The impact of motor vehicle control technologies on future photochemical ozone formation in the United Kingdom

Legislation to control motor vehicle exhaust emissions has been introduced in the United Kingdom in stages since the early 1970s. Recently, a further step has been taken towards reducing future exhaust emissions of carbon monoxide, unburnt hydrocarbons and oxides of nitrogen in the 'Luxembourg agreement' (Lubinska, 1985). In this paper, the possible impact of these proposed controls on photochemical air pollution formation in the United Kingdom is investigated, including an evaluation of the relative merits of the two principal emission control options for petrol-driven cars: 'Lean Burn' engines and 'Catalyst' exhaust gas treatment.     

Verification of a source-oriented externally mixed air quality model during a severe photochemical smog episode

The CIT/UCD three-dimensional source-oriented externally mixed air quality model is tested during a severe photochemical smog episode (Los Angeles, 7–9 September 1993) using two different chemical mechanisms that describe the formation of ozone and secondary reaction products. The first chemical mechanism is the secondary organic aerosol mechanism (SOAM) that is based on SAPRC90 with extensions to describe the formation of condensable organic products. The second chemical mechanism is the caltech atmospheric chemistry mechanism (CACM) that is based on SAPRC99 with more detailed treatment of organic oxidation products.The predicted ozone concentrations from the CIT/UCD/SOAM and the CIT/UCD/CACM models agree well with the observations made at most monitoring sites with a mean normalized error of approximately 0.4–0.5. Good agreement is generally found between the predicted and measured NO_x concentrations except during morning rush hours of 6–10 am when NO_x concentrations are under-predicted at most locations. Total VOC concentrations predicted by the two chemical mechanisms agree reasonably well with the observations at three of the four sites where measurements were made. Gas-phase concentrations of phenolic compounds and benzaldehyde predicted by the UCD/CIT/CACM model are higher than the measured concentrations whereas the predicted concentrations of other aromatic compounds approximately agree with the measured values.The fine airborne particulate matter mass concentrations (PM_2.5) predicted by the UCD/CIT/SOAM and UCD/CIT/CACM models are slightly greater than the observed values during evening hours and lower than observed values during morning rush hours. The evening over-predictions are driven by an excess of nitrate, ammonium ion and sulfate. The UCD/CIT/CACM model predicts higher nighttime concentrations of gaseous precursors leading to the formation of particulate nitrate than the UCD/CIT/SOAM model. Elemental carbon and total organic mass are under-predicted by both models during morning rush hour periods. When this latter finding is combined with the NO_x under-predictions that occur at the same time, it suggests a systematic bias in the diesel engine emissions inventory. The mass of particulate total organic carbon is under-predicted by both the UCD/CIT/SOAM and UCD/CIT/CACM models during afternoon hours. Elemental carbon concentrations generally agree with the observations at this time. Both the UCD/CIT/SOAM and UCD/CIT/CACM models predict low concentrations of secondary organic aerosol (SOA) (<3.5 μg m⁻³) indicating that both models could be missing SOA formation pathways. The representation of the aerosol as an internal mixture vs. a source-oriented external mixture did not significantly affect the predicted concentrations during the current study.     

Measurements of gaseous hydrogen peroxide in southern England during a photochemical episode

Simultaneous measurements of gaseous hydrogen peroxide and ozone made in southern England are reported. The hydrogen peroxide measurements are the first reported for the United Kingdom and show clear diurnal trends and correlate with ozone measurements. Measurements were made during a photochemical episode when a peak hydrogen peroxide concentration of 2.5 microg m(-3) was recorded with a simultaneous peak of 168 microg m(-3) in the ozone concentration. From observations on the rate of decay in the measured concentrations, an evening-time deposition velocity of 0.28 cm s(-1) was derived for hydrogen peroxide.     

