Simulation of ozone intrusion caused by a tropopause fold and cut-off low

A tropopause fold and cut-off low developed over Europe at the end of April 1982 and enhanced the exchange of air between the stratosphere and troposphere. The episode has been simulated using the EURAD model which has been designed for long-range transport simulation for European conditions. Applying a linear relationship between potential vorticity and ozone, concentration fields of the tracer and their changes due to outflow of ozone-rich air from the stratosphere could be simulated. A considerable decrease of stratospheric ozone was also obtained. This indicates noticeable mixing of tropospheric air with reduced ozone content into the stratosphere during the episode. Strong downward fluxes more than an order of magnitude larger than normal when averaged over the model domain show up around levels close to the tropopause. Obviously, dynamical processes fovern teh ozone budget o the upper troposphere during the vigorous intrusion event. Drastic increases of ozone also occur in the lower troposphere but are probably underestimated since vertical mixing by clouds is not taken into account in the simulation experiments. It is intended to explore the interaction of ozone of stratospheric and tropospheric (anthropogenic) origin in further experiments.     

On the mean daily and seasonal variations of the vertical ozone profiles in the lower troposphere

During the 15 year period that the Zugspitze cable car has operated between the valley (1 km a.s.l.) and Zugspitze peak (3 km a.s.l.) at the northern border of the Bavarian Alps, it has been used for investigating the profiles of meteorological and atmospheric electrical parameters, and Aitken nuclei. This cable railway is rather steep and is suspended mostly far away from the ground. From 1980 to 1982 nearly 2000 ozone profiles were additionalyrecorded. The data collected offer a profound basis in order to study the time variations of the lower tropospheric ozone profile depending on the hour of the day during all the seasons. In this paper the following are reported: the shape and time behaviour of ozone profiles in different seasons depending on the vertical mixing intensity, stratospheric intrusions and the penetration depth of the stratospheric O₃.     

基于OMI数据的中国中东部城市近地面臭氧时空分布特征研究

利用OMI卫星反演数据分析了2005—2014年中国中东部地区对流层臭氧变化趋势.结果表明,近10年来对流层臭氧总柱浓度混合比例较稳定,但近地面浓度明显增加,特别是在冬季臭氧上升速度达40%.同时分析了京津冀、长三角、珠三角地区10个重点城市的臭氧数据,发现京津冀地区的臭氧涨幅超过其他两个地区,其中,长三角地区臭氧混合比例最高,而珠三角地区相对较稳定.利用臭氧激光雷达和地面臭氧监测数据对卫星反演结果进行比较显示了较好的一致性,证明使用卫星反演的数据来研究长时间范围内近地层的臭氧变化是一种可行的方法.     

Methane reductions: Implications for global warming and atmospheric chemical change

Atmospheric methane (CH₄) concentrations have more than doubled over the last two centuries. These increases may contribute to global warming, enhance formation of tropospheric ozone, suppress OH and affect stratospheric ozone. Calculations show that stabilization of CH₄ could reduce projected temperature increases and possibly mitigate background tropospheric O₃ increases due to increasing levels of CH₄.     

The effect of aircraft emissions on tropospheric ozone in the northern hemisphere

The effect of aircraft emissions on tropospheric ozone was studied using a two-dimensional zonal model, of longitude vs altitude, extending between 30°–60°N. An emission inventory for the 1987 civil aircraft fleet was constructed based on fuel usage and civil aviation statistics. The addition of the 1987 civil emissions to a modelled standard atmosphere caused increases in concentrations of O₃ (12%; 10 ppbv), NO_x (40%; 20 pptv) and OH (10%) between 8 and 12 km altitude. A doubling and tripling of the emissions corresponding to a present day inclusion of military aircraft and a future scenario, respectively, caused the increase in O₃ to double (19%) and almost triple (25%). The lightning source of NO_x was found to be an important parameter. When this source was ommitted the change in O₃ at the cruise flight altitude increased to 16%, with respect to a standard atmosphere not containing a lightning source of NO_x.     

