NUMERICAL SIMULATION OF OZONE DISTRIBUTIONS AND ITS VARIATION MECHANISM*

A 2-D global chemistry-transport model is set up in this paper.The model simulates the atmospheric ozone distributions well with specified dynamical conditions.The analysis of ozone variation mechanism shows that ozone is chemically in quasi-equilibrium except for the polar night region where the variation of ozone concentration is under the control of dynamical processes,that the oxygen atoms which produce ozone are mainly provided by the photolysis of O₂ in the upper stratosphere and by the photolysis of NO₂ in the lower stratosphere and the troposphere.and that the ozone is destroyed mainly by NO_x:the reactions between NO_x and O₃ and the odd oxygen cycle contribute 80% to more than 90% of the ozone destruction.     

Convective Redistribution of Ozone and Oxides of Nitrogen in the Troposphere over Europe in Summer and Fall

The fluxes of ozone and NO_x out of the atmospheric boundary layer (ABL) over Europe are calculated in a mesoscale chemical transport model (MCT) and compared with the net chemical production or destruction of ozone and the emissions of precursors within the ABL for two 10 days' periods which had quite different synoptic situations and levels of photochemical activity (1–10 July 1991 (JUL91) and 26 October–4 November 1994 (ON94)). Over the European continent, about 8% of the NO_x emissions were brought from the ABL to the free troposphere as NO_x, while about 15% of the NO_x emissions were brought to the free troposphere as NO_y–NO_x, i.e. as PAN or HNO₃. The convection dominates over the synoptic scale vertical advection as a transport mechanism both for NO_x and NO_y out of the boundary layer in the summertime high pressure situation (JUL91), while in the fall situation (ON94) the convective part was calculated to be the smallest. NO_x was almost completely transformed to NO_y–NO_x or removed within the ABL. Also for NO_y the major part of the atmospheric cycle is confined to the ABL both for JUL91 and ON94. The vertical transport time out of the ABL is of the order of 100h both for the total model domain and over the European continent. The net convective exchange of ozone from the ABL is not a dominant process for the amount of ozone in the ABL averaged over 10 days and the whole domain, but convection reduces the maximum ozone concentration in episodes significantly. The ozone producing efficiency of NO_x is calculated to increase with height to typically 15–20 in the upper half of the troposphere from around 5 in the ABL, but in the middle free troposphere the concentration of NO_x is often too low to cause net chemical formation of ozone there.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

The role of precursor emissions on ground level ozone concentration during summer season in Poland

Three online coupled chemical transport model simulations were analyzed for three summer months of 2015 in Poland. One of them was run with default emission inventory, the other two with NO_x and VOC emissions reduced by 30%, respectively. Obtained ozone concentrations were evaluated with data from air quality measurement stations and ozone sensitivity to precursor emissions was estimated by ozone concentration differences between simulations and with the use of indicator ratios. They were calculated based on modeled mixing ratios of ozone, total reactive nitrogen and its components, nitric acid and hydrogen peroxide. The results show that the model overestimates ozone concentrations with the largest errors in the morning and evening, which is primarily related to the way vertical mixing is resolved by the model. Better model performance for ozone is achieved in rural than urban environment, as PBL and mixing mechanisms play more significant role in urban areas. Modeled ozone shows mixed sensitivity to precursor concentrations, similarly to other European regions, but indicator ratios have different values than are found in literature, particularly H₂O₂/HNO₃ is larger than in southern Europe. However, indicator ratios often differ between locations and transition values need to be established individually for a given region.     

Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

Ozone control strategy modeling and evaluation for Athens,Greece: ROG vs. NO x effectiveness and the impact of using different wind field preparation techniques

Summary The CIT photochemical model was used to investigate the effectiveness of ozone control strategies for Athens, Greece. A unique aspect of this study was the use of two different wind fields, one from a prognostic model, and the other derived with objective analysis procedures. This allows investigating to what degree the wind fields both derived using accepted methods, influence control strategy evaluation. Strategies investigated included reducing ROG and NO _x , and combinations of the two. For the period studied, the use of different meteorological field preparation techniques did not influence the direction of the ozone response to controls. In both cases (i.e. using prognostic or objective analysis wind fields), reducing NO _x led to predicted increases in ozone levels at the measurement stations, and ROG control lowered ozone. PAN concentrations respond similarly to ozone. However, use of the two different wind fields significantly impacted the degree and spatial locations of the responses. Use of the objective analysis fields showed greater response to emission controls because of the lower wind velocities generated. The influence of the biogenic emissions were found to be small. Also, a number of key data necessary for future studies of this kind were identified, as well as modeling domain questions.With 14 Figures     

