Enhancements of Major Aerosol Components Due to Additional HONO Sources in the North China Plain and Implications for Visibility and Haze

The Weather Research and Forecasting/Chemistry model(WRF-Chem) was updated by including photoexcited nitrogen dioxide(NO2) molecules,heterogeneous reactions on aerosol surfaces,and direct emissions of nitrous acid(HONO) in the Carbon-Bond Mechanism Z(CBM-Z).Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components.We calculated percentage changes of major aerosol components and concentration ratios of gas NO y(NOyg) to NO y and particulate nitrates(NO-3) to NO y due to the three additional HONO sources in the North China Plain in August of 2007.Our results indicate that when the three additional HONO sources are included,WRF-Chem can reasonably reproduce the HONO observations.Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO,nitrates(NO 3),ammonium(NH + 4),and PM 2.5(concentration of particulate matter of 2.5 μm in the ambient air) across the North China Plain.The three additional HONO sources produced a～5%-20% increase in monthly mean daytime concentration ratios of NO-3 /NO y,a ～15%-52% increase in maximum hourly mean concentration ratios of NO-3 /NO y,and a ～10%-50% increase in monthly mean concentrations of NO-3 and NH+4 across large areas of the North China Plain.For the Bohai Bay,the largest hourly increases of NO-3 exceeded 90%,of NH+4 exceeded 80%,and of PM 2.5 exceeded 40%,due to the three additional HONO sources.This implies that the three additional HONO sources can aggravate regional air pollution,further impair visibility,and enhance the incidence of haze in some industrialized regions with high emissions of NO x and particulate matter under favorable meteorological conditions.     

Intercomparison of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>, SO<Subscript>2</Subscript>, O<Subscript>3</Subscript>, and aromatic hydrocarbons measured by a commercial DOAS system and traditional point monitoring techniques

A field-based intercomparison study of a(DOAS) instrument (OPSIS AB, Sweden) andcommercial Differential Optical Absorption Spectroscopydifferent point-sample monitoring techniques (PM, basedon an air monitoring station, an air monitoring vehicle, and various chemical methods) was conducted inBeijing from October 1999 to January 2000. The mixing ratios of six trace gases including NO, NO2, SO2,03, benzene, and toluene were monitored continuously during the four months. A good agreement betweenthe DOAS and PM data was found for NO2 and SO2. However, the concentrations of benzene, toluene,and NO obtained by DOAS were significantly lower than those measured by the point monitors. Theozone levels monitored by the DOAS were generally higher than those measured by point monitors. Theseresults may be attributed to a strong vertical gradient of the NO-O3-NO2 system and of the aromatics atthe measurement site. Since the exact data evaluation algorithm is not revealed by the manufacturer ofthe DOAS system, the error in the DOAS analysis can also not be excluded.     

The Role of Planetary Boundary-Layer Parameterizations in the Air Quality of an Urban Area with Complex Topography

The effect of different planetary boundary-layer (PBL) parameterization schemes on the spatial distribution of atmospheric pollution over the complex topography of the greater Athens area is investigated. Four PBL schemes originally implemented in a numerical meteorological model and a fifth one simulating the urban effect are examined. Two different atmospheric conditions are analyzed; a typical summer and a typical winter pollution episode. The relative importance of chemical and physical processes of the pollution predictions is discussed using process analysis. It is revealed that, for primary pollutants, a local scheme seems more adequate to represent the maximum observed concentrations while, completely different in structure, a non-local scheme reproduces the mean observed values in the basin. Concerning secondary pollutants, peak concentration differences, due to the different PBL schemes, are smoothed out. Nevertheless, the PBL scheme selection shapes the horizontal and the vertical extension of maximum values. The non-local and semi non-local schemes are superior to the others, favouring strong vertical mixing and transport towards the surface. The stronger turbulence accommodated effectively by the semi non-local urban scheme enhances ozone production along the sea-breeze axis and preserves the high ozone concentrations during the nighttime hours in the urban core.     

