热带深对流云对CO、NO、NOx和O3的垂直输送作用

利用2005年11月至2006年2月ACTIVE (Aerosol and Chemical Transport in tropIcal conVEction) 外场试验期间在澳大利亚北部达尔文地区取得的CO、O3、NO和NOx飞机探测资料, 并结合HYSPLIT后向轨迹模式结果, 分析这几种气体成分在对流卷云砧内外的分布情况, 并探讨热带深对流云对于污染气体的垂直输送作用。分析结果显示, 在孤立对流云卷云砧中, 云砧内部O3、NO、NOx浓度均大于云外; 而CO则不同, 只有在近地面浓度高时才如此, 在近地面浓度较小时, 卷云砧内部的浓度反而小于云外。进一步分析造成这两类气体分布差异的原因, 发现CO主要借助深对流云将对流层下层以及对流云周围环境中的CO夹卷并动力垂直输送到对流云顶部卷云砧中, 而对于O3、NO和NOx来说, 除了上述作用以外, 还可能与对流云内部其他物理机制(如闪电), 造成新的O3、NO和NOx有关, 这些新生气体随着风暴内部强烈的上升气流被最终输送进云砧中。     

应用查表法模拟区域对流层O3、Nox分布和演化的研究

应用STEM-II气相光化学模式探讨了影响对流层O3、NOx气相光化学转化率的各物理、化学因子。表明在我国多数地区光化学污染物特征(NMHC/NOx较高)下,光辐射强度、温度、初始O3浓度和NOx浓度是影响O3、NOx气相光化学转化率的主要因子。将以上因子分档组合,计算并建立了各种情况下O3、NOx气相光化学转化率的查算表,并将之用于模拟区域O3、NOx的演化和分布。结果表明,与光化学模式直接耦合计算法相比,该方法既能显著缩短计算时间,又能基本反映大气化学反应的非线性过程,并与直接耦合法符合得较好。     

三维对流云对大气光化学组分的再分布作用及其化学效应

利用一个三维的冰雹云模式与化学组分输送模块耦合，得到云输送引起大气光化学组分的再分布，然后用一个包含详细气相化学反应机制的箱模式研究了云输送引起的气相体积分数的变化及其对大气化学系统产生的影响。结果表明，云输送后O3体积分数大于无云个例，但其后两天内两者的变化趋势相差不大；HNO3、NO2、NO3、PAN等的体积分数均明显高于无云个例，分别增长了87％、70％、62％和49％，其中NO2体积分数的增加主要由于云输送造成，而NO3、HNO3、PAN主要是输送对化学扰动的结果。两天内OH和HO2自由基体积分数比无云个例平均增长了13％和11％。     

区域化学输送模式中NOx和O3源示踪法的引入

发展了化学输送模式中氮氧化合物(NOx)和臭氧(O3)的一种源示踪方法,对这种示踪法及其应用模式作了详细介绍,并结合臭氧光化学反应机理的分析描述了NOx和O3示踪物浓度方程的推导过程。将这种示踪法引用到区域化学输送模式中,并以太原和石家庄地表NOx人为排放产生的活性氮化物和臭氧为例,演示了污染物向北京的输送过程,模拟的O3,NOx和NOz示踪物浓度时空分布与O3,NOx和NOz在大气中的衰减尺度分析一致,表明该示踪法是一种有效的研究区域氮氧化物以及臭氧来源和输送转化过程的方法。个例模拟分析结果显示:太原和石家庄的地表人为排放产生的NOx本身并不能输送到北京,但通过它们产生的O3和HNO3可以输送到北京,对北京地表附近大气污染造成影响。     

对流层O3区域输送的定量评估方法研究

主要介绍一个可用于化学输送模式的对流层O3来源和过程追踪技术。该方法可定量估算不同区域的光化学反应通过输送过程对目标地区O3浓度的贡献,并且克服了光化学非线性特征对估算结果的影响。以研究2001年中国南部和北部光化学生成O3的输送为例,通过与改进的敏感性分析方法比较,系统评估了该方法的合理性。比较结果表明,两种方法的估算结果在水平、垂直分布和典型输送个例等方面具有良好的一致性,说明污染物来源和过程追踪技术可以为量化区域输送对目标地区O3浓度的影响提供合理结果。个例模拟分析的结果也表明,中国南部和北部光化学生成的O3可以通过输送对整个东亚O3产生重要影响,并且在不同的季节呈现不同的特征。     