A Retrospective Analysis of Ozone Formation in the Lower Fraser Valley,British Columbia,Canada. Part II: Influence of Emissions Reductions on Ozone Formation

A mechanistic exploration of how ozone formation in the Lower Fraser Valley (LFV) has changed over a 20-year (1985–2005) retrospective period was performed using numerical models, observations, and emissions data from four key episodes selected from the 20-year period. The motivation for this study was the observed differences in trends in summertime episodic ozone concentrations recorded at various monitoring stations within the valley; stations in the western part of the valley have generally shown a noticeable reduction in episodic ozone concentrations whereas stations in the eastern part of the valley have shown little or no improvement in their maximum 8-hour averaged ozone concentrations. Concurrent with these air quality changes, there has been a well-documented reduction in ozone precursor emissions along with an observed shift in the population patterns within the valley over the 20-year period. Ozone formation for four episodes, encompassing the different meteorological regimes that occur during LFV ozone events and spanning the retrospective period, were investigated using the Weather Research and Forecasting (WRF)-Sparse Matrix Operator Kernel Emission (SMOKE)-Community Multiscale Air Quality (CMAQ) modelling system. For each episode, two simulations, intended to isolate the effects of emission changes from meteorological changes, were performed: one with emissions set at the 1985 level and the other with emissions set at the 2005 level. Based on analysis of the model output, observational data, and precursor emission inventories, we find that the Port Moody station in the western LFV remains a volatile organic compound (VOC)-sensitive location; the central part of the LFV around the town of Chilliwack has generally changed from being VOC-limited to being NO_x-limited; the easternmost part of the valley around the town of Hope has been and remains NO_x-limited. Furthermore, based on the observational data and numerical model output, ozone production efficiency as a function of NO has increased noticeably at Chilliwack and likely in the other eastern parts of the valley. This efficiency increase has likely offset some of the benefits resulting from local NO_x emission reductions.

RÉSUMÉ?[Traduit par la rédaction] Nous avons effectué une exploration mécaniste de la façon dont la formation de l'ozone dans la vallée du bas Fraser (VBF) a changé au cours d'une période rétrospective de 20 ans (1985–2005) en nous servant de modèles numériques, d'observations et de données sur les émissions pour quatre épisodes clés choisis dans la période de 20 ans. Ce sont les différences observées entre les tendances dans les concentrations épisodiques d'ozone enregistrées à certaines stations de surveillance dans la vallée qui ont motivé cette étude : les stations dans la partie ouest de la vallée ont généralement affiché une réduction notable des concentrations épisodiques d'ozone alors que les stations dans la partie est de la vallée n'ont montré que peu ou pas d'amélioration dans les valeurs maximales des concentrations moyennes d'ozone sur 8 heures. Concurremment avec ces changements dans la qualité de l'air, il s'est produit une réduction bien documentée dans les émissions de précurseurs de l'ozone en même temps qu'un déplacement observé dans les configurations de population dans la vallée au cours de la période de 20 ans. Nous avons étudié la formation d'ozone au cours de quatre épisodes, englobant les différents régimes météorologiques survenus lors des événements d'ozone dans la VBF et couvrant la période rétrospective, à l'aide du système de modélisation SMOKE (Sparse Matrix Operator Kernel Emissions) – CMAQ (Community Multiscale Air Quality) du WRF (Weather Research and Forecasting). Pour chaque épisode, nous avons effectué deux simulations visant à isoler l'effet des changements dans les émissions de l'effet des changements météorologiques, l'une avec les émissions réglées au niveau de 1985 et l'autre avec les émissions réglées au niveau de 2005. En nous basant sur l'analyse de la sortie du modèle, les données d'observation et les inventaires des émissions de précurseurs, nous trouvons que la stations de Port Moody dans l'ouest de la VBF demeure un endroit sensible aux composés organiques volatiles (COV); la partie centrale de la VBF, autour de la ville de Chilliwack, a généralement changé de « limitée par les COV » à « limitée par les NO_x »; la partie la plus à l'est de la vallée, autour de la ville de Hope, était et est restée « limitée par les NO_x ». De plus, d'après les données d'observation et la sortie du modèle numérique, l'efficacité de la production d'ozone en fonction de NO a notablement augmenté à Chilliwack et vraisemblablement dans les autres parties de l'est de la vallée. Cette augmentation d'efficacité a probablement annulé certains gains provenant des réductions dans les émissions locales de NO_x.     

