An empirical model for predicting urban roadside nitrogen dioxide concentrations in the UK

An annual mean concentration of 40 μg m⁻³ has been proposed as a limit value within the European Union Air Quality Directives and as a provisional objective within the UK National Air Quality Strategy for 2010 and 2005, respectively. Emissions reduction measures resulting from current national and international policies are likely to deliver significant reductions in emissions of oxides of nitrogen from road traffic in the near future. It is likely that there will still be exceedances of this target value in 2005 and in 2009 if national measures are considered in isolation, particularly at the roadside. It is envisaged that this `policy gap’ will be addressed by implementing local air quality management to reduce concentrations in locations that are at risk of exceeding the objective. Maps of estimated annual mean NO₂ concentrations in both urban background and roadside locations are a valuable resource for the development of UK air quality policy and for the identification of locations at which local air quality management measures may be required. Maps of annual mean NO₂ concentrations at both background and roadside locations for 1998 have been calculated using modelling methods, which make use of four mathematically straightforward, empirically derived linear relationships. Maps of projected concentrations in 2005 and 2009 have also been calculated using an illustrative emissions scenario. For this emissions scenario, annual mean urban background NO₂ concentrations in 2005 are likely to be below 40 μg m⁻³, in all areas except for inner London, where current national and international policies are expected to lead to concentrations in the range 40–41 μg m⁻³. Reductions in NO_x emissions between 2005 and 2009 are expected to reduce background concentrations to the extent that our modelling results indicate that 40 μg m⁻³ is unlikely to be exceeded in background locations by 2009. Roadside NO₂ concentrations in urban areas in 2005 and 2009 are expected to be significantly higher than in background locations. 21% of urban major road links are expected to have roadside NO₂ greater than or equal to 40 μg m⁻³ in 2005 for our illustrative emissions scenario. The continuing downward trend in traffic emissions is likely to further reduce the number of links exceeding this value by 2009, with about 6% of urban major road links predicted to have concentrations higher than 40 μg m⁻³. The majority of these links are in the London area. The remaining links are generally confined to the most heavily trafficked roads in other big cities.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Measurements of nitrogen dioxide on Funen using diffusion tubes

Monitoring of nitrogen dioxide (NO₂) by passive sampling on the Danish island Funen (Fyn) show that the concentration of nitrogen dioxide is low (2–20 ppb). The level of NO₂ in rural and suburban areas is governed by imported airpollution, and elevated NO₂ concentrations due to local traffic are of limited importance. These results are supported by diffusion denuder measurements of nitric acid (HNO₃) and particulate nitrate. Measurements of NO₂ with chemiluminescence and diffusive passive sampling showed good agreement between the methods. The special mounting device for the diffusive samplers used in this work seem to have reduced the turbulence at the open end of the tube. The product from the reaction between nitrogen dioxide and triethanolamine was investigated and tentatively identified as triethanolamine N-oxide, which is in accordance with the observed 1 : 1 stoechiometry in the conversion of NO₂ to nitrite ions.     

Assessment of air quality benefits from national air pollution control policies in China. Part II: Evaluation of air quality predictions and air quality benefits assessment

Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM_2.5, particles with aerodiameter less than or equal to 2.5 μm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO₂) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality.The air quality improvement that would result from the targeted sulfur dioxide (SO₂) and nitrogen oxides (NO_x) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO₂ concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30–60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM_2.5 can also decline by 3–15 μg m^?3 (4–25%) due to the lower SO₂ and sulfate concentrations. If similar controls are implemented for NO_x emissions, NO_x concentrations are estimated to decrease by 30–60% as compared with the 2010 BAU scenario. The annual mean PM_2.5 concentrations will also decline by 2–14 μg m^?3 (3–12%). In addition, the number of ozone (O₃) non-attainment areas in the northern China is projected to be much lower, with the maximum 1-h average O₃ concentrations in the summer reduced by 8–30 ppb.     

Spatial distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

Aircraft measurements of O3, NOx,CO, VOCs,and SO2 in the Yangtze River Delta region