青藏高原深对流及其在对流层—平流层物质输送中作用的研究进展

深对流能够向上对流层—下平流层（UTLS）输送大量水汽和污染物,对对流层顶的辐射平衡、平流层的臭氧恢复以及全球气候变化都有着重要的影响。近年来,一系列重要的观测事实发现,青藏高原和亚洲季风区是对流层向平流层物质输送（TST）的重要窗口。本文介绍了近年来取得的一些主要进展和成果,包括:（1）通过卫星观测在青藏高原—亚洲季风区上空发现水汽、气溶胶的极大值区和臭氧的极小值区;（2）深对流活动的主要观测途径和通过卫星观测识别深对流的方法;（3）青藏高原深对流向平流层物质输送的物理过程;（4）青藏高原深对流与亚洲季风区、热带海洋地区深对流的结构差异以及不同环境场对深对流物质输送过程的影响。     

应用查表法模拟区域对流层O3、Nox分布和演化的研究

应用STEM-II气相光化学模式探讨了影响对流层O3、NOx气相光化学转化率的各物理、化学因子。表明在我国多数地区光化学污染物特征(NMHC/NOx较高)下，光辐射强度、温度、初始O3浓度和NOx浓度是影响O3、NOx气相光化学转化率的主要因子。将以上因子分档组合，计算并建立了各种情况下O3、NOx气相光化学转化率的查算表，并将之用于模拟区域O3、NOx的演化和分布。结果表明，与光化学模式直接耦合计算法相比，该方法既能显著缩短计算时间，又能基本反映大气化学反应的非线性过程，并与直接耦合法符合得较好。     

一次对流层异常臭氧次峰的观测研究及其动力输送过程的分析

文中分析了 1996年 8月 1日发生在西宁 (36 .4 3°N ,10 1.4 5°E ,海拔 :2 2 96m)地区对流层异常臭氧次峰现象。观测资料揭示了高空低压槽东移是臭氧次峰的主要天气特征。三维后向轨迹计算表明 ,尽管代表臭氧次峰的气团可以追溯到中亚地区 ,但是明显的气团向下输送则发生在新疆、青海间的高空低压槽内。中尺度模拟进一步确认了对流层顶折叠和平流层向下输送是臭氧次峰出现的动力机制。臭氧次峰在对流层高度位置与准无辐散层有关     

NOx与NMHC的变化对O3 生成量的影响

利用LLA-C光化学反应机制,在NOx体积分数φ变化范围很广（1.75～350.0,单位为10-9,以下同）的条件下,选择18种NMHC与NOx的体积分数比（2.0～200.0）模拟分析在什么条件下NMHC的改变对臭氧生成量不大敏感而主要依赖于NOx的大小,同时给出相应条件下OH模拟值的变化。结果表明,OH峰值均出现在φ(NMHC/NOx)≈8.0。所找条件是φ(NOx)≤50.0时要求φ(NMHC/NOx)≥60.0;φ(NOx)>50.0时需要8.0≤φ(NMHC/NOx)≤28.0。相应O3生成量的最大误差小于20%。该条件正适合我国典型污染城市当前φ(NOx)水平和φ(NMHC/NOx)范围,可用于我国区域尺度空气质量模拟。与实测资料的对比还有待进一步开展。     

我国北方地区对流层中下层臭氧收支

为了揭示我国北方地区对流层中下层臭氧(O₃) 的形成机理以及周边地区的污染输送对我国北方地区对流层中下层O₃收支的影响, 在与外场观测数据比较分析的基础上, 利用全球化学输送模式(MOZART-2) 采用收支分析方法定量分析了影响我国北方地区对流层中下层O₃的各个物理化学过程。结果表明:我国北方地区对流层下层O₃最重要的来源是光化学生成作用, 约占总来源的58.3%(41.5 Tg), 光化学生成反应中HO₂对于O₃生成的贡献最大; 最大的汇是干沉降过程, 约占总汇的43.2%(26.2Tg); 水平净输送作用对我国北方地区对流层中下层O₃收支的影响非常大, 在我国北方地区对流层下层, 41.6%左右的O₃来自水平净输送, 随高度增加, 水平输送影响增大, 我国北方地区对流层中层大约81.5%的O₃来自水平净输送。     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 2. Model Chemistry and Comparison of Modelled CH4, CO, and O3 with Surface Measurements

