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.     

A numerical study of tropospheric ozone in the springtime in East Asia

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ)coupled with the Regional Atmospheric Modeling System (RAMS)is applied to East Asia to study the transport and photochemical transformation of tropospheric ozone in March 1998．The calculated mixing ratios of ozone and carbon monoxide are compared with ground 1evel observations at three remote sites in Japan and it is found that the model reproduces the observed features very well．Examination of several high episodes of ozone and carbon monoxide indicates that these elevated levels are found in association with continental outflow,demonstrating the critical role of the rapid transport of carbon monoxide and other ozone precursors from the continental boundary layer．In comparison with available ozonesonde data,it is found that the model-calculated ozone concentrations are generally in good agreement with the measurements,and the stratospheric contribution to surface ozone mixing ratios is quite limited．     

复杂地形上气象场对空气质量数值模拟 结果影响的研究

利用WRF模式三种边界层参数化方案(YSU、MYJ、ACM2)产生的气象场分别驱动多尺度空气质量模式CMAQ,对兰州市西固区冬季2005年1月27日至2月2日期间SO₂和NO₂浓度进行了数值模拟,将模拟结果与同期监测的污染物浓度进行对比分析,结果表明:WRF模式不同边界层参数化方案模拟输出的气象场驱动CMAQ模式所模拟的SO₂和NO₂浓度均可以反映出污染物的时空变化特征,CMAQ模式具有模拟复杂下垫面高分辨率污染物输送特征的能力;WRF模式的边界层参数化方案选为局地与非局地闭合方案(ACM2)时,模拟的气象场驱动CMAQ模式得到的空气污染物浓度分布特征最优,这主要是由于ACM2的湍流输送机制较为合理,模拟的边界层低层气象场更接近实际,从而可以较好地模拟污染物的输送特征;当CMAQ模式的垂直混合方案与WRF模式的湍流输送方案一致时(均采用ACM2方案),模式间的兼容性好.     

A 10-year study of background surface ozone concentrations on the island of Gozo in the Central Mediterranean

A 10-year study of surface ozone mixing ratios in the Central Mediterranean was conducted based on continuous ozone measurements from 1997 to 2006 by a background regional Global Atmospheric Watch (GAW) station on the island of Gozo. The mean annual maximum mixing ratio is of the order of 66 ppbv in April–May with a broad secondary maximum of 64 ppbv in July–September. No long-term increase or decrease in the background level of surface ozone could be observed over the last 10 years. This is contrary to observations made in the Eastern Mediterranean, where a slow decrease in the background ozone mixing ratio was observed over the past 7 years. Despite the very high average annual ozone mixing ratio exceeding 50 ppbv—in fact, the highest average background ozone mixing ratio ever measured in Europe—, the diurnal O _{3 max}/O _{3 min} index of <1.40 indicates that the island of Gozo is a good site for measuring background surface ozone. However, frequent photosmog events from June to September during the past 10 years with ozone mixing ratios exceeding 90 ppbv indicate that the Central Mediterranean is prone to long-range transport of air pollutants from Europe by northerly winds. This was particularly evident during the so-called “August heatwave” of the year 2003 when the overall ozone mixing ratio was 4.6 ppbv higher than the average of all other 9 months of August since 1997. Air mass back-trajectory analysis of the August 2003 photosmog episodes on Gozo confirmed that ozone pollution originated from the European continent. Regression analysis was used to analyse the 10-year data set in order to model the behaviour of the ozone mixing ratio in terms of the meteorological parameters of wind speed, relative humidity, global radiation, temperature, month of year, wind sector, atmospheric pressure, and time of day (predictors). Most of these predictors were found to significantly affect the ozone mixing ratios. From March to November, the monthly average of the AOT40 threshold value for the protection of crops and vegetation against ozone was constantly exceeded on Gozo during the past 10 years.     