对流层物质垂直交换模式中的参数化处理

为了研究对流层(TL)中垂直涡旋扩散系数(K_z)随高度变化的参数化形式对物质垂直交换的贡献,用“高分辨TL物质交换模式”(EM3)对5种不同K_z型进行了数值对比模拟,结果表明:KK_z型较好地描述了行星边界层(PBL)内受下垫面影响的高频湍流和PBL以上TL由各种动力学和热力学过程产生的切变湍流;垂直运动和K_z对PBL下层的物质输送到TL上层和从源高度向下输送到PBL低层两者均有重要作用;垂直运动的作用具有间隙性,而K_z是连续的.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> change over China and its influences

A 3-D chemical transport model (OSLO CTM2) is used to investigate the impact of the increase of NOx emission over China. The model is capable to reproduce basically the seasonal variation of surface NOx and ozone over eastern China. NOx emission data and observations reveal that NOx over eastern China increases quite quickly with the economic development of China. Model results indicate that NOx concentration over eastern China increasingly rises with the increase of NOx emission over China, and accelerates to increase in winter. When the NOx emission increases from 1995 to its double, the ratio of NO2/NOx abruptly drops in winter over northern China. Ozone at the surface decreases in winter with the continual enhancement of the NOx level over eastern China, but increases over southern China in summertime. It is noticeable that peak ozone over northern China increases in summer although mean ozone changes little. In summer, ozone increases in the free troposphere dominantly below 500 hPa.Moreover, the increases of total ozone over eastern China are proportional to the increases of NOx emission.In a word, the model results suggest that the relationship between NOx and ozone at the surface would change with NOx increase.     

全边界层选用相似理论对O3、NOx浓度及沉降的影响

将广泛应用于东亚地区的LLA(Lurmann Lloyd Atkinson)化学机制耦合到欧拉型区域空气质量模式(RAQM),并考虑区域污染物长期模拟研究中降水随时间变化的非均匀性,讨论了湍流参数化过程中相似理论在近地层和全边界层的应用对湍流垂直扩散系数(Kz)与干沉降速度(V),O3与NOx浓度的影响。结果表明,全边界层应用相似理论明显低估了Kz值,近地层50m处Kz值被低估20%以上,750m处其值被低估约70%;O3、NOx的干沉降速度在日本东部与南部海域被低估了10%以上,在朝鲜半岛东部和西部海域模拟值普遍偏高。Kz和干沉降速度的不同直接影响污染物的浓度和沉降量分布。Kz值的被低估对NOx浓度有明显影响,在近地层50m处NOx浓度最大可增加约30%,整个边界层中NOx平均浓度除台湾省东北海域外普遍增加5%~20%。O3浓度则受干沉降作用的影响较大。虽然近地层、全边界层分别应用相似理论都较好地模拟了O3与NOx峰值浓度出现的时间,但相似理论应用于全边界层会引起较大的误差。即使是大区域、长期空气质量模拟研究,也建议相似理论仅应用于近地层,且模式第一层高度应设置在常通量层内。     

边界层方案对华北低层O3垂直分布模拟的影响

利用WRF-Chem模式,采用3种边界层参数化方案 (YSU, MYJ和ACM2),针对1个晴空、静稳日 (2013年8月26日20:00—27日20:00(北京时)) 进行模拟,着重分析不同边界层参数化方案对夜间残留层形成及日出前后O₃浓度垂直分布形式的模拟效果,并与固城站地面及垂直同步观测资料进行对比。结果表明:3种边界层参数化方案均能够模拟出温度及风速的区域分布形式以及风温垂直结构的变化特征;相比之下,MYJ方案模拟的夜间边界层高度较YSU方案和ACM2方案明显偏高,该对比结果可能是导致近地面污染物浓度模拟差异的重要原因;在夜间稳定层结至日出后稳定状态打破的边界层结构演变过程中,采用YSU方案和ACM2方案模拟的温度和风速垂直扩线形式与观测结果更为接近;同样采用非局地闭合的YSU方案和同时考虑局地和非局地闭合的ACM2方案,对于边界层高度内O₃浓度垂直分布形式的模拟效果具有明显优势。     