In part two of this series of papers on the IMS model, we present the chemistry reaction mechanism usedand compare modelled CH₄, CO, and O₃ witha dataset of annual surface measurements. The modelled monthly and 24-hour mean tropospheric OH concentrationsrange between 5–22 × 10⁵ moleculescm^–3, indicating an annualaveraged OH concentration of about 10 × 10⁵ moleculescm^–3. This valueis close to the estimated 9.7 ± 0.6 × 10⁵ moleculescm^–3 calculated fromthe reaction of CH₃CCl₃ with OH radicals.Comparison with CH₄ generally shows good agreementbetween model and measurements, except for the site at Barrow where modelledwetland emission in the summer could be a factor 3 too high.For CO, the pronounced seasonality shown in the measurements is generally reproduced by the model; however, the modelled concentrations are lower thanthe measurements. This discrepancy may due to lower the CO emission,especially from biomass burning,used in the model compared with other studies.For O₃, good agreement between the model and measurements is seenat locations which are away from industrial regions. The maximum discrepancies between modelled results and measurementsat tropical and remote marine sites is about 5–10 ppbv,while the discrepancies canexceed 30 ppbv in the industrial regions.Comparisons in rural areas at European and American continental sites arehighly influenced by the local photochemicalproduction, which is difficult to model with a coarse global CTM.The very large variations of O₃ at these locations vary from about15–25 ppbv in Januaryto 55–65 ppbv in July–August. The observed annual O₃amplitude isabout 40 ppbv compared with about 20 ppbv in the model. An overall comparison of modelled O₃ with measurements shows thatthe O₃seasonal surface cycle is generally governed bythe relative importance of two key mechanisms that drivea springtime ozone maximum and asummertime ozone maximum.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 3. Comparison of Modelled C2–C5 Hydrocarbons with Surface Measurements

In part 3 of this series of papers on a new 3-D global troposphericchemical transport model, using an Integrated Modelling System (IMS), anevaluation of the model performance in simulating global distributions andseasonal variations for volatile organic compounds (VOCs) in the atmosphere,is presented. Comparisons of model OH concentrations with previous modelstudies show consistent modelled OH levels from the subtropics tomidlatitudes, while more discrepancies occur over the tropical lowlatitudes, with IMS predicting the highest levels of OH. The close agreementbetween modelled OH concentrations over midlatitudes, where high surfaceNO_xand VOC concentrations are also found, is indicative of the strongphotochemical coupling between NO_x, VOCs and O₃ overthese latitudes. IMSOH concentrations in the Northern Hemisphere (NH) midlatitudes during summerare generally lower than available measurements, implying that models ingeneral are underestimating OH levels at this location and time of year.Substantial differences between model OH concentrations over low latitudesclearly highlight areas of uncertainty between models. IMS OH concentrationsare the highest in general of the models compared, one possible reason isthat biogenic emissions of species such as isoprene and monoterpenes arehighest in IMS, leading to higher O₃ levels and hence higher OH.Generally, the IMS VOC concentrations show a similar seasonality to themeasurements at most locations. In general though, IMS tends to underestimatethe NH wintertime VOC maximum and overestimate the NH summertime VOCminimum. Such an overestimate in summer could be due to IMSunderestimating OH levels, or an overestimation of VOC emissions or possiblya problem with model transport, all of these possibilities are explored.Except for n-pentane, the model underprediction of a VOC maximum during theNH winter month strongly suggests a missing emission mechanism in the modelor an underestimate of an existing one. It is very likely that there is alack of time varying emission sources in the model to account for theseasonal change in emission behaviour such as increasing energy usage (e.g.,electricity and gas), road transportation, engine performance, and otheranthropogenic factors which show strong seasonal characteristics. Theanomalous overprediction of wintertime n-pentane compared with its closesummertime prediction with the measurements suggest that emissions in thiscase may be too high.     

利用卫星资料分析对流层臭氧柱总量分布特征及其可能的原因

利用卫星资料计算得到的对流层臭氧柱总量数据分析了近20年来全球对流层臭氧柱总量的全球分布特征,并对我国对流层臭氧的季节变化做了研究。利用对流层污染测量仪（MOPITT）的CO和全球臭氧监测仪（GOME）和大气制图扫描成像吸收光谱仪（SCIAMACHY）的NO2数据分析了关于对流层臭氧的分布特征及其原因。得出中高纬度地区对流层臭氧浓度存在规律的年内变化,对流层臭氧高浓度值的分布及变化与人类活动有密切关切。     

The Radiative-Dynamical Effects of High Cloud on Global Ozone Distribution

Previous studies (e.g., Dessler et al., 1996; Haigh, 1984) have discussed the effect of cloud on modelled ozone distribution through changes in the radiative heating in the lower stratosphere. Here the relationship is investigated using an interactive chemical-radiative- transport 2D model. It is shown that, while similar cooling in the lower stratosphere due to high cloud is found, the effect on ozone is not as previously expected. The inclusion of high cloud is found to bring about a warming of the troposphere, resulting in a net heating in the lower stratosphere. This strengthens the circulation, leading to a decrease in total tropical ozone. Importantly, the effect of the cloud-induced temperature changes on heating rates does not combine linearly with the direct radiative effect of cloud changes. The possibility of a link between the high cloud increases and total ozone decreases observed in some regions during strong El Niño episodes is investigated. The possible impact on ozone of a global trend in high cloud cover is also discussed.     

Identifying the Origin of Anomalous High Tropospheric Ozone in the Ozonesonde Data at Uccle by Comparison with Nearby De Bilt

Abstract

The ozonesonde stations at Uccle (Belgium) and De Bilt (Netherlands), separated by only 175?km, offer a unique opportunity to test the influence of different ozonesonde types and different correction strategies, as well as to detect the presence of inhomogeneities in the ozonesonde time series resulting from changes in sounding equipment (solution, radiosonde, ozonesonde, interface, sounding software, etc.). In particular, we highlight a 2.5 year period (beginning of 2007 to mid-2009) of anomalous high tropospheric ozone values measured by ozonesondes at Uccle and compare these with the observations from De Bilt. Because the ozone deviations are only observed in the free troposphere where ozone concentrations are relatively low, and not in the boundary layer or the stratosphere, this issue is directly related to the sensitivity of ozonesondes. Therefore, the effect of every instrumental change, even though small, during this 2.5 year anomalous period is analyzed considering a change in the radiosounding equipment, different ozonesonde batches, operational differences at the stations, differences on ascent and descent during the anomalous period; an environmental cause is also examined. Unfortunately, one single, specific cause for the observed high tropospheric ozone values at Uccle could not be identified. There are two explanations consistent with the observations and not ruled out by the analysis here: 1) the majority of the ozonesondes used at Uccle between March 2007 and August 2009 needed longer conditioning of their sensors and, therefore, behaved more accurately at low ozone concentrations during their descent or when used a second time, and 2) an environmental origin arising from a local difference in the air mass between Uccle and De Bilt and between the ascent and descent.     

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.     

高NOx条件下非甲烷烃体积分数的变化对O3生成量的影响

利用ＬＬＡ－Ｃ光化学反应机制,在ＮＯＸ保持高值不变时,模拟分布范围很广的８种初始［ＮＭＨＣ］／［ＮＯｘ］（１０９／１０９）（１．０、３．０、７．１、１４．３、２８．６、５７．２、１００．０、２００．０）条件下臭氧体积分数的变化。模拟结果表明,当［ＮＭＨＣ］／［ＮＯｘ］≥１５．０时,臭氧生成量对ＮＭＨＣ的改变不大敏感而主要依赖于ＮＯｘ的大小。但是,当非甲烷烃与氮氧化物的比北较低（＜７．０）时,臭氧生成量紧密地依赖于非甲烷烃体积分数。进一步的验证工作还有待于加强。     

Tropospheric Box-Modelling and Analytical Studies of the Hydroxyl (OH) Radical and Related Species: Comparison with Observations

Calculated and observed hydroxyl (OH) fields are presented. Calculated OH was obtained in three ways using (1) a photochemical box-model (2) a simple OH steady state approach and (3) a variant on (2) – the multiple equation steady state approach which assumes steady state for OH, HO2 and RO2 and hence obtains three simultaneous, non linear, equations. All three methods used data collected in June 1995 during the Weybourne Atmospheric Observatory Summer Experiment (WAOSE'95). Julian Days 169, 178, 179 and 180 displayed especially good data capture and were consequently chosen for study. The two steady state methods are essentially driven purely by observations and derive OH from the ratio of the relevant source and sink terms. The box-model was constrained where possible to observations; remaining unmeasured volatile organic compounds (VOCs) were initialised to an arbitrary low value of 10 ppt. Agreement between theory and experiment was usually around 50% and often better than this value, especially on J169, though discrepancies of up to a factor of 3 were occasionally apparent. Despite the inherent scatter, neither the box-model nor the simple steady state method were found to consistently over-estimate OH (a common feature of many numerical approaches) although this did occur to a certain extent using the multiple equation steady state approach, probably due to breakdowns in the steady state approximation. More data spread was evident in the box-model approach compared with the other methods. An analysis of the major sources and sinks of OH is presented for the three methods of calculation. Calculated and observed peroxy radicals are also presented. Calculated peroxy radicals were generally lower than that observed at night yet higher, sometimes by up to a factor of 7, during the day. Possible explanations for this result are explored.