On the influence of meteorological input on photochemical modelling of a severe episode over a coastal area

The modelling reconstruction of the processes determining the transport and mixing of ozone and its precursors in complex terrain areas is a challenging task, particularly when local-scale circulations, such as sea breeze, take place. Within this frame, the ESCOMPTE European campaign took place in the vicinity of Marseille (south-east of France) in summer 2001. The main objectives of the field campaign were to document several photochemical episodes, as well as to constitute a detailed database for chemistry transport models intercomparison.CAMx model has been applied on the largest intense observation periods (IOP) (June 21–26, 2001) in order to evaluate the impacts of two state-of-the-art meteorological models, RAMS and MM5, on chemical model outputs. The meteorological models have been used as best as possible in analysis mode, thus allowing to identify the spread arising in pollutant concentrations as an indication of the intrinsic uncertainty associated to the meteorological input.Simulations have been deeply investigated and compared with a considerable subset of observations both at ground level and along vertical profiles. The analysis has shown that both models were able to reproduce the main circulation features of the IOP. The strongest discrepancies are confined to the Planetary Boundary Layer, consisting of a clear tendency to underestimate or overestimate wind speed over the whole domain.The photochemical simulations showed that variability in circulation intensity was crucial mainly for the representation of the ozone peaks and of the shape of ozone plumes at the ground that have been affected in the same way over the whole domain and all along the simulated period. As a consequence, such differences can be thought of as a possible indicator for the uncertainty related to the definition of meteorological fields in a complex terrain area.     

A comparison of measured and simulated ozone concentrations in the rural areas of the eastern United States during summer 1995

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP). The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

A comparison of two different approaches for mapping potential ozone damage to vegetation. A model study

Two very different types of approaches are currently in use today for indicating risk of ozone damage to vegetation in Europe. One approach is the so-called AOTX (accumulated exposure over threshold of Xppb) index, which is based upon ozone concentrations only. The second type of approach entails an estimate of the amount of ozone entering via the stomates of vegetation, the AFstY approach (accumulated stomatal flux over threshold of Y nmol m(-2) s(-1)). The EMEP chemical transport model is used to map these different indicators of ozone damage across Europe, for two illustrative vegetation types, wheat and beech forests. The results show that exceedences of critical levels for either type of indicator are widespread, but that the indicators give very different spatial patterns across Europe. Model simulations for year 2020 scenarios suggest reductions in risks of vegetation damage whichever indicator is used, but suggest that AOT40 is much more sensitive to emission control than AFstY values.     

A simple semi-empirical photochemical model for the simulation of ozone concentration in the Seoul metropolitan area in Korea

O₃ concentrations were simulated over the Seoul metropolitan area in Korea using a simple semi-empirical reaction (SEGRS) model which consists of generic reaction set (GRS), photochemical reaction set, and the diagnostic wind field generation model. The aggregated VOC emission strength was empirically scaled by the comparison of the simulated slope of (O₃–2NO–NO₂) concentration as a function of cumulative actinic light flux against measurements on high surface ozone concentration days with the relatively weak easterly geostrophic winds at the 850 hPa level in summer when the effect of horizontal advection was fairly small. The results indicated that the spatial distribution patterns and temporal variations of spatially averaged ground-level ozone concentrations were quite well simulated compared with those of observations with the modified volatile organic compound (VOC) emission strength. The diurnal trend of the surface ozone concentration and the maximum concentration compared observations were also quite reasonably simulated. However, the maximum ozone concentration occurring time at Seoul lagged about 2 h and the ozone concentration in the suburban area was slightly overestimated in the afternoon due to the influx of high ozone concentration from the urban area. It was found that the SEGRS model could be effectively used to simulate or predict the ground-level ozone concentration reasonably well without heavy computational cost provided the emission of ozone precursors are given.     

A comparison of simulated and observed ozone mixing ratios for the summer of 1998 in Western Europe

This study describes and evaluates the newly developed European scale Eulerian chemistry transport model CHIMERE-continental. The model is designed for seasonal simulations and real time forecasts without the use of super-computers. For the purpose of model evaluation simulated ozone mixing ratios for the period between 1 May 1998 and 30 September 1998 are compared to observational data from 115 European surface sites. In order to facilitate the interpretation of future forecasts a statistic is established to estimate the reliability of a simulated pollution level. Besides this, the comparison is done by means of time series, scatter plots, a spectral analysis and the calculation of RMS-errors and biases of the model results corresponding to each observation site. It turns out that the mean RMS-error of the simulated daily maximum ozone mixing ratio for the sites considered a priori as well suited for a model comparison is about 10 ppb. For the same period but a reduced number of sites observed concentrations of NO₂ and ethene are compared to simulated values. Difficulties encountered with the representativeness of observations when trying to evaluate a mesoscale air pollution model are discussed.     

