Photochemical dispersion modeling: Review of model concepts and applications studies

Over the last decade, the development and application of sophisticated atmospheric models that simulate the transport and dispersion of ozone and its precursors have advanced rapidly. Further advancements are most likely to be found in more complete temporal and spatial characterization of photochemical smog formation processes via measurement. This paper provides an overview of the development of atmospheric photochemical dispersion models, first discussing in general terms the various physical processes occurring in the atmosphere that govern the formation, transport, and ultimate fate of ozone. Procedures for representing these physical processes in mathematical terms are presented next. Nearly all of the photochemical models in use today are derived from the semiempirical atmospheric diffusion equation, though theoretical formulations vary depending on which of the various terms in the pollutant mass balance equation are deemed significant for the application at hand. Examples of recent applications of the range of available photochemical model are presented, together with estimates of the accuracy of each generic modeling concept. Several topics warranting future research are identified, including the need to incorporate explicitly more of the stochastic (or probabilistic) nature of the atmosphere into the form of current photochemical model predictions (i.e., estimates of the variance and higher order moments of the predicted concentration distribution).     

A preliminary study of ozone trend and its impact on environment in Hong Kong

As far as the impact of air pollutants on human health being is concerned, ozone (O3) is one of the most pollutant sources, and, in particular, the ground level ozone is responsible for a variety of adverse effects on both human being and plant life. To protect the population from such adverse health effects, early information and precautions about the high ozone level need to be ascertained. In this study, statistical characteristics of ground level ozone is analyzed according to field monitoring data in mixed residential, commercial and industrial areas, e.g., Tsuen Wan area in Hong Kong. The study deals with the characteristics of hourly and daily mean ozone levels under different climatic conditions such as temperature, solar radiation (SR), wind speed (WS), and other pollutant concentration levels. The study aims to investigate the importance of meteorological factors and their impact on relevant pollutant concentration levels from a chemical aspect. Further, reasons for the spatial and temporal variation of ozone levels are discussed. All these results will provide a physical basis for accurately predicting ozone concentration in similar research.     

Prediction of maximum daily ozone level using combined neural network and statistical characteristics

Analysis and forecasting of air quality parameters are important topics of atmospheric and environmental research today due to the health impact caused by air pollution. As one of major pollutants, ozone, especially ground level ozone, is responsible for various adverse effects on both human being and foliage. Therefore, prediction of ambient ozone levels in certain environment, especially the ground ozone level in densely urban areas, is of great importance to urban air quality and city image. To date, though several ozone prediction models have been established, there is still a need for more accurate models to develop effective warning strategies. The development of such models is difficult because the meteorological variables and the photochemical reactions involved in ozone formation are very complex. The present work aims to develop an improved neural network model, which combines the adaptive radial basis function (ARBF) network with statistical characteristics of ozone in selected specific areas, and is used to predict the daily maximum ozone concentration level. The improved method is trained and testified by hourly time series data collected at three air pollutant-monitoring stations in Hong Kong during 1999 and 2000. The simulation results demonstrate the effectiveness and the reliability of the proposed method.     

Photochemical smog effects in mixed conifer forests along a natural gradient of ozone and nitrogen deposition in the San Bernardino Mountains

Toxic effects of photochemical smog on ponderosa and Jeffrey pines in the San Bernardino Mountains were discovered in the 1950s. It was revealed that ozone is the main cause of foliar injury manifested as chlorotic mottle and premature needle senescence. Various morphological, physiological and biochemical alterations in the affected plants have been reported over a period of about 40 years of multidisciplinary research. Recently, the focus of research has shifted from studying the effects of ozone to multiple pollutant effects. Recent studies have indicated that the combination of ozone and nitrogen may alter biomass allocation in pines towards that of deciduous trees, accelerate litter accumulation, and increase carbon sequestration rates in heavily polluted forests. Further study of the effects of multiple pollutants, and their long-term consequences on the mixed conifer ecosystem, cannot be adequately done using the original San Bernardino Mountains Air Pollution Gradient network. To correct deficiencies in the design, the new site network is being configured for long-term studies on multiple air pollutant concentrations and deposition, physiological and biochemical changes in trees, growth and composition of over-story species, biogeochemical cycling including carbon cycling and sequestration, water quality, and biodiversity of forest ecosystems. Eleven sites have been re-established. A comparison of 1974 stand composition with data from 2000 stand composition indicate that significant changes in species composition have occurred at some sites with less change at other sites. Moist, high-pollution sites have experienced the greatest amount of forest change, while dryer low-pollution sites have experienced the least amount of stand change. In general, ponderosa pine had the lowest basal area increases and the highest mortality across the San Bernardino Mountains.     