Impact of precursor levels and global warming on peak ozone concentration in the Pearl River Delta Region of China

The relationship between the emission of ozone precursors and the chemical production of tropospheric ozone(O3) in the Pearl River Delta Region(PRD) was studied using numerical simulation.The aim of this study was to examine the volatile organic compound(VOC)-or nitrogen oxide(NOx =NO+NO2)limited conditions at present and when surface temperature is increasing due to global warming,thus to make recommendations for future ozone abatement policies for the PRD region.The model used for this application is the U.S.Environmental Protection Agency’s(EPA’s) third-generation air-quality modeling system;it consists of the mesoscale meteorological model MM5 and the chemical transport model named Community Multi-scale Air Quality(CMAQ).A series of sensitivity tests were conducted to assess the influence of VOC and NOx variations on ozone production.Tropical cyclone was shown to be one of the important synoptic weather patterns leading to ozone pollution.The simulations were based on a tropicalcyclone-related episode that occurred during 14-16 September 2004.The results show that,in the future,the control strategy for emissions should be tightened.To reduce the current level of ozone to meet the Hong Kong Environmental Protection Department(EPD) air-quality objective(hourly average of 120 ppb),emphasis should be put on restricting the increase of NOx emissions.Furthermore,for a wide range of possible changes in precursor emissions,temperature increase will increase the ozone peak in the PRD region;the areas affected by photochemical smog are growing wider,but the locations of the ozone plume are rather invariant.     

Heterogeneous Chemistry and the O3 Budget in the Lower Mid-Latitude Stratosphere

A photochemical box model including a detailed heterogeneous chemistrymodule has been used to analyze in detail the effects of temperature andaerosol surface area on odd oxygen production/depletion in the lowerstratosphere at 30° S. Results show that for background aerosolloading, the hydrolysis of BrONO₂ and N₂O₅are most important atall temperatures studied except when the temperature falls below about205 K, when ClONO₂ hydrolysis becomes most important. Thisprocessing leads to removal of active nitrogen to form nitric acid andenhancement of HO_x, BrO_x, ClO_x levels. Detailed O₃ budgets asa function of temperature are presented showing how ozone loss andproduction terms vary with changes in stratospheric sulfate aerosol loadingfor the individual families. For (most) aerosol loading levels, thelargest ozone losses occurred at warmer temperatures due to the strongtemperature dependence of the NO_x ozone-destroying reactions. Theexception to this occurred for the conditions representative of volcanicloading, which showed a strong increase in ozone destruction due toincreases in destruction from the ClO_x and HO_x families.The ozoneproduction term k[NO][HO₂] did not show a strong dependence oneithertemperature or aerosol loading, due to the offsetting effect of reducedNO_xand increased HO_x concentrations.     

Surface ozone values in anomalous summer 2010 measured in Obninsk

Given and analyzed are the results of the measuring of concentration of ozone O₃, nitrogen oxides NO_x, and carbon monoxide CO at the surface as well as the sum of hydrocarbons and the aerosol optical depth in Obninsk (Kaluga oblast) during the warm period 2010 and 2011. The relationship between the air temperature and the maximum daily ozone values in May–September 2010 are characterized by the higher correlation coefficient than in May–September 2011: 0.82 ± 0.05 versus 0.64 ± 0.07. Increased concentration of surface ozone in Obninsk in July–August 2010 as compared to the similar period in 2011 were caused by the higher concentrations of the compounds-predecessors of ozone. The concentration of O₃ in August 2010 exceeded 200μg/m³ and was never registered in Obninsk during the observation period of 2004–2011. This is associated with the air masses that came to Obninsk from the areas with peat and forest fires that resulted in the dramatic increase in surface concentrations of NO_x, CO, and hydrocarbons.     