In this study, air pollutants, including ozone (O₃), nitrogen oxides (NO_x = NO + NO₂), carbon monoxides (CO), sulfur dioxide (SO₂), and volatile organic compounds (VOCs) measured in the Yangtze River Delta (YRD) region during several air flights between September/30 and October/11 are analyzed. This measurement provides horizontal and vertical distributions of air pollutants in the YRD region. The analysis of the result shows that the measured O₃ concentrations range from 20 to 60 ppbv. These values are generally below the US national standard (84 ppbv), suggesting that at the present, the O₃ pollutions are modest in this region. The NO_x concentrations have strong spatial and temporal variations, ranging from 3 to 40 ppbv. The SO₂ concentrations also have large spatial and temporal variations, ranging from 1 to 35 ppbv. The high concentrations of CO are measured with small variations, ranging from 3 to 7 ppmv. The concentrations of VOCs are relatively low, with the total VOC concentrations of less than 6 ppbv. The relative small VOC concentrations and the relative large NO_x concentrations suggest that the O₃ chemical formation is under a strong VOC-limited regime in the YRD region. The measured O₃ and NO_x concentrations are strongly anti-correlated, indicating that enhancement in NO_x concentrations leads to decrease in O₃ concentrations. Moreover, the O₃ concentrations are more sensitive to NO_x concentrations in the rural region than in the city region. The ratios of Δ[O₃]/Δ[NO_x] are ?2.3 and ?0.25 in the rural and in the city region, respectively. In addition, the measured NO_x and SO₂ concentrations are strongly correlated, highlighting that the NO_x and SO₂ are probably originated from same emission sources. Because SO₂ emissions are significantly originated from coal burnings, the strong correlation between SO₂ and NO_x concentrations suggests that the NO_x emission sources are mostly from coal burned sources. As a result, the future automobile increases could lead to rapid enhancements in O₃ concentrations in the YRD region.     

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

Application of a Lagrangian particle model to assess the impact of harbour,industrial and urban activities on air quality in the Taranto area,Italy

This paper evaluates the relative impact on air quality of harbour emissions, with respect to other emission sources located in the same area. The impact assessment study was conducted in the city of Taranto, Italy. This area was considered as representative of a typical Mediterranean harbour region, where shipping, industries and urban activities co-exist at a short distance, producing an ideal case to study the interaction among these different sources. Chemical and meteorological field campaigns were carried out to provide data to this study. An emission inventory has been developed taking into account industrial sources, traffic, domestic heating, fugitive and harbour emissions. A 3D Lagrangian particle dispersion model (SPRAY) has then been applied to the study area using reconstructed meteorological fields calculated by the diagnostic meteorological model MINERVE. 3D short term hourly concentrations have been computed for both all and specific sources. Industrial activities are found to be the main contributor to SO₂. Industry and traffic emissions are mainly responsible for NO_x simulated concentrations. CO concentrations are found to be mainly related to traffic emissions, while primary PM₁₀ simulated concentrations tend to be linked to industrial and fugitive emissions. Contributions of harbour activities to the seasonal average concentrations of SO₂ and NO_x are predicted to be up to 5 and 30 μg m⁻³, respectively to be compared to a overall peak values of 60 μg m⁻³ for SO₂ and 70 μg m⁻³ for NO_x. At selected urban monitoring stations, SO₂ and NO_x average source contributions are predicted to be both of about 9% from harbour activities, while 87% and 41% respectively of total concentrations are predicted to be of industrial origin.     

Modelling of indoor exposure to nitrogen dioxide in the UK

A dynamic multi-compartment computer model has been developed to describe the physical processes determining indoor pollutant concentrations as a function of outdoor concentrations, indoor emission rates and building characteristics. The model has been parameterised for typical UK homes and workplaces and linked to a time-activity model to calculate exposures for a representative homemaker, schoolchild and office worker, with respect to NO₂. The estimates of population exposures, for selected urban and rural sites, are expressed in terms of annual means and frequency of hours in which air quality standards are exceeded. The annual mean exposures are estimated to fall within the range of 5–21 ppb for homes with no source, and 21–27 ppb for homes with gas cooking, varying across sites and population groups. The contribution of outdoor exposure to annual mean NO₂ exposure varied from 5 to 24%, that of indoor penetration of outdoor air from 17 to 86% and that of gas cooking from 0 to 78%. The frequency of exposure to 1 h mean concentrations above 150 ppb was very low, except for people cooking with gas.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Atmospheric deposition of nitrogen emitted in the Metropolitan Area of Buenos Aires to coastal waters of de la Plata River

The Metropolitan Area of Buenos Aires (MABA) is the third mega-city in Latin America. Atmospheric N emitted in the area deposits to coastal waters of de la Plata River. This study describes the parameterizations included in DAUMOD-RD (v.3) model to evaluate concentrations of nitrogen compounds (nitrogen dioxide, gaseous nitric acid and nitrate aerosol) and their total (dry and wet) deposition to a water surface. This model is applied to area sources and CALPUFF model to point sources of NO_x in the MABA. The models are run for 3 years of hourly meteorological data, with a spatial resolution of 1 km². Mean annual deposition is 69, 728 kg-N year^?1 over 2 339 km² of river. Dry deposition contributions of N-NO₂, N-HNO₃ and N-NO₃^? to this value are 44%, 22% and 20%, respectively. Wet deposition of N-HNO₃ and N-NO₃^? represents 3% and 11% of total annual value, respectively. This very low contribution results from the rare occurrence of rainy hours with wind blowing from the city to the river. Monthly dry deposition flux estimated for coastal waters of MABA varies between 7 and 13 kg-N km^?2 month^?1. These results are comparable to values reported for other coastal zones in the world.     

Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

Historical changes in atmospheric nitrogen deposition to Cape Cod,Massachusetts, USA

We reconstructed the historical trends in atmospheric deposition of nitrogen to Cape Cod, Massachusetts, from 1910 to 1995 by compiling data from literature sources, and adjusting the data for geographical and methodological differences. The reconstructed data suggest that NO₃-N wet deposition to this region increased from a low of 0.9 kg N ha⁻¹ yr⁻¹ in 1925 to a high of approximately 4 kg N ha⁻¹ yr⁻¹ around 1980. The trend in NO₃-N deposition has remained since the early 1980s at around 3.6 kg N ha⁻¹ yr⁻¹. In contrast, NH₄-N wet deposition decreased from more than 4 kg N ha⁻¹ yr⁻¹ in the mid 1920s to about 1.5 kg N ha⁻¹ yr⁻¹ from the late-1940s until today. Emissions of NO_x-N in the Cape Cod airshed increased at a rate of 2.1 kg N ha⁻¹ per decade since 1910, a rate that is an order of magnitude higher than NO₃-N deposition. Estimates of NH₃ emissions to the northeast United States and Canada have decreased slightly throughout the century, but the decrease in reconstructed N-NH₄⁺ deposition rates does not parallel emissions estimates. The trend in reconstructed total nitrogen deposition suggests an overall increase through the century at a rate of 0.26 kg N ha⁻¹ per decade. This overall increase in deposition may expose coastal forests to rates of nitrogen addition that, if exceeded, could induce nitrogen saturation and increase nitrogen loads to adjoining estuaries.     

Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.     

Statistical and diagnostic evaluation of a new-generation urban dispersion modelling system against an extensive dataset in the Helsinki area

We have developed a modelling system for predicting the traffic volumes, emissions from stationary and vehicular sources, and atmospheric dispersion of pollution in an urban area. This paper describes a comparison of the NO_x and NO₂ concentrations predicted using this modelling system with the results of an urban air quality monitoring network. We performed a statistical analysis to determine the agreement between predicted and measured hourly time series of concentrations at four permanently located and three mobile monitoring stations in the Helsinki Metropolitan Area in 1996–1997 (at a total of ten urban and suburban measurement locations). At the stations considered, the so-called index of agreement values of the predicted and measured time series of the NO₂ concentrations vary between 0.65 and 0.82, while the fractional bias values range from −0.29 to +0.26. In comparison with corresponding results presented in the literature, the agreement between the measured and predicted datasets is good, as indicated by these statistical parameters. The seasonal variations of the NO₂ concentrations were analysed in terms of the relevant meteorological parameters. We also analysed the difference between model predictions and measured data diagnostically, in terms of meteorological parameters, including wind speed and direction (the latter separately for two wind speed classes), atmospheric stability and ambient temperature, at two monitoring stations in central Helsinki. The modelling system tends to overpredict the measured NO₂ concentrations both at the highest (u⩾6 m s⁻¹) and at the lowest wind speeds (u<2 m s⁻¹). For higher wind speeds, the modelling system overpredicts the measured NO₂ concentrations in certain wind direction intervals; specific ranges were found for both monitoring stations considered. The modelling system tends to underpredict the measured concentrations in convective atmospheric conditions, and overpredict in stable conditions. The possible physico-chemical reasons for these differences are discussed.     

Using NOx and CO monitoring data to indicate fine aerosol number concentrations and emission factors in three UK conurbations

It is increasingly accepted that although exposure to elevated concentrations of PM₁₀ is associated with an increased risk of mortality and morbidity, the relationship may not be causal. Rather, there is evidence that number concentrations may be a more appropriate metric than mass concentrations in evaluating health risk. Number concentrations are not routinely monitored and spatial and temporal patterns are poorly quantified. CO and NO_x are co-pollutants with their major urban source in common with fine particles, i.e. road vehicle emissions; are routinely monitored in many cities and are also related to ill health. Datasets of particle number concentration measurements from approximately month-long field campaigns in Manchester, Edinburgh and Birmingham (UK) are compared with simultaneous concentrations of CO and NO_x from nearby fixed monitors. It was found that it might be possible to reliably predict particle number concentrations (diameters>100 nm) on an hourly basis in Manchester city centre from knowledge of NO_x or CO concentrations alone. The influences of meteorology, spatial variability in emissions and lack of co-location upon the correlations are investigated using cluster analysis. The cluster analysis revealed that these relationships may vary between cities and are dependent upon monitor location but in ways that can be ascribed. For two out of three sites there existed a linear relationship between average cluster aerosol and gas concentrations. This indicates that although airmass aging disrupts the short-term linear relationship, the relationship in the average survives. An emission ratio of particles (approx. 100–500 nm diameter) to NO_x of approximately 50 cm⁻³ ppb⁻¹ was estimated in Manchester and Birmingham. Particle mass spectrometry measurements indicated that organic compounds dominated these particles and an emission rate of 0.58 ton km⁻² a⁻¹ of organic particulate matter from road transport has been estimated for the Greater Manchester conurbation.     