Calculation of the depletion of airborne pollutant plumes through dry deposition processes

The depletion of airborne pollutant plumes resulting from dry deposition on ground surfaces should be taken into account when estimating pollutant concentrations in air at distances downwind from their sources. This can be done by using a reduced release rate instead of the actual release rate for the pollutant in atmospheric dispersion equations. The reduced release rate is the actual rate of release multiplied by a depletion fraction. Depletion fractions for use with the Gaussian atmospheric dispersion equation of Pasquill and Gifford were calculated by numerical integration for downwind distances ranging from 35 to 90 000 m for release heights from 1 to 400 m, and they are tabulated for convenient interpolation for intermediate values of distance and release height. Pasquill atmospheric stability categories A-G are included. The listed values are for a deposition velocity of 0.01 m/s and a wind speed of 1 m/s but can be easily converted to apply to other deposition velocities and wind speeds. The tabulated values may be applied for downwind distances close enough to the point of release that the Gaussian model may be assumed to be realistic and where the vertical dispersion of the plume has not yet been significantly affected by the overlying atmospheric lid.     

Air pollution in the semitropical Saudi urban area

This paper presents the outcome of research conducted in the city of Jeddah, Saudi Arabia. Analysis of recorded meteorological elements shows that the atmosphere of the area favors the accumulation of air pollutants. Dustfall rates were measured at 22 stations in different districts. High rates of dustfall were found in all districts, with maximum recorded values in central urban and industrial districts. Collected samples were analyzed to determine the causes of these excessive precipitations. Suspended particulate matter and other pollutants were found to exceed air quality standards set to meet environmental requirements. Carbon monoxide was found to exceed the air quality standard of 9 μL/L. Concentrations of photochemical oxidants indicated the possibility of Los Angeles-type photochemical smog formation. Geographic distribution of pollutant concentrations and chemical constituents of particulates were found to be influenced by both manmade and natural causes. Results are discussed and several conclusions are given.     

High-resolution spatial analysis of stomatal ozone uptake in arable crops and pastures

Ozone effects on plants depend on atmospheric transport and stomatal uptake. Thus, ozone-risk assessments should use measured ozone concentrations and account for the influence of atmospheric conditions and soil moisture on stomatal and nonstomatal ozone deposition. This requires disaggregated data for the physical input parameters and species-specific data for specific stomatal conductance (g(s)). In this study, an approach was developed based on a resistance analogue transport model. This model requires interpolated routine-measuring data for ozone concentration at 3-5 m height, wind speed, precipitation, and soil moisture content as inputs to estimate the amount of ozone taken up by wheat (Triticum aestivum) and grass/clover pastures with a 1x1-km resolution. The model was applied to the area under agricultural production in Switzerland. Using data for June 1994, the calculations revealed that the median of the distribution of stomatal ozone uptake was 88% higher in wheat compared to grassland. This was mainly due to the higher maximum stomatal conductance in wheat. Because ozone flux to soil and to external plant surfaces was comparable in both vegetation types, the difference in the stomatal fluxes was mainly responsible for distinct differences in flux partitioning. In both cases, only about 11% of the total cumulative flux was absorbed by external plant surfaces, whereas the soil was a strong sink responsible for as much as 50% of the total flux into grasslands. The higher-ozone flux to wheat resulted in clearly lower-ozone concentrations at canopy height, but no significant correlation between cumulative canopy-level ozone exposure, expressed as accumulated exposure above 40 ppb (AOT40), and stomatal uptake was found. Thus, to estimate the ozone risk for crops using a flux-based approach may lead to results that differ substantially from those obtained with a concentration-based approach.     