武汉市2018年4—9月臭氧及其前体物非线性关系研究

近年来武汉市臭氧污染日益严峻,成为影响空气质量达标的瓶颈,弄清臭氧及其前体物非线性关系是臭氧防控的关键和基础.本研究基于武汉中心城区2018年4—9月臭氧及其前体物在线观测数据,分析出武汉市臭氧浓度受前体物和气象条件等因素的共同影响,呈较为明显的季节变化和日变化特征.观测期间武汉市大气挥发性有机物（VOCs）平均体积分数为32.5×10^-9,烷烃是武汉市VOCs的主要组分,其次是含氧VOCs （OVOCs）和卤代烃.利用基于观测的模型定量分析臭氧与前体物之间的关系,发现削减VOCs会引起臭氧生成潜势的显著下降,而削减氮氧化物则会使臭氧生成潜势升高,说明武汉市臭氧生成处于VOCs控制区.在人为源VOCs中,间/对二甲苯和邻二甲苯的相对增量反应活性（RIR）最高,是影响臭氧生成的关键组分.     

基于CMAQ-MCM模型的长三角地区夏季臭氧和大气氧化性影响的研究

传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O₃））前体物的氧化反应,具有一定的不确定性,导致模拟结果产生偏差.针对该问题,本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM）,模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O₃和其前体物随时间的变化趋势.对模拟的O₃日最大8 h平均浓度的统计分析表明,徐州表现最好（标准平均误差=-0.15,标准平均偏差=0.23）.在长三角地区,居民源对挥发性有机物（VOCs）的贡献最大,占39.08%,其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小,约为2.11%.对活性氧化氮（NO_y）的分析表明,其主要组分是NO_x（80%）,其次是硝酸（HNO₃）（<10%）.O₃的空间分布与NO_y和NO_x非常相似.HCHO等其他氧化产物的分布与NO_x相似,这很可能是由于在高NO_x条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似,表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.     

Effects of turbulence on gas-phase atmospheric chemistry: Calculation of the relationship between time scales for diffusion and chemical reaction

Summary Non-uniform mixing of gas-phase trace species may limit the accuracy of the predictions of Eulerian transport/transformation models if the chemical reactions are rapid enough to be diffusion limited. If a reaction is diffusion limited, its average reaction rate might not be accurately represented by those models that assume instantaneous uniform mixing. One possible consequence of this artificial dilution is the overprediction of ozone and hydroxyl radicals. We have determined which reactions in the Regional Acid Deposition Model Gas-Phase Chemical Mechanism (Stockwell et al., 1990) are diffusion limited for a typical atmospheric condition through the calculation of Damköhler numbers. Damköhler numbers are defined to be the ratio of the diffusion mixing time to the chemical reaction time for a given chemical reaction (McRae et al., 1982; Hill, 1976). The reactions of hydroxyl radicals and the reactions of peroxy radicals with NO are diffusion limited under typical atmospheric conditions. Both sets of reactions are especially significant because NO_x and organic species strongly affect ozone and hydroxyl radical concentrations. It is suggested that Damköhler numbers could be used to help determine the placement of Eulerian model boundaries and to determine model grid structure.With 2 Figures     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

The potential impact of the reaction OH+ClO→HCl+O2 on polar ozone photochemistry

We call attention to the likely importance of the potential reaction OH+ClOHCl+O₂. It may only be a minor channel for the reaction of OH with ClO, which is often ignored in models, but if it occurs it considerably increases the rate of recovery of HCl after an air parcel has encountered a polar stratospheric cloud (PSC). The net effect of this reaction on the ozone concentration depends on the relative HCl concentration and whether the air parcel is in a PSC. When an air parcel is in a PSC and the HCl concentration is less than the sum of the HOCl and ClONO₂ concentrations, heterogeneous ClO _x production is rate limited by the production of HCl. Under these conditions the reaction allows HCl to be reprocessed more rapidly by the heterogeneous reactions of HCl with HOCl and ClONO₂. This allows high ClO _x concentration to be maintained for longer, and at a slightly higher level, than would otherwise be possible which in turn leads to more ozone depletion. When there are PSCs but HCl is in excess, or outside of the PSC regions (i.e. during the recovery phase), the reaction will always reduce the ClO/HCl ratio and hence slightly reduce the ozone loss.     