A Technique for Estimating Polar Ozone Loss: Results for the Northern 1991/92 Winter Using EASOE Data

In this paper we describe a technique for estimating chemical ozone loss in the Arctic vortex. Observed ozone and temperature profiles are combined with the model potential vorticity field to produce time series of vortex averaged ozone mixing ratios on chosen isentropic surfaces. Model-derived radiative heating rates and observed vertical gradients of ozone are then used to estimate the change in ozone that would occur due to diabatic descent. Discrepancies with the observed ozone are interpreted as being of chemical origin, assuming that there is negligible horizontal transport or mixing of air into the vortex. The technique is illustrated using ozone sonde measurements collected during the 1991/92 European Arctic Stratospheric Ozone Experiment (EASOE), meteorological analyses from the European Centre for Medium-range Weather Forecasts (ECMWF) and radiative heating rates extracted from the Global Atmospheric Modelling Programme (UGAMP) 3D General Circulation Model. Our results show that there was photochemical ozone destruction inside the Arctic vortex in early 1992 with a loss between 475 K and 550 K (around 20 km) of 0.32±0.15 ppmv in the first 20 days of January, equivalent to a rate of 0.51±0.24%/day (at the 95% confidence level).     

Interpretation of Mid-Stratospheric Arctic Ozone Measurements Using a Photochemical Box-Model

In this study measurements of mid-stratospheric Arctic ozone are compared with model simulations. The measurements obtained at Spitsbergen (79°N, 12°E) by ground based millimeter-wave radiometry exhibit large day to day variabilities as well as periods with low ozone. To interpret these measurements, calculations were made using the new photochemical box-trajectory model BRAPHO, with air parcel trajectories calculated from analyzed wind fields. Using a relatively simple approach, the model reproduces the observed ozone variability well, including inter-annual variations. The explanation for the observed ozone behavior is that at these altitudes ozone is determined by what we call dynamically controlled photochemistry. This means that the photochemical evolution of the ozone volume mixing ratio is mainly controlled by the atmospheric dynamics, in particular the solar zenith angle the air parcel has experienced.     

Model analysis of seasonal variations in tropospheric ozone and carbon monoxide over East Asia

Temporal-spatial variations in tropospheric ozone concentrations over East Asia in the period from 1 January 2000 to 31 December 2004 were simulated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the Regional Atmospheric Modeling System (RAMS). The simulated concentrations of ozone and carbon monoxide were compared with ground level observations at two remote sites, Ryori (39.03°N, 141.82°E) and Yonagunijima (24.47°N, 123.02°E). The co...     

C2-C7 Hydrocarbon Concentrations in Arctic Snowpack Interstitial Air: Potential Presence of Active Br within the Snowpack

Samples of interstitial air from within the snow pack on an ice floe on the Arctic Ocean were collected during the April 1994 Polar Sunrise Experiment. The concentrations of C₂-C₇ hydrocarbons are reported for the first time in the snow pack interstitial air. Alkane concentrations tended to be higher than concentrations in free air samples above the snow but very similar to winter measurements at various locations in the Arctic archipelago. However, ethyne concentrations in both interstitial and free air were highly correlated with ozone mixing ratios, consistent with previous demonstrations of the effects of Br atom chemistry. The analysis of total bromine within the snow pack indicate an enrichment in total Br at the interface layer between snow and free troposphere. The mixing ratios of some brominated compounds, such as CHBr₃ and CHBr₂Cl, are found to be higher in this top layer of snow relative to the boundary layer. Results were inconclusive due to the limited number of samples, but suggest the possible presence of active bromine in the snow pack and also that some differences exist between chemical reactions occurring in interstitial air compared to air in the boundary layer.     

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.     