夏秋季节焦化厂附近大气中臭氧及其前体物变化特征和臭氧生成潜势分析

2012年6—10月,在我国北方某焦化厂厂界附近开展了O3、NO x、CO体积分数在线监测及VOCs样品采集分析工作,获得了夏、秋两季焦化厂厂界O3及其前体物的体积分数及其日变化趋势。焦化厂厂界附近O3、NO、CO体积分数均呈单峰型日变化,O3体积分数的季节差异不明显,夏季仅略高于秋季,而NO、CO体积分数秋季高于夏季,作为二次反应产物的NO2,其变化幅度秋季比夏季强烈。夏季TVOCs在各监测时段的小时体积分数呈现先上升后下降的日变化趋势,而秋季则呈现逐渐下降的日变化趋势。由较小VOCs/NO x的比值可初步判断,该焦化厂所在区域的大气光化学臭氧生成潜势处于VOCs控制区。在焦化厂下风向厂界附近,夏、秋两季TVOCs平均体积分数分别为(43.8±45.0)×10-9和(26.7±29.6)×10-9,苯系物、烷烃、烯烃的平均体积分数分别为(34.3±28.1)×10-9和(14.4±14.8)×10-9、(5.3±11.8)×10-9和(7.0±7.7)×10-9、(4.3±5.0)×10-9和(5.3±7.1)×10-9。夏、秋两季焦化厂附近臭氧生成潜势贡献最大的是苯系物(47.6%~65.8%),其次是烯烃(28.0%~41.9%),再次是烷烃(6.3%~10.5%)。     

Process analysis of a regional air pollution episode over Pearl River Delta Region,China, using the MM5-CMAQ model

This study focuses on the influences of a warm high-pressure meteorological system on aerosol pollutants, employing the simulations by the Models-3/CMAQ system and the observations collected during October 10–12, 2004, over the Pearl River Delta (PRD) region. The results show that the spatial distributions of air pollutants are generally circular near Guangzhou and Foshan, which are cities with high emissions rates. The primary pollutant is particulate matter (PM) over the PRD. MM5 shows reasonable performance for major meteorological variables (i.e., temperature, relative humidity, wind direction) with normalized mean biases (NMB) of 4.5–38.8% and for their time series. CMAQ can capture one peak of all air pollutant concentrations on October 11, but misses other peaks. The CMAQ model systematically underpredicts the mass concentrations of all air pollutants. Compared with chemical observations, SO₂ and O₃ are predicted well with a correlation coefficient of 0.70 and 0.65. PM_2.5 and NO are significantly underpredicted with an NMB of 43% and 90%, respectively. The process analysis results show that the emission, dry deposition, horizontal transport, and vertical transport are four main processes affecting air pollutants. The contributions of each physical process are different for the various pollutants. The most important process for PM₁₀ is dry deposition, and for NO_x it is transport. The contributions of horizontal and vertical transport processes vary during the period, but these two processes mostly contribute to the removal of air pollutants at Guangzhou city, whose emissions are high. For this high-pressure case, the contributions of the various processes show high correlations in cities with the similar geographical attributes. According to the statistical results, cities in the PRD region are divided into four groups with different features. The contributions from local and nonlocal emission sources are discussed in different groups.

Implications: The characteristics of aerosol pollution episodes are intensively studied in this work using the high-resolution modeling system MM5/SMOKE/CMAQ, with special efforts on examining the contributions of different physical and chemical processes to air concentrations for each city over the PRD region by a process analysis method, so as to provide a scientific basis for understanding the formation mechanism of regional aerosol pollution under the high-pressure system over PRD.     

Interannual variation in meteorologically adjusted ozone levels in the eastern United States: A comparison of two approaches

Assessing the influence of abatement efforts and other human activities on ozone levels is complicated by the atmosphere's changeable nature. Two statistical methods, the dynamic linear model (DLM) and the generalized additive model (GAM), are used to estimate ozone trends in the eastern United States and to adjust for meteorological effects. The techniques and resulting estimates are compared and contrasted for four monitoring locations chosen through principal components analysis to represent regional patterns of ozone concentrations. After adjustment for meteorological influence, overall downward trends are evident at all four locations from 1997 to 2004. The results indicate that the two methods’ estimates of ozone changes agree well. When such estimates are needed quickly, or when many similar, but separate analyses are required, the ease of implementation and relative simplicity of the GAMs are attractive. The DLMs are much more flexible, readily addressing such issues as autocorrelation, the presence of missing values, and estimation of long-term trends or cyclical patterns. Implementation of DLMs, however, is typically more difficult, and especially in the absence of an experienced practitioner, they may be better reserved for in-depth analyses.     