南京及周边黑碳气溶胶对臭氧影响的观测分析和数值模拟

利用南京地面站点2016-2017年黑碳气溶胶(Black Carbon,BC)和臭氧(O3)逐小时观测资料,对比分析了不同季节BC与近地面O3的关系.结果 表明,高BC(高于平均值)影响下的O3质量浓度值明显比低BC(低于平均值)影响下的O3质量浓度值低,这种抑制作用在秋冬季明显高于春夏季,且BC与O3的负相关性在秋...     

A vertical profile of Ozone concentration in the atmosphericboundary layer over central Taiwan

Summary  In the central region of Taiwan, ozone episodes occur most often during autumn. Two field experiments were conducted during the autumns of 1998 and 1999 to analyze the vertical profile of the boundary layer and determine its effects on ozone concentration over the region. The vertical virtual potential temperature and wind profiles were derived from tethersonde data. The NO_x, NMHC and O₃ concentration vertical profiles were monitored up to a height of 500 meters using black-covered Teflon tedler sampling bags. During the experimental periods, nighttime terrestrial long wave radiation could cause the inversion height to reach 500 meters by the following morning. It was shown that these types of synoptic structures suppress the vertical diffusion of NO_x, NMHC and O₃. During the daytime, measurements indicate that pollutants were well mixed in the upper portion of the mixing layer. At night, the ground level ozone concentration was on the decrease but increased with altitude to a height of 500 m. The NO_x decreased with altitude whereas the NMHC showed no significant variations. Received April 13, 2000 Revised July 24, 2000     

A numerical model for one‐dimensional simulation of stratospheric chemistry

Abstract

We describe a one‐dimensional (1‐D) numerical model developed to simulate the chemistry of minor constituents in the stratosphere. The model incorporates most of the chemical species presently found in the upper atmosphere and has been used to investigate the effect of increasing chlorofluorocarbon (CFC) emissions on ozone (O₃).

Our calculations confirm previous results that O₃ depletions in the 20–25 km region, the region of the O₃ maximum, are very sensitive to the relative abundances of Cl_x and NO_y in the lower stratosphere for high Cl_x amounts. The individual abundances of lower stratospheric Cl_x and NO_y amounts are very sensitive to upper tropospheric mixing ratios, which, in turn, are determined largely by surface input fluxes and heterogeneous loss processes. Thus the behaviour of column O₃ depletions at high Cl_x levels is greatly affected, albeit indirectly, by tropospheric processes. For high Cl_x levels the O_x flux from the stratosphere to the troposphere is dramatically reduced, leading to a large reduction in tropospheric O₃. Some of the variation between different published 1‐D model results is most likely due to this critical dependence of O₃ depletion on NO_y‐Cl_x ratios.

Model simulations of time‐dependent CFC effects on ozone indicate that if CFCs were to remain at constant 1980 emission rates while N₂O increased at 0.25% a^?1 and CH₄ increased at 1% a^?1, we could expect a 2.2% decrease in total column O₃ (relative to the 1980 atmosphere) by the year 2000. However, if CFC emission rates were to increase by 3% a^?1 (current estimates are 5–6% a^?1), we would predict a depletion of 2.7% by the year 2000. The calculations for times beyond the year 2000 suggest that the effects on total O₃ will begin to accelerate. If methyl chloroform emissions are added at 7% a^?1 (current estimates are 7–9% a^?1) to the above CFC‐N₂O‐CH₄ scenario we calculate total O₃ depletions by the year 2000 that are 41% larger than those calculated without. This suggests that if the emissions of methyl chloroform continue to increase at their present rate then methyl chloroform could have a significant effect upon total O₃.