臭氧层损耗影响低层大气质量的新认识

近年来有关平流层臭氧损耗影响低层大气质量的研究表明 ,在污染相对轻的地方 ,可以观测到加强的光化学反应过程 ;在污染地区 ,最终的影响与大气中存在的痕量物质间的相互作用有很大关系 ,这些通常会被人为排放带来的影响所掩盖 ;越来越多的证据表明 ,臭氧层损耗与气候变化之间的相互作用是至关重要的涉及全球变化的问题 ,是今后活跃的科学研究领域。     

天津中心城区夏季非甲烷有机化合物组成特征及其臭氧产生潜力分析

大气中非甲烷有机化合物(NMOCs)作为臭氧产生前体物之一,其浓度与组成特征研究对于研究地面臭氧形成的机制有重要的科学意义.选择夏季时段从2009年8月6日到13日在天津中心城区气象局铁塔站位对NMOCs进行采样分析,采样频次为每日5次,采样时间从7:30am到23:00pm间隔2～3h采样1次.天津城区NMOCs的含...     

上海市城区春节和“五一”节期间大气挥发性有机物的组成特征

挥发性有机物(VOCs)是对流层臭氧和二次有机气溶胶等二次污染生成过程的关键前体物.研究VOCs的浓度水平、组成特征和反应活性对揭示复合型大气污染的形成机制具有重要意义.本研究利用在线气相-氢离子火焰法测量了2009年春节和"五一"节期间上海市城区大气中56种VOCs.结果表明,上海市城区大气受机动车尾气排放源影响明显,VOCs浓度日变化特征呈双峰状,与上下班交通高峰基本吻合.大气中VOCs平均体积分数为(28.39±18.35)×10-9;各组分百分含量依次为:烷烃46.6%,芳香烃27.0%,烯烃15.1%,乙炔11.2%.用OH消耗速率和臭氧生成潜势(OFP)评估了VOCs大气化学反应活性,结果表明,上海市城区大气VOCs化学反应活性与VOCs体积浓度相关性良好;VOCs活性与乙烯相当,平均化学反应活性较强;OH消耗速率贡献最大的物种是烯烃51.2%和芳香烃31.8%;OFP贡献最大的物种是芳香烃53.4%和烯烃30.2%;对臭氧生成贡献最大的关键活性物种为丙烯、乙烯、甲苯、二甲苯以及丁烯类物质.     

天津武清大气挥发性有机物光化学污染特征及来源

大气VOCs(挥发性有机物)是臭氧的重要前体物之一,研究其光化学污染特征和来源对控制近地面臭氧污染具有重要意义. 于2006年8月10日—9月18日在天津郊区武清采用在线监测的方法,同步观测了VOCs、O₃和NO₂等气态污染物,以及温度和紫外辐射等气象因子. 对9月10—15日臭氧浓度较高时段VOCs的浓度水平、化学反应活性、臭氧生成潜势和来源进行了分析. 结果表明:天津郊区武清环境空气中VOCs体积混合比平均浓度为24.6×10-9;VOCs主要由烷烃和烯烃组成,机动车排放、轻烃工艺、生物排放、沼气和碳氢溶剂是其重要来源. 根据等效丙烯浓度和MIR方法评估,烯烃对臭氧光化学产生的贡献占主导性地位,其中异戊二烯、丙烯、二甲苯和甲苯是臭氧生成潜势较大的物种. 通过与天津城区比较发现,郊区与城区的大气VOCs不仅组成不同,而且化学活性物种也不同.      

The vertical distribution of aerosols and acid related compounds in air and cloudwater