An empirical approach for the prediction of annual mean nitrogen dioxide concentrations in London

Annual mean limits for NO₂ concentrations have been set in the European Union, which will be most challenging to meet in large urban conurbations. In this paper, we discuss techniques that have been developed to predict current and future NO₂ concentrations in London, utilising ambient data. Hourly average NO_x (NO+NO₂) and NO₂ concentrations are used to calculate NO_x frequency distributions. By defining relationships between the annual mean NO_x and NO₂ at different sites, it is possible to investigate different NO_x reduction strategies. The application of the frequency distribution approach to monitoring sites in London shows that given the likely change in emissions by 2005, it is unlikely that much of central and inner London will meet the objective. The approaches used suggest that meeting the objective in central London will be the most challenging for policy makers requiring NO_x concentrations as low as 30 ppb, compared with values closer to 36–40 ppb for outer London. Predictions for 2005 indicate that concentrations of NO₂ up to 6 ppb in excess of the objective are likely in central London.     

A new measurement method for nitrogen oxides in the air using an annular diffusion scrubber coated with titanium dioxide

A new convenient measurement method of nitrogen oxides (NO_x) in the ambient air was developed. The collection of NO_x is performed by an annular diffusion scrubber coated with a mixture of titanium dioxide (TiO₂) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) and the analysis is carried out by ion chromatography with conductivity detection. Under ultraviolet light (UV) illumination, TiO₂ produces reactive oxygen species such as super oxide (O₂⁻), hydroxyl radical (OH·) and peroxyhydroxyl radical (HO₂·), by which nitric oxide (NO) is oxidized to nitrogen dioxide (NO₂), and is further oxidized to nitric acid (HNO₃). The yielded HNO₃ and NO₂ are effectively adsorbed on the surface of TiO₂ and hydroxyapatite. The collection efficiencies of NO and NO₂ by the annular diffusion scrubber coated with the catalysts under UV illumination are higher than 98%, respectively, at the air flow rate of 0.2–1.0 l min⁻¹. After the collection of NO_x, by feeding deionized water into the annular diffusion scrubber, HNO₃ and NO₂ which adsorbed on the catalysts are extracted as forms of nitrite ion (NO₂⁻) and nitrate ion (NO₃⁻). The extraction efficiencies of NO and NO₂ are almost 100%. The activity of the washed catalysts can be completely recovered by drying with the purified air. Further, a simultaneous separated measurement of NO and NO₂ can be performed by utilizing the UV illumination dependence. This method was applied to the measurement of NO_x in the ambient air. The NO_x concentration measured by this method was in good agreement with that obtained using the chemiluminescence NO_x analyzer.     

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.     

Anthropogenic NOx emissions in Asia in the period 1990–2020

Nitrogen oxides emissions in Asia during the period 1990–2020 due to anthropogenic activity are presented. These estimates are based on the RAINS-ASIA methodology (Foell et al., 1995, Acid Rain and Emission Reduction in Asia, World Bank), which includes a dynamic model for energy forecasts, and information on 6 energy sectors and 9 fuel types. The energy forecasts are combined with process emission factors to yield NO_x emission estimates at the country level, the regional level, and on a 1 degree by 1 degree grid. In 1990 the total NO_x emissions are estimated to be ∼19 Tg NO₂, with China (43%), India (18%) and Japan (13%) accounting for 75% of the total. Emissions by fuel are dominated by burning of hard coal and emissions by economic activity are dominated by the power, transport, and industrial sectors. These new estimates of NO_x emissions are compared with those published by Hameed and Dignon (1988, Atmospheric Environment 22, 441–449) and Akimoto and Narita (1994, Atmospheric Environment 28, 213–225). Future emissions under a no-further-control scenario are also presented. During the period 1990–2020 the NO_x emissions increase by 350%, to ∼86 Tg NO₂. The increase in NO_x emissions by sector and end-use varies between countries, but in all countries this increase is strongest in the power and transport sectors. These results highlight the dynamic nature of energy use in Asia, and the need to take the rapid growth in NO_x emissions in Asia into account in studies of air pollution and atmospheric chemistry.