Ecological issues related to ozone: agricultural issues

Research on the effects of ozone on agricultural crops and agro-ecosystems is needed for the development of regional emission reduction strategies, to underpin practical recommendations aiming to increase the sustainability of agricultural land management in a changing environment, and to secure food supply in regions with rapidly growing populations. Major limitations in current knowledge exist in several areas: (1) Modelling of ozone transfer and specifically stomatal ozone uptake under variable environmental conditions, using robust and well-validated dynamic models that can be linked to large-scale photochemical models lack coverage. (2) Processes involved in the initial reactions of ozone with extracellular and cellular components after entry through the stomata, and identification of key chemical species and their role in detoxification require additional study. (3) Scaling the effects from the level of individual cells to the whole-plant requires, for instance, a better understanding of the effects of ozone on carbon transport within the plant. (4) Implications of long-term ozone effects on community and whole-ecosystem level processes, with an emphasis on crop quality, element cycling and carbon sequestration, and biodiversity of pastures and rangelands require renewed efforts.The UNECE Convention on Long Range Trans-boundary Air Pollution shows, for example, that policy decisions may require the use of integrated assessment models. These models depend on quantitative exposure-response information to link quantitative effects at each level of organization to an effective ozone dose (i.e., the balance between the rate of ozone uptake by the foliage and the rate of ozone detoxification). In order to be effective in a policy, or technological context, results from future research must be funnelled into an appropriate knowledge transfer scheme. This requires data synthesis, up-scaling, and spatial aggregation. At the research level, interactions must be considered between the effects of ozone and factors that are either directly manipulated by man through crop management, or indirectly changed. The latter include elevated atmospheric CO(2), particulate matter, other pollutants such as nitrogen oxides, UV-B radiation, climate and associated soil moisture conditions.     

A new conceptual model for quantifying transboundary contribution of atmospheric pollutants in the East Asian Pacific rim region

Transboundary transport of air pollution is a serious environmental concern as pollutant affects both human health and the environment. Many numerical approaches have been utilized to quantify the amounts of pollutants transported to receptor regions, based on emission inventories from possible source regions. However, sparse temporal–spatial observational data and uncertainty in emission inventories might make the transboundary transport contribution difficult to estimate. This study presents a conceptual quantitative approach that uses transport pathway classification in combination with curve fitting models to simulate an air pollutant concentration baseline for pollution background concentrations. This approach is used to investigate the transboundary transport contribution of atmospheric pollutants to a metropolitan area in the East Asian Pacific rim region. Trajectory analysis categorized pollution sources for the study area into three regions: East Asia, Southeast Asia, and Taiwan cities. The occurrence frequency and transboundary contribution results suggest the predominant source region is the East Asian continent. This study also presents an application to evaluate heavy pollution cases for health concerns. This new baseline construction model provides a useful tool for the study of the contribution of transboundary pollution delivered to receptors, especially for areas deficient in emission inventories and regulatory monitoring data for harmful air pollutants.     

Health effects of oxidants

Oxidants of significance to human health include ozone, nitrogen dioxide, and peroxyacetylnitrate. All of these compounds are involved in complex photochemical reactions which makes quantification and prediction of their individual health effects difficult. Ozone causes trauma to lung tissues and interferes with enzyme systems in the lungs and other tissues causing a broad range of symptoms. Measurable health impacts can occur at concentrations as low as 390 μg/m³. Acute effects of ozone exposure are reversible at normal urban concentrations (80–120 μg/m³). A special problem of concern, however, is increased susceptibility to infectious diseases contracted through the lungs. Nitrogen dioxide also causes trauma to lung tissues and interferes with enzyme systems. Measurable impacts can occur at concentrations as low as 100 μg/m³, but recovery is rapid and it is not known whether repeated exposures at this level have cumulative effects or predispose the lungs to permanent damage. Chronic exposure of laboratory animals to higher nitrogen dioxide levels can cause emphysema-like conditions and reduction in resistance to respiratory infection. Epidemiological studies of children in houses with gas stoves confirm the finding of reduced resistance to respiratory infection. The U.S. EPA estimates that health effects may occur in young children exposed to concentrations in excess of 280 to 560 μg/m³ one-hour average. These concentrations occur routinely in houses having gas stoves. Peroxyacetylnitrate is a powerful eye irritant in photochemical smog. Other health effects are similar to those of ozone, but less important because of the relatively low concentrations of this pollutant compared to other oxidants.     

