Suzhou

The concentrations of air pollutants such as nitrogen oxides and ozone characterised by very fast chemical reactions can significantly vary within urban street-canyon due to the short distances between sources and receptor. With the primary objective to analyse this issue, NO, NO₂, NO_x, O₃, BTX, and wind flow field were continuously measured for 1 week at two heights (a street-level yard and a 25-m-high rooftop) in an urban canyon in Suzhou (China). The yard ozone concentrations were found to be up to six times lower than on the roof. Different frequency distributions (FD), dynamical and chemical processes of the pollutant variations from yard to roof are discussed to explain the findings. The predominant factors for the dissimilar pollutant vertical diffusion at the two measurement locations were associated to dissimilar fluid-dynamic and heterogeneous removal effects that likely induced dissimilar ozone chemical processes relative to NO_x and BTX precursors.     

A gas/aerosol air pollutants study over the urban area of Rome using a comprehensive chemical transport model

The aim of this study was to identify areas of potential relevant exposure to pollutants within Rome's urban core. To meet this goal, intensive field campaigns were conducted and simulations were performed, using the flexible air quality regional model (FARM), to study winter and summer pollution episodes. The simulations were performed using a complete emission inventory that included traffic flow model results of the Roman street network to better describe, with respect to the available diffuse national emission inventory, the hourly variation of traffic emissions in the city. The meteorological reconstruction was performed by means of both prognostic and diagnostic models by using experimental data collected during the field campaigns. To evaluate the capability of the FARM model to capture the main features of the selected episodes, a comparison of modelled results against observed air quality data for different pollutants was performed at urban and rural sites. FARM performed well in predicting ozone (O₃) and nitrogen dioxide (NO₂) concentrations, showing a good reproduction of both daily peaks and their diurnal variations. The model also showed a good capability to reproduce the magnitude of volatile alkane, aromatic and carbonyl compound concentrations. PM₁₀ model results revealed the tendency to under-predict the observed values. PM composition model results were compared with observed data, evidencing good results for elemental carbon (EC), nitrate (NO₃⁻) and ammonium (NH₄⁺), underestimation for sulphate (SO₄²⁻) and poor performance for organic matter (OM). The soil components of PM were found to be significantly under-predicted by the model, especially during Saharan dust episodes. Overall, the study results show large areas of high O₃ and PM₁₀ concentrations where levels of pollutants should be carefully monitored and population exposure evaluated.     

A numerical experiment of roadside diffusion under traffic-produced flow and turbulence

Roadside air pollution due to heavy traffic is one of the unsettled issues in the atmospheric environment in urban areas. As a practical application of a Computational Fluid Dynamics (CFD) model, a coupled mesoscale-CFD model was applied to the Ikegamicho area of Kawasaki City, Japan. For this study, the effects of traffic-produced flow and turbulence (TPFT) on the dispersion of the pollutants near the heavy traffic road were mainly investigated in an actual urban area. First, a series of preliminary CFD calculations was conducted for a road tunnel field experiment to obtain a fitting parameter for the traffic-produced flow. The calculation was then performed for 24 h in December 2005 around Ikegamicho, and the results were compared with the data at a roadside monitoring post in the area, located 10 m from the boundary of the ground road. In general, the effect of traffic-produced flow and turbulence was limited at the downstream side of the roads. The maximum concentration of NO_x was reduced and smoothed out along the traffic flow by the traffic-produced flow and turbulence on the road. The effects of traffic-produced turbulence on the dispersion of pollutants were greater than those of traffic-produced flow; however, the effects of traffic-produced flow were not negligible. The concentration of pollutants was not particularly dependent on the turbulent Schmidt number because most of the emission sources were introduced as volume sources in the present calculations, and the effect caused by differences in the material diffusion coefficient was not particularly significant at the outside of the road.     

Influence of nocturnal vertical stability on daytime chemistry: A one-dimensional model study

Nocturnal chemistry can play an important role in determining the initial morning conditions for daytime chemistry in urban areas. However, the impact on daytime O₃ levels is difficult to assess as the suppression of vertical trace gas transport leads to highly altitude dependent nocturnal chemistry, in particular with respect to the removal and conversion of nitrogen oxides (NO_x) and volatile organic compounds (VOC). One-dimensional (1-D) chemical transport model calculations for different nighttime vertical stabilities and different ozone formation regimes (i.e. NO_x- vs. VOC-sensitive) were performed assuming a 1000 m high daytime boundary layer and a growing nocturnal boundary layer reaching 200 m height at the end of the night. Exclusion of NO₃ chemistry from the model leads to daytime O₃ concentration changes from ?4% to +16% for different O₃ sensitivities. In all cases strong nocturnal vertical concentration profiles of NO_x, O₃, NO₃ and N₂O₅ and a dependence of these profiles on vertical stability were found at night. The nocturnal NO_x loss averaged over the lowest 1000 m changes by 9–24% for different vertical stabilities and ozone sensitivities. The impact of nocturnal vertical stability leads to 7–12% difference in O₃ concentration in the morning and ～0–2.5% in the afternoon.