Sensitivity of PBL model predictions to model design and uncertainties in environmental inputs

A simple time-dependent one-dimensional model of the planetary boundary layer (PBL) is described and used to examine the degree to which model design decisions affect model output variables. The model's sensitivity to changes in the environmental conditions is also explored. Averages of the surface fluxes, near-ground wind speeds and other PBL properties from 48 h simulations are compared to control runs. The model-calculated surface fluxes are most sensitive, in decreasing order of importance, to the vertical grid spacing, the form of closure between the surface temperature and the atmosphere, the use of vertical diffusivity smoothing, the choice of maximum time step and choice of turbulence closure scheme. These fluxes are relatively insensitive to mixing-length scaling or choice of implicit time step weighting factor. Sensitivity to changes in soil type exceeds any of the design criteria tested. The modeled fluxes are moderately sensitive to small variations in the horizontal pressure gradient, to unsteadiness in the geostrophic wind and to variations in surface roughness. They are relatively insensitive to uncertainties in local vertical velocities and small (25%) variations applied separately to soil thermal diffusivity or heat capacity. The sensitivity of the average PBL depth (Z _i ) to model and environmental changes are similar to those of surface fluxes except thatZ _i is more sensitive to changes in mixing length, albedo and imposed vertical velocity then are the surface fluxes.     

Estimates of anthropogenic CO<Subscript>2</Subscript> uptake in a global ocean model

A global ocean general circulation model (L30T63) is employed to study the uptake and distribution of anthropogenic CO₂ in the ocean. A subgrid-scale mixing scheme called GM90 is used in the model. There are two main GM90 parameters including isopycnal diffusivity and skew (thickness) diffusivity. Sensitivities of the ocean circulation and the redistribution of dissolved anthropogenic CO₂ to these two parameters are examined. Two runs estimate the global oceanic anthropogenic CO₂ uptake to be 1.64 and 1.73 Pg C yr^-1 for the 1990s, and that the global ocean contained 86.8 and 92.7 Pg C of anthropogenic CO₂ at the end of 1994, respectively. Both the total inventory and uptake from our model are smaller than the data-based estimates. In this presentation, the vertical distributions of anthropogenic CO₂ at three meridional sections are discussed and compared with the available data-based estimates. The inventory in the individual basins is also calculated. Use of large isopycnal diffusivity can generally improve the simulated results, including the exchange flux, the vertical distribution patterns, inventory, storage, etc. In terms of comparison of the vertical distributions and column inventory, we find that the total inventory in the Pacific Ocean obtained from our model is in good agreement with the data-based estimate, but a large difference exists in the Atlantic Ocean, particularly in the South Atlantic. The main reasons are weak vertical mixing and that our model generates small exchange fluxes of anthropogenic CO₂ in the Southern Ocean. Improvement in the simulation of the vertical transport and sea ice in the Southern Ocean is important in future work.     

适用于GRAPES模式C-P边界层方案的设计和实现

基于K廓线闭合方案,通过考虑不稳定边界层和稳定边界层中热量交换系数在半层上求取及下边界条件的设置,将温湿倾向在整层上直接计算,设计了Charney-Phillips跳点（简称C-P跳点）的边界层方案,使之与GRAPES全球模式的C-P跳点相协调,解决了Lorenz跳点物理过程与C-P跳点动力框架耦合时插值造成的不协调问题,同时避免了耦合时反复插值造成的误差,提高了边界层物理过程参数化方案及其反馈的准确性和合理性。试验表明:C-P跳点边界层方案因为避免了温度和湿度在垂直方向上的插值,消除了温湿变量在垂直方向上的锯齿状抖动,使温湿廓线分布更合理,减小了模式预报误差,形势场的预报效果也得到一定改善。C-P边界层方案的应用提升了GRAPES全球模式的总体预报性能。     