长三角城市群臭氧浓度的时空分异及驱动因素

运用克里金插值、空间自相关分析、冷热点分析和地理探测等定量分析方法，对长三角城市群2015~2017年O3浓度的时空分异特征及驱动因素进行了探讨。结果表明：（1）2015~2017年长三角城市群O3浓度呈上升趋势，O3日最大8 h滑动平均值第90百分位数平均浓度由149 μg/m3上升到166 μg/m3，平均超标率由9.3%上升到12.1%，以O3为首要污染物的天数占超标总天数的比例由32.3%上升到46.4%。（2）受气温和降水量年际波动的影响，各年份O3月均浓度变化曲线形状不同。但O3超标都主要发生在4~9月，超标天数分别占2015、2016、2017年的88.3%、98.2%和97.0%。（3）由于安徽O3浓度快速上升，长三角城市群O3浓度空间分布格局由东高西低演变为北高南低，且同质化增强、异质性减弱。（4）随着O3浓度的上升，O3浓度热点区由环太湖地区向南京都市圈扩展，冷点区在安徽有明显收缩。（5）地理探测表明，长三角城市群O3浓度空间分异主要受经济规模、城市化和排放源等社会经济因素驱动，且均呈正向影响。自然因素中的降水量和风速呈负向影响，分别对O3有显著的清除和扩散作用。     

长江三角洲城市群空气质量时空分布特征

基于数理统计、空间插值技术、相关性分析与GIS地图表达,研究长江三角洲城市群AQI及各空气含量因子污染浓度的时间、空间分布特征。通过提取国务院最新规划的长江三角洲城市群空间分布数据,划分研究区为"一核五圈",探讨了空气质量指数的时间变化特征和AQI、首要污染物的空间分布规律,定量评价了AQI与其污染因子的相关性,结果表明:(1)时间变化上,长三角城市群空气质量季均变化规律为夏季最好,冬季最差;月均变化呈波浪形分布,在1月份的平均浓度皆为最高;周均变化为:在一周后半段达到一周最大值;(2)空间分布上,分季节看,AQI在春、秋、冬三季空间梯度变化显著,呈现北高、南低的分布格局。在首要污染物的分布上,以PM_(2.5)和O_3均分长三角地区;(3)PM_(2.5)含量空间分布与AQI有较高相似性,均处于北高南低的分布状态,臭氧分布呈现东高西低,即较发达的城市臭氧含量相对较高的空间分布格局。最后通过相关性计算,AQI与PM_(2.5)相关性显著,与O_3没有明显相关性,为长三角大气污染防治提供依据。     

香格里拉区域大气本底站地面臭氧浓度的变化特征

对2009年香格里拉区域大气本底站地面臭氧观测结果进行分析,研究其浓度水平、变化特征、影响因素及其区域代表性。结果表明:香格里拉站地面O₃月均值浓度在21.8~57.7 ppb,年平均值为38.0±12.1 ppb,在春季最高,平均值为54.1 ppb,在夏季最低,平均值为28.0 ppb。O₃小时均值浓度超过60 ppb的小时数占总有效小时数的6.6%,超过40 ppb的小时数占43.0%。与相近纬度中国东部地区区域大气本底站地面臭氧观测结果相比,香格里拉站体现出不同的O₃日变化和季节变化特征,具有特殊的地域特征。影响香格里拉站的气流主要来自于其西南方向,3 d的后向轨迹可追溯到孟加拉湾东北部地区。偏南的气流主要出现在夏秋季节,O₃浓度相对低,偏北的气流以冬春为主,O₃浓度相对高。     

Interactions between diesel emissions and gaseous copollutants in photochemical air pollution: Some health implications