Estimates of the Chemical Budget for Ozone at Waliguan Observatory

Waliguan Observatory (WO) is an in-land Global Atmosphere Watch (GAW) baseline station on the Tibetan plateau. In addition to the routine GAW measurement program at WO, measurements of trace gases, especially ozone precursors, were made for some periods from 1994 to 1996. The ozone chemical budget at WO was estimated using a box model constrained by these measured trace gas concentrations and meteorological variables. Air masses at WO are usually affected by the boundary layer (BL) in the daytime associated with an upslope flow, while it is affected by the free troposphere (FT) at night associated with a downslope flow. An anti-relationship between ozone and water vapor concentrations at WO is found by investigating the average diurnal cycle pattern of ozone and water vapor under clear sky conditions. This relationship implies that air masses at WO have both the FT and BL characteristics. Model simulations were carried out for clear sky conditions in January and July of 1996, respectively. The chemical characteristics of mixed air masses (MC) and of free tropospheric air masses (FT) at WO were investigated. The effects of the variation in NO_x and water vapor concentrations on the chemical budget of ozone at WO were evaluated for the considered periods of time. It was shown that ozone was net produced in January and net destroyed in July for both FT and MC conditions at WO. The estimated net ozone production rate at WO was –0.1 to 0.4 ppbv day^–1 in FT air of January, 0.0 to 1.0 ppbv day^–1 in MC air of January, –4.9 to –0.2 ppbv day^–1 in FT air of July, and –5.1 to 2.1 ppbv day^–1 in MC air of July.     

Interaction of atmospheric chemistry and climate and its impact on stratospheric ozone

The interactively coupled chemistry-climate model ECHAM4.L39(DLR)/CHEM is employed in sensitivity calculations to investigate feedback mechanisms of dynamic, chemical, and radiative processes. Two multi-year model simulations are carried out, which represent recent atmospheric conditions. It is shown that the model is able to reproduce observed features and trends with respect to dynamics and chemistry of the troposphere and lower stratosphere. In polar regions it is demonstrated that an increased persistence of the winter vortices is mainly due to enhanced greenhouse gas mixing ratios and to reduced ozone concentration in the lower stratosphere. An additional sensitivity simulation is investigated, concerning a possible future development of the chemical composition of the atmosphere and climate. The model results in the Southern Hemisphere indicate that the adopted further increase of greenhouse gas mixing ratios leads to an intensified radiative cooling in the lower stratosphere. Therefore, Antarctic ozone depletion slightly increases due to a larger PSC activity, although stratospheric chlorine is reduced. Interestingly, the behavior in the Northern Hemisphere is different. During winter, an enhanced activity of planetary waves yields a more disturbed stratospheric vortex. This "dynamical heating" compensates the additional radiative cooling due to enhanced greenhouse gas concentrations in the polar region. In connection with reduced stratospheric chlorine loading, the ozone layer clearly recovers.     

Comparison of two gas-phase chemical kinetic mechanisms of ozone formation over Europe

Two recent gas-phase chemical kinetic mechanisms for tropospheric ozone formation, one based on the lumped-structure approach (CB05) and the other based on the lumped-molecule approach (RACM2), are compared for simulations of ozone over Europe. The host air quality model is POLAIR3D of the Polyphemus modeling platform. A one-month period (15 July to 15 August 2001) is simulated. Model performance is satisfactory with both mechanisms. Overall, the two mechanisms give similar results with a domain-averaged difference of 3 ppb and a mean fractional absolute difference of 5% (values averaged over the month for the daily 8-h average maximum ozone concentrations). This difference results from different treatments in the two mechanisms for both inorganic and organic chemistry. Differences in the treatment of the inorganic chemistry are due mainly to differences in the kinetics of two reactions: NO + O₃ \(\longrightarrow\) NO₂ + O₂ and NO + HO₂ \(\longrightarrow\) NO₂ + OH. These differences lead to a domain-averaged difference in ozone concentration of 5%, with RACM2 kinetics being more conducive to ozone formation. Differences in the treatment of organic chemistry lead to a domain-averaged difference in ozone concentration of 3%, with CB05 chemistry being more conducive to ozone formation. This average difference results in part from compensating effects among various VOC classes and some significant differences are identified at specific locations (the coastline of northern Africa and eastern Europe: 9%) and for specific organic classes (aldehydes, biogenic alkenes and aromatics). Differences in the treatment of the organic chemistry result from various aspects. For some VOC classes, such as aldehydes and biogenic alkenes, the more detailed explicit treatments using more model species in RACM2 lead to either greater or lower reactivity depending on the assumptions made for the oxidation products. For other VOC species, such as aromatics, the assumptions made about the major chemical oxidation pathways (aromatic alcohol formation in CB05 vs. ring opening in RACM2) affect the ozone formation significantly. Reconciliation of different chemical kinetic mechanisms will require experimental data to reduce current uncertainties in the kinetic (e.g., NO oxidation) and mechanistic (e.g., aromatics oxidation) representations of major chemical pathways.     