Vertical profiles (surface to 5 km) of aerosol particle number concentration, NO_y′ mixing ratio, and cloudwater SO₄²⁻ and NO₃⁻ equivalent concentration were obtained in three field studies: North Bay, Ontario, during the summer of 1982 and the winter of 1983–1984, and Syracuse, New York, during the fall of 1984. The measurements from these locations and different seasons are compared. Generally, airborne concentrations are highest with air-mass back trajectories from the south and lowest with back trajectories from the north. For the southerly trajectories, median particle number concentrations (0.2–2 μm) near ground level (950 mb) vary from 1700 cm⁻³ during the summer project to 800 cm⁻³ during the winter project. At 700 mb, the south trajectory particle number concentration ranged between 60 and 170 cm⁻³. Median NO_y′ mixing ratios for southerly back trajectories were approximately 6 and 9 ppb at 950 mb and 0.4 and 0.8 ppb at 700 mb for the fall and winter projects, respectively. Comparison of particle number concentration profiles outside of cloud with cloud droplet plus interstitial aerosol particle number concentrations inside cloud indicate that cumulus clouds can transport aerosols vertically from below cloud base. In contrast, stratiform clouds have similar concentrations inside the clouds as outside at the same altitude. The vertical variations of cloudwater sulphate and nitrate concentrations and the NO₃⁻/SO₄²⁻ equivalent concentration ratio are discussed for each of the three field studies.     

上海市城区VOCs的年变化特征及其关键活性组分

2010年在上海市城区开展了为期一年的连续观测,采用自动在线GC-FID方法定量测试了大气中56个VOCs物种的浓度.结果发现,上海市城区大气VOCs的全年小时体积分数为(2.47~301.48)×10^-9,平均体积分数为(26.45±23.36)×10^-9,其中,烷烃占46.72%,芳香烃占33.18%,烯烃占11.33%,乙炔占8.76%.T/B(甲苯/苯)为3.51±2.40,表明气团除受机动车影响外,受溶剂、油气和LPG挥发等其他VOCs排放的影响也比较突出;E/E(乙烷/乙炔)为0.98±0.68,表明气团存在老化现象,且春冬季节气团光化学年龄相对较短,夏秋季节光化学年龄相对较长.VOCs的浓度水平和组成在不同风向风速影响下存在一定差异,西南部石化和化工企业排放的VOCs对城区的影响明显,其主要物种为芳香烃和烯烃;该地区气团的OH消耗速率常数(K^OH)为8.05×10^-12 cm³·分子^-1·s^-1,平均VOCs最大O₃增量反应活性(4.00 mol·mol^-1)与乙烯相当,平均反应活性较强;对OH消耗速率(L^OH)贡献率最大的是烯烃(42.21%)和芳香烃(40.83%),对臭氧生成潜势(OFP)贡献率最大的是芳香烃(62.75%)和烯烃(21.70%),VOCs的关键活性组分是二甲苯、甲苯、乙苯、乙烯、丙烯、反-2-丁烯及异戊二烯.     

Life-cycle assessment of four types of floor covering

Four types of floor covering have been investigated with respect to their environmental impact: linoleum, cushion vinyl, tufted carpet with a woollen pile and tufted carpet with a polyamide pile. The analysis relates to all stages in the life-cycle (from ‘cradle to grave’) and focuses on floor coverings for domestic use. The analysis is performed by means of the method for life-cycle assessment (Dutch approach). Each floor covering is assessed with regard to its environmental impact. This impact can be of various type: depletion of raw materials, cumulative energy requirement, global warming, acidification, tropospheric ozone creation, stratospheric ozone depletion, eutrophication, production of waste and human health. The inventory of environmental interventions (materials, energy requirements, waste and emissions to air, water and soil) was fairly complete. Most interventions relating to the processes that make up the life-cycle of the floor coverings in question could be quantified. A large part of the data is associated with the process energy requirement. In general these data are quite reliable. The results of the impact assessment for linoleum differs considerably from those for other types of floor coverings. Linoleum turns out to be the most environmentally favourable floor covering. It was not possible to differentiate between the environmental impact of cushion vinyl, tufted carpet with a woollen pile and tufted carpet with a polyamide pile.     