Evaluation of the use of photochemical indicators to assess ozone—NOx—VOC sensitivity in the Southwestern Iberian Peninsula

Understanding the chemical links between ozone (O₃) and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), is important for designing effective photochemical smog reduction strategies. This chemical relationship will determine which precursor (NOx or VOC) emission reduction will be more effective for decreasing the ozone formation. Under certain conditions, ozone levels decrease as a result of a reduction in NOx emissions but do not respond significantly to changes in VOC emissions (NOx-sensitive condition), while under other conditions ozone concentrations decrease in response to reductions in VOCs and may even increase when NOx emissions are reduced (VOC-sensitive conditions). Indicator species can be used to assess the sensitivity of ozone to changes in the emissions of its precursors. These indicators are species or species ratios involved in ozone photochemistry which reflect the primary chemical process through which the ozone was formed. In this work we use the MM5-CAMx model system to explore the behaviour of various indicator species during two meteorological situations featuring different atmospheric conditions in a complex terrain area. The results show that indicators based on nitrogen compounds (i.e,. NOy and NOz) are suitable for defining the transition range from VOC- to NOx-sensitive chemistry, and that despite the uncertainties associated with the use of chemical indicators, the ratios O₃/NOy and O₃/NOz may provide a simple and useful way to summarize the response of ozone to changes in NOx and VOC emissions in Southwestern Spain.     

Variations in CO,O<Subscript>3</Subscript> and black carbon aerosol mass concentrations associated with planetary boundary layer (PBL) over tropical urban environment in India

Carbon monoxide (CO), Ozone (O₃) and Black Carbon (BC) aerosol mass concentrations in relation to planetary boundary layer (PBL) height measurements were analyzed from January–December, 2008 over tropical urban environment of Hyderabad, India. DMSP-OLS night-time satellite data were analyzed for fire occurrence over the region and its correlation with pollution concentrations over the urban region. Results of the study suggested considerable increase in CO and BC concentrations during early morning hours. Higher concentration of BC, CO and ozone was observed during pre-monsoon, post-monsoon and winter and lowest concentrations exhibited during monsoon season. NCEP/NCAR reanalysis winds suggested long range transport of aerosols and trace gases from forest fires are enhancing the pollutant concentrations over the study area.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

边界层参数化和湿过程对切变线低涡发展影响的中尺度模拟

1981年8月14至22日,在青藏高原东侧陕、甘、川毗邻区,出现了一次持续暴雨过程.对其主过程的涡度诊断表明,切变线低涡初生於青藏高原东侧低空,其后,不仅出现了高、低空涡度中心的叠加和耦合过程,而且在行星边界层(PBL)内发生了迅速加强过程.这种过程与切变低涡的持续发展相伴. 一系列48和72小时中尺度数值模拟结果揭示:只有高分辨PBL参数化的湿物理过程,才能较好地模拟出切变低涡在PBL内的突然加强及其涡度演变和垂直结构;而总体PBL参数化,虽然其涡度演变和垂直结构也能基本模拟出来,但不能模拟出切变线低涡在PBL内的迅速加强;总体PBL参数化干过程的模拟结果指出,该方案较前两种湿过程方案均差,特别是被模拟系统的强度明显减弱,位置偏离. 模拟与诊断和观测之间的比较揭示,尽可能仔细地改进PBL参数化和湿物理过程,才有可能改进对这类中尺度系统发生和发展的模拟.     

An empirical model for estimating stratospheric ozone vertical distributions over China

Based on the Stratospheric Aerosol and Gas Experiment (SAGE) II and the Halogen Occultation Experiment (HALOE) ozone profiles and the Total Ozone Mapping Spectrometer (TOMS) total ozone data sets, an empirical model for estimating the vertical distribution of stratospheric ozone over China is proposed. By using this model, the vertical distribution of stratospheric (16–50 km) ozone can be estimated according to latitude, month and total ozone. Comparisons are made between the modeled ozone profiles and the ...     