Asian monsoon simulations by Community Climate Models CAM4 and CCSM4

This study examines the ability of Community Atmosphere Model (CAM) and Community Climate System Model (CCSM) to simulate the Asian summer monsoon, focusing particularly on inter-model comparison and the role of air–sea interaction. Two different versions of CAM, namely CAM4 and CAM5, are used for uncoupled simulations whereas coupled simulations are performed with CCSM4 model. Ensemble uncoupled simulations are performed for a 30 year time period whereas the coupled model is integrated for 100 years. Emphasis is placed on the simulation of monsoon precipitation by analyzing the interannual variability of the atmosphere-only simulations and sea surface temperature bias in the coupled simulation. It is found that both CAM4 and CAM5 adequately simulated monsoon precipitation, and considerably reduced systematic errors that occurred in predecessors of CAM4, although both tend to overestimate monsoon precipitation when compared with observations. The onset and cessation of the precipitation annual cycle, along with the mean climatology, are reasonably well captured in their simulations. In terms of monsoon interannual variability and its teleconnection with SST over the Pacific and Indian Ocean, both CAM4 and CAM5 showed modest skill. CAM5, with revised model physics, has significantly improved the simulation of the monsoon mean climatology and showed better skill than CAM4. Using idealized experiments with CAM5, it is seen that the adoption of new boundary layer schemes in CAM5 contributes the most to reduce the monsoon overestimation bias in its simulation. In the CCSM4 coupled simulations, several aspects of the monsoon simulation are improved by the inclusion of air–sea interaction, including the cross-variability of simulated precipitation and SST. A significant improvement is seen in the spatial distribution of monsoon mean climatology where a too-heavy monsoon precipitation, which occurred in CAM4, is rectified. A detailed investigation of this significant precipitation reduction showed that the large systematic cold SST errors in the Northern Indian Ocean reduces monsoon precipitation and delays onset by weakening local evaporation. Sensitivity experiments with CAM4 further confirmed these results by simulating a weak monsoon in the presence of cold biases in the Northern Indian Ocean. It is found that although the air–sea coupling rectifies the major weaknesses of the monsoon simulation, the SST bias in coupled simulations induces significant differences in monsoon precipitation. The overall simulation characteristics demonstrate that although the new model versions CAM4, CAM5 and CCSM4, are significantly improved, they still have major weaknesses in simulating Asian monsoon precipitation.     

Surface Trace Gases at a Rural Site between the Megacities of Beijing and Tianjin

The North China Plain （NCP） has recently faced serious air quality problems as a result of enhanced gas pollutant emissions due to the process of urbanization and rapid economic growth. To explore regional air pollu- tion in the NCP, measurements of surface ozone （O3）, nitrogen oxides （NOx）, and sulfur dioxide （SO2） were car- ried out from May to November 2013 at a rural site （Xianghe） between the twin megacities of Beijing and Tianjin. The highest hourly ozone average was close to 240 ppbv in May, followed by around 160 ppbv in June and July. High ozone episodes were more notable than in 2005 and were mainly associated with air parcels from the city cluster in the hinterland of the polluted NCP to the southwest of the site. For NOx, an important ozone precur- sor, the concentrations ranged from several ppbv to nearly 180 ppbv in the summer and over 400 ppbv in the fall. The occurrence of high NOx concentrations under calm condi- tions indicated that local emissions were dominant in Xianghe. The double-peak diurnal pattern found in NOx concentrations and NO/NOx ratios was probably shaped by local emissions, photochemical removal, and dilution re- sulting from diurnal variations of surface wind speed and the boundary layer height. A pronounced SO2 daytime peak was noted and attributed to downward mixing from an SO2-rich layer above, while the SO2-polluted air mass transported from possible emission sources, which differed between the non-heating （September and October） and heating （November） periods, was thought to be responsible for night-time high concentrations.     