重庆市O3污染日的大气环流分型与传输特征

通过分析重庆市主城区2015~2019年O₃浓度和气象要素观测数据,发现主城区O₃超标日数、超标日O₃中位值和90百分位浓度值均呈现逐年升高趋势,O₃与温度成正相关、与相对湿度成负相关,高O₃浓度对应每日最高温度区间为35℃以上以及相对湿度区间70%以下.采用T-mode主成分分析法(PCT)对2015~2019年的4~9月850hPa低层位势高度场和风场进行分型,总结出重庆市O₃污染期间主要有8种天气类型,其中有利于出现高浓度O₃现象的天气类型分别是低压西北侧型(T1)、低压后部型(T4)和高压西侧(T3),对应O₃平均超标率分别为34.6%、17.0%和14.2%.利用HYSPLIT4模型后向轨迹聚类方法和潜在源贡献算法(PSCF),计算得到O₃污染日的气团主要以中短距离输送为主,主要传输轨迹来自北、东北、南以及西南四个方向,从2015~2019年,主要污染来源有一个明显的从北转南的趋势,O₃污染的潜在源贡献分析结果与全市工业源NO_x、VOCs排放量空间分布的一致性较高.     

深圳臭氧污染日的VOCs组成与来源特征

由于挥发性有机物（VOCs）是O₃生成的关键前体物,因此了解VOCs的污染特征以及主要来源对控制O₃污染具有重要的意义.本研究于2019年9~10月在深圳市开展了在线VOCs观测,共计监测104个物种.观测期间,臭氧超标率达17.8%.TVOCs总浓度为38.9×10^-9,污染日浓度明显高于非污染日.从大类物种来看,浓度从高到低依次为烷烃>含氧有机物（OVOCs）>卤代烃>芳香烃>烯烃>乙炔>乙腈,臭氧生成潜势（OFP）中芳香烃、OVOCs以及烯烃贡献较大.由PMF源解析模型分析结果可知,VOCs主要来源包括生物质燃烧、汽油挥发、机动车尾气、工业过程以及溶剂使用等,而其中对OFP贡献较大的排放源为溶剂使用（45.8%）、机动车尾气（27.3%）.臭氧污染日发生时,清晨低风速可能导致了机动车尾气与汽油挥发源在交通早高峰快速积累,而当日高温亦会加快汽油源与溶剂源组分挥发并促进光化学反应.     

Deactivation of Cu-SAPO-34 by urea-related deposits at low temperatures and the regeneration

Selective catalytic reduction(SCR) with urea catalyzed by Cu-SAPO-34 is an effective method to eliminate NO_x from diesel exhaust. However, urea-related deposits may form during cold-start and urban driving due to low exhaust temperatures. The activity of CuSAPO-34 at 175°C is significantly degraded by urea exposure, and 300°C is required for regeneration. Through in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) and temperature-programmed hydrolysis studies, the dominant stable deposit at 175°C is identified as biuret, which can be eliminated at 300°C. The urea-derived deactivation and regeneration mechanisms of Cu-SAPO-34 were compared with those of anatase-supported catalysts.     

A two-year study of ozone behaviour at rural and forested sites in Eastern France

Ozone and other gases measurements in three rural sites of different altitudes in eastern France (an area with important forest decline) were used as a basis to understand the mechanisms controlling the ozone behaviour in the lower troposphere. An analysis is presented of the annual variation of the background tropospheric ozone level in order to evaluate its contribution to the surface ozone level. The frequency of occurrence of simultaneous elevated ozone episodes at one urvan and the three rural sites was examined in order to determine the major cause of high ozone levels. The relation between elevated ozone concentrations and wind direction was also investigated. It was found that the majority of high ozone concentration episodes take place simultaneously at the three sites, showing an elevated occurrence of episodes of regional origins. Most of the episodes are associated with the east wind sector.     

Heterogeneous chemistry on polar stratospheric clouds

Polar stratospheric clouds play a crucial role in the depletion of stratospheric ozone over Antarctica in the spring months. The cloud particles promote the conversion of the inert chlorine reservoirs HCl and ClONO₂ to Cl₂, which is photolytically active. Furthermore, the clouds lead to the removal of nitric acid and nitrogen oxides from the gas phase, facilitating the destruction of ozone by catalytic cycles involving chlorine free radicals.     