A complete assessment of the health effects of diesel emissions must take into account the possible chemical transformations (and associated biological impacts) of particulate organic matter (POM) due to reactions with the many gaseous copollutants which have now been unambiguously demonstrated to be present in atmospheres burdened by photochemical air pollution. These copollutants include the “trace” species, nitric (HNO₃) and nitrous (HONO) acids, the nitrate radical (NO₃), formaldehyde (H₂CO) and formic acid (HCOOH), as well as the criteria pollutants, ozone (O₃) and nitrogen dioxide (NO₂). Techniques for establishing the atmospheric concentrations of the trace pollutants (and their spatial and temporal variations) are briefly described, and we present results of investigations into the reactions of polycyclic aromatic hydrocarbons (PAH) coated on filters and exposed to ambient concentrations of O₃ and NO₂. Environmental health implications of these results are discussed and include the potential for sampling “artifacts” and their possible effects on the correlation (or lack thereof) between ambient PAH levels and urban lung cancer rates, as well as the problems associated with understanding the appropriate POM “dose” to be employed in animal testing and assessments of impacts on human health.     

Paradoxical ozone associations could be due to methyl nitrite from combustion of methyl ethers or esters in engine fuels

We review studies of the effects of low ambient ozone concentrations on morbidity that found a negative coefficient for ozone concentration. We call this a Paradoxical Ozone Association (POA). All studies were in regions with methyl ether in gasoline. All but one study carefully controlled for the effects of other criterion pollutants, so the phenomenon cannot be attributed to them. One was in southern California in mid-summer when ozone levels are highest. Because ozone is created by sunlight, the most plausible explanation for a POA would be an ambient pollutant that is rapidly destroyed by sunlight, such as methyl nitrite (MN). A previously published model of engine exhaust chemistry suggested methyl ether in the fuel will create MN in the exhaust. MN is known to be highly toxic, and closely related alkyl nitrites are known to induce respiratory sensitivity in humans. Support for the interpretation comes from many studies, including three linking asthma symptoms to methyl tertiary butyl ether (MTBE) and the observation that a POA has not been seen in regions without ether in gasoline. We also note that studies in southern California show a historical trend from more significant to less significant ozone-health associations. The timing of those changes is consistent with the known timing of the introduction of gasoline oxygenated with MTBE in that region.     

The Bulgarian Emergency Response System for dose assessment in the early stage of accidental releases to the atmosphere

The Bulgarian Emergency Response System (BERS) is being developed in the Bulgarian National Institute of Meteorology and Hydrology since 1994. BERS is based on numerical weather forecast meteorological information and a numerical long-range dispersion model accounting for the transport, dispersion, chemical and radioactive transformations of pollutants. In the present paper, the further development of this system for a mixture of radioactive gaseous and aerosol pollutants is described. The basic module for the BERS, the numerical dispersion model EMAP, is upgraded with a “dose calculation block”. Two scenarios for hypothetical accidental atmospheric releases from two NPPs, one in Western, and the other in Eastern Europe, are numerically simulated. The effective doses from external irradiation, from air submersion and ground shinning, effective dose from inhalation and absorbed dose by thyroid gland formed by 37 different radionuclides, significant for the early stage of a nuclear accident, are calculated as dose fields for both case studies and discussed.     

Comparison of temporal and Spatial Characteristics of Ozone Pollution at Ground Level in the Eastern China

Monitoring data from ozone（O3） automatic stations in three typical cities with different climatic areas in the southern and northern parts of eastern China are used to analyze temporal and spatial characteristics of ozone pollution at ground level. The results show that ozone pollution level has distinct regional differences and the concentration in the suburbs is higher than that in the urban areas. The seasonal variation of ozone concentration in different climatic areas is greatly affected by the variation of precipitation. Ozone concentration in Shenyang and Beijing , in the temperate zone, has one perennial peak concentration, occurring in early summer, May or June. Ozone concentration in Guangzhou, in sub-tropical zone, has two peak values year round. The highest values occur in October and the secondary high value in June. The ozone season in the south is longer than that in the north. The annual average daily peak value of ozone concentrations in different climates usually occur around 3 pm. The diurnal variation range of ozone concentration declines with the increase of latitude. Ozone concentration does not elevate with the increase of traffic flow. Ozone concentration in Guangzhou has a distinct reverse relation to CO and NOx. This complicated non-linearity indicates that the equilibrium of ozone photochemical reaction has regional differences. Exceeding the rate of Beijing＇s lh ozone concentration is higher than that of Guangzhou, whereas the average 8h ozone level is lower than that of Guangzhou, indicating that areas in low latitude are more easily affected by moderate ozone concentrations and longer exposure. Thus, China should work out standards for 8h ozone concentration.     