Evaluation of near surface ozone in air quality simulations forced by a regional climate model over Europe for the period 1991–2000

This study aims to evaluate near surface ozone simulated with the modelling system RegCM3/CAMx against ozone measurements from the EMEP database for the recent decade 1991–2000. The RegCM3/CAMx simulations were performed on a 50 km × 50 km grid over Europe driven either by ERA-40 reanalysis (hereafter referred as ERA simulation) or the global circulation model (GCM) ECHAM5 (hereafter referred as ECHAM simulation). A set of statistical metrics is used for the model evaluation, including temporal correlation coefficient, the ratio of the standard deviations and the bias of simulated versus observed values. Overall, a good agreement is found for both ERA and ECHAM simulations at the majority of the selected EMEP stations in all metrics throughout the year based either on monthly or daily ozone values. Based on these results, it is assessed that the modelling system RegCM3/CAMx is suitable to be used for present and future regional climate-air quality simulations with emphasis on near surface ozone. The ERA simulations reproduce more accurately the observed ozone values in comparison to ECHAM simulations because the meteorology of the ERA experiment is closer to real atmospheric conditions than the GCM based experiment. On a seasonal basis, both ERA and ECHAM simulations exhibit a seasonally dependent bias, with winter and spring ozone values being generally under-estimated by the model and summer and autumn values being slightly overestimated. This seasonally dependent bias is also evident from median and peak midday ozone values. However, the highest observed midday ozone peaks in summer, with values higher than 80 ppbv, could not be captured either by ERA or ECHAM simulations. An analysis of day-time and night-time ERA and ECHAM modelled ozone values shows that CAMx performs better during the day-time.     

Estimating the ozone formation potential of volatile aromatic compounds in vehicle tunnels.

Two vehicle tunnels located in the Taipei area were selected to study the ozone formation potential of volatile aromatic compounds (VACs). Air samples in the two tunnels were collected using canisters. Analysis of VACs was conducted with a gas chromatograph equipped with a mass spectrometer. The total VOCs concentrations in Zefun tunnel ranged from 483.5 to 1032.2 (micrograms/m3) which increased with the increase in traffic volume. In the Lishin tunnel, the total VACs concentration ranged from 356.6 to 1961.3 (micrograms/m3) which was not well correlated with the traffic volume. The most predominant VACs in these vehicle tunnels were toluene and xylenes. Although the traffic volume and types of vehicles were not exactly the same, the characteristic ratios of the VACs concentrations were found to be similar. These results indicated that the existence of a specific characteristic ratio of VAC concentration was affected by the mobile sources. The maximum ozone formation potential resulted from the vehicles in the Lishin motorcycle tunnel which had higher values than the Zefun tunnel and much higher than the SPECIATE databases in the US via weighting the maximum incremental reactivity (MIR) scale.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

Effects of land use data on dry deposition in a regional photochemical model for eastern Texas

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O3 mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O3 decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O3 mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O3 mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O3 mixing ratios of approximately 2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

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.     

Development of a regional oxidant model and application to the northeastern United States

Elevated oxidant concentrations due to the long-range transport of ozone and its precursors have been observed in many rural areas in the continental United States. The oxidation processes associated with ozone formation in the atmosphere have many important implications for regional air quality problems, such as regional haze and acid deposition. This paper describes the development and evaluation of a mesoscale photochemical air quality simulation model (RTM-III) covering the northeastern United States. The model considers an area 2080 km in the E-W direction by 1840 km in the N-S direction, with a spatial resolution on the order of 80 x 80 km, and a temporal resolution on the order of one hour. Data collected during an episode in July 1978 by the EPRI Sulfate Regional Experiment is used for testing and evaluating the model. In a comparison of hourly predictions with observations, the model predictions, with a few exceptions where local influences are suspected, generally track the measured spatial pattern and diurnal variation of ozone concentrations quite well. The correlation coefficient matched by time and location over more than 1500 pairs of hourly predicted and observed ozone concentrations is 0.7.