Trends in ground level ozone concentrations in the European Union

Following the Council Directive 92/72/EEC on air pollution by ozone the Member States of the European Union have to inform the European Commission on ozone concentrations and exceedances of threshold values within their territory. Using the available information covering the period of 5 years (1994–1998), the data has been analysed for a possible trend in statistical parameters (50- and 98-percentiles) and number and severity of exceedances. Time series are relatively short but the data suggest that there might be a small increasing trend in the 50 percentile values. The ozone peak values, expressed as 98-percentile values or as number of exceedance days tend to decrease. However, these conclusions must be interpreted carefully as on the short time scales considered here meteorological variations and inter-annual changes may play an important role. The decrease in peak values is most likely caused by the decrease in European ozone precursor emissions since 1990; insufficient data is available to explain the increasing 50-percentile values. Possible explanations are an increase in tropospheric ozone background values caused by a world-wide increase in CH₄, CO and NO_x emissions or a reduced ozone titration by reduced NO_x emissions on the local scale. The data submitted under the ozone directive is insufficient to provide firm conclusions on this point.     

Observation-based sources evolution of non-methane hydrocarbons (NMHCs) in a megacity of China

Both concentrations and emissions of many air pollutants have been decreasing due to implement of control measures in China, in contrast to the fact that an increase in emissions of non-methane hydrocarbons (NMHCs) has been reported. This study employed seven years continuous NMHCs measurements and the related activities data of Shanghai, a megacity in China, to explore evolution of emissions and effectiveness of air pollution control measures. The mixing ratio of NMHCs showed no statistical interannual changes, of which their compositions exhibited marked changes. This resulted in a decreasing trend of ozone formation potential by 3.8%/year (p < 0.05, the same below), which should be beneficial to ozone pollution mitigation as its production in Shanghai is in the NMHCs-limited regime. Observed alkanes, aromatics and acetylene changed by +3.7%/year, -5.9%/year and -7.4%/year, respectively, and alkenes showed no apparent trend. NMHCs sources were apportioned by a positive matrix factorization model. Accordingly, vehicular emissions (-5.9%/year) and petrochemical industry emissions (-7.1%/year) decreased significantly, but the decrease slowed down; significant reduction in solvent usage (-9.0%/year) appeared after 2010; however, emissions of natural gas (+12.6%/year) and fuel evaporation (with an increasing fraction) became more important. The inconsistency between observations and inventories was found in interannual trend and speciation as well as source contributions, emphasizing the need for further validation in NMHCs emission inventory. Our study confirms the effectiveness of measures targeting mobile and centralized emissions from industrial sources and reveals a need focusing on fugitive emissions, which provided new insights into future air policies in polluted region.     

Significant contribution of spring northwest transport to volatile organic compounds in Beijing

High values of ozone (O₃) occur frequently in the dry spring season; thus, understanding the evolution characteristics of volatile organic compounds (VOCs) in spring is of great significance for preventing O₃ pollution. In this study, a total of 101 VOCs from April 16 to May 21, 2019, were quantified using an online gas chromatography mass spectrometer/flame ionization detector (GCMS/FID). The results indicated that the observed concentration of total VOCs (TVOCs) was 30.4 ± 17.0 ppbv, and it was dominated by alkanes (44.3%), followed by oxygenated VOCs (OVOCs) (17.4%), halocarbons (12.7%), aromatics (9.5%), alkenes (8.2%), acetylene (5.3%) and carbon disulfide (2.5%). The average mixing ratio of VOCs showed obvious diurnal variation (high at night, low during daytime). We conducted a source apportionment study based on 32 major VOCs using positive matrix factorization (PMF), and coal + biomass burning (25.2%), diesel exhaust (16.0%), gasoline exhaust + evaporation (17.4%), secondary + long-lived species (16.7%), biogenic sources (4.3%), industrial emissions (9.3%) and solvent use (11.2%) were identified as major sources of VOCs. In addition to local emissions, most of the atmospheric VOCs were derived from long-distance air masses (65.7%), and the average mixing ratio of VOCs in the northwest direction was 29.4 ppbv. Combined with the results of the potential source contribution function (PSCF) indicate that research should focus on the local emissions of combustion, transportation sources and solvents usage to control atmospheric VOCs. Additionally, transmission of the northwest air mass is an important component that cannot be ignored during spring in Beijing.