Use of kriging models to predict 12-hour mean ozone concentrations in Metropolitan Toronto-A pilot study

Ozone concentrations exhibit spatial variability within metropolitan areas, resulting in significantly different personal exposures among individuals. This paper uses the statistical technique, kriging, to explore the 12-h daytime (8am–8pm) ozone spatial variation and to predict mean outdoor ozone levels at home sites within the Toronto metropolitan area. Outdoor ozone measurements taken in the Toronto metropolitan area between June and August 1992 are used in kriging models to predict outdoor ozone concentrations. The performance of the model is evaluated by comparing actual home outdoor measurements with predicted values. Results indicate that kriging predictions are more accurate than using only the closest stationary ambient site measurements for determining home outdoor ozone concentrations within the metropolitan area. The average variogram obtained from pooling data throughout the entire sampling period shows a clear spatial trend in the outdoor ozone variation. Kriging predictions using the parameters from the average variogram perform as well as those using variograms from individual days. An approach for minimizing sample bias can be used to increase the accuracy of the predictions; cross-validation suggests that it is a reasonable procedure.     

Modelling of water-ozone reaction system

Mass transfer and reaction kinetics of raw Nile water ozonation are examined. The contact system is a perfectly mixed reactor, and ozone is bubbled through a glass diffuser at different supply rates. The ozone residual is detected for different reaction time intervals. A simple mathematical model is proposed to describe the mechanism of the ozone reactions in the reactor. The proposed model quite accurately describes the mass transfer behaviour in the reactor and determines the ozone dissociation rate constant, together with the effect of the chemical reaction on the ozone transfer. A linear relationship is observed between the ozone feed rate and the ozone residual. First order reaction kinetics describes fairly well the autodecomposition and the global reaction rates of ozone in raw water. The mass transfer coefficient is about 0.18 min⁻¹. The dissociation and the reaction rate constants are evaluated to be 0.33 mg L⁻¹ and 0.19 mg L⁻¹min⁻¹.     

Comparison of temporal and Spatial Characteristics of Ozone Pollution at Ground Level in the Eastern China

Abstract

Monitoring data from ozone(O₃ automatic stations in three typical cities with different climatic areas in the southern and northern parts of eastern China are used to analyze temporal and spatial characteristics of ozone pollution at ground level. The results show that ozone pollution level has distinct regional differences and the concentration in the suburbs is higher than that in the urban areas. The seasonal variation of ozone concentration in different climatic areas is greatly affected by the variation of precipitation. Ozone concentration in Shenyang and Beijing, in the temperate zone, has one perennial peak concentration, occurring in early summer, May or June. Ozone concentration in Guangzhou, in sub-tropical zone, has two peak values year round. The highest values occur in October and the secondary high value in June. The ozone season in the south is longer than that in the north. The annual average daily peak value of ozone concentrations in different climates usually occur around 3 pm. The diurnal variation range of ozone concentration declines with the increase of latitude. Ozone concentration does not elevate with the increase of traffic flow. Ozone concentration in Guangzhou has a distinct reverse relation to CO and NO_x. This complicated non-linearity indicates that the equilibrium of ozone photochemical reaction has regional differences. Exceeding the rate of Beijing's 1h ozone concentration is higher than that of Guangzhou, whereas the average 8h ozone level is lower than that of Guangzhou, indicating that areas in low latitude are more easily affected by moderate ozone concentrations and longer exposure. Thus, China should work out standards for 8h ozone concentration.