Stable Carbon Isotope Ratios and the Photochemical Age of Atmospheric Volatile Organic Compounds

Abstract

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) has been widely studied. In addition to the atmospheric levels of VOCs and NO_x, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NO_x are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NO_x mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NO_x in this environment and at this time of the year.     

Modeling of Regional High Ozone Episode Observed at Two Mountain Sites (Mt. Tai and Huang) in East China

A high O₃ episode was observed during 23–25 May 2004 at two high-mountain sites reflecting the regional pattern of air pollutants over East China. This episode lasted about three days with the maximum hourly O₃ mixing ratios reaching 111 and 114 ppbv at Mt. Tai and Huang, respectively. Backward trajectories and meteorological analysis indicated that regional transport, associated with a weak high pressure system over the East China Sea, might play an important role in the formation of this high ozone episode. The nested air quality prediction modeling system (NAQPMS) was applied to investigate the formation and evolution of this high O₃ event. The comparison of model results with observations showed that NAQPMS successfully reproduced the main observed patterns of O₃ and meteorological parameters during the simulated period. The model results with emission over the Yangtze Delta and the East Central China switched on/off clearly showed that ozone and its precursors transported from the Yangtze Delta and the East Central China enhanced the high ozone episode at two sites, with a contribution of 20%–50% during the episode. In addition, based on process analysis with the model, chemical production and regional transport appeared to be the main causes of high ozone episode involving a large amount of high-ozone air masses and precursors transported from the surrounding areas. The horizontal transport is more active during the period of high ozone episode than that during the non-episode at Mt. Tai as well as Mt. Huang.     

Effects of atmospheric boundary layer mixing representations on vertical distribution of passive and reactive tracers

Summary A one-dimensional chemistry-boundary layer model was used to study the effects of differing representations of atmospheric boundary layer (ABL) processes on simulated concentrations of passive and chemically reactive tracers. Two local- and two nonlocal-closure ABL schemes were used to perform numerical simulations during convective conditions in the ABL. Observational data from the First International Statellite Land Surface Climatology Project (ISLSCP) Field Experiment (FIFE) were used to provide initial meteorological conditions while representative chemical concentrations and surface and elevated emission rates were used to provide initial chemical conditions and chemical sources to the one-dimensional model. Two sets of numerical simulations were performed using the four ABL schemes. The first set simulated bottom-to-top mixing characteristics, and the second set simulated top-to-bottom mixing characteristics. Model simulations were performed for 12h starting from 0700LT 11 July 1987.Our analysis indicate that the simulated concentrations of both passive and reactive chemical species were sensitive to the type of ABL scheme used to represent turbulent mixing processes. Characteristic features associated with each scheme (e.g., growth and intensity of mixing in the ABL) contributed to the differences among the simulated species concentrations. For some of the chemical species these differences were large, particularly in the surface layer and in the interfacial layers of the ABL. In turn, differences caused by the differing mixing representations resulted in different chemical production/destruction rates. As a consequence, the simulated species concentrations differed among the simulations. We also found that chemical species concentrations were more sensitive to the type of ABL scheme in the bottom-to-top mixing simulations than in the top-to-bottom simulations.With 10 Figures     

Aircraft measurements and model simulations of stratospheric ozone and N2O: implications for chemistry and transport processes in the models

Airborne measurements of stratospheric ozone and N₂O from the SCIAMACHY (Scanning Imaging Absorption Spectrometer) Validation and Utilization Experiment (SCIA-VALUE) are presented. The campaign was conducted in September 2002 and February–March 2003. The Airborne Submillimeter Radiometer (ASUR) observed stratospheric constituents like O₃ and N₂O, among others, spanning a latitude from 5°S to 80°N during the survey. The tropical ozone source regions show high ozone volume mixing ratios (VMRs) of around 11 