A HIGH RESOLUTION MODEL FOR CHEMICAL SPECIES EXCHANGE IN TROPOSPHERE

Based on the regional acid deposition model(RADM),a high resolution model for species exchange in thetroposphere(EM3)is designed.EM3 differs considerably in the following 5 aspects from RADM.First,the vertical gridlevels in the planetary boundary layer(PBL)are increased.Second,layered vertical eddy diffusivity patterns in thetroposphere(TL)are considered.Third,layered horizontal eddy diffusivity patterns within TL is used.Fourth,new drydeposition velocity pattern including the effect of plant canopy layer(CL)vertical structure is adopted.Fifth,advectivescheme of second-order moment conservation with less numerical diffusion is used.OSCAR 4 case is comparativelysimulated with both EM3 and RADM.The results show that 3-D distribution laws of chemical species in whole TL areforecasted by EM3 better than by RADM.Under the same conditions,all ratios of the central concentrations simulatedwith both models in lower PBL are more than 1.8,the maximum can be more than 3.     

A parameterization of the nocturnal ozone reduction in the residual layer by verticla downward mixing during summer smog situations using sodar data

The reduction of ozone in the nocturnal residual layer by vertical mixing to the surface was investigated for several summer smog episodes on the Swiss plateau in the years 1990 and 1991. Using a limited data set of SODAR measurements and surface ozone concentrations, a parameterization of the ozone depletion in the nocturnal residual layer due to vertical mixing to the ground is proposed. This model is not intended to be physically complete but is rather simple with limited input information required. The nocturnal ozone reduction within the whole planetary boundary layer (nocturnal boundary layer plus residual layer) over the complex terrain of the Swiss plateau for the days investigated is between 20 and 50%.     

A numerical method for determining the dry deposition of atmospheric trace gases

A diagnostic deposition model based on generally accepted micrometeorological ideas on the transfer of momentum, sensible heat and matter near the Earth's surface is presented. The parameterization of fluxes is based on the flux-gradient relationships in the turbulent region of the surface layer and the sublayer Stanton number as well as the Reynolds analogy between concentration, temperature and wind velocity distributions in the underlying sublayer. The model requires only vertical profile data of wind velocity, dry- and wet-bulb temperatures and trace gas concentrations from the turbulent part of the surface layer.The method has been applied to vertical profile data collected in field experiments such as the GREIV I 1974 project and the Great Plains Turbulence Project. In order to illustrate the way in which the model can be used to evaluate deposition fluxes and velocities of reactive trace gases, it has been applied to observed concentrations of NO, NO₂ and ozone.Presented at the Symposium on Environmental Meteorology, Würzburg, FRG, September 29 to October 1, 1987.     

利用探空资料验证GOME卫星臭氧数据

利用1996年3月-2003年6月部分时段拉萨、西宁、北京3个站的臭氧探空资料验证了GOME（Global Ozone Monitoring Experiment）卫星臭氧廓线及对流层臭氧柱总量。对比结果表明:在对流层中下层,拉萨和西宁两地GOME与探空的平均偏差小于5%,北京地区平均偏差小于10%;在对流层上层/平流层下层,拉萨和西宁平均偏差小于10%,北京小于20%;在平流层中上层3个站的平均偏差均小于5%。在对流层上层/平流层下层区域,GOME与臭氧探空的平均偏差在北京明显高于拉萨和西宁。3个地区对流层柱总量的平均偏差都在10%以内,表明该资料可用于研究我国对流层臭氧总量的变化规律。同时段的GOME最低层（0~2.5km）月平均臭氧浓度对比结果显示,GOME结果同地面臭氧观测值有很好的相关性,GOME臭氧浓度反映了拉萨、瓦里关、临安地面臭氧浓度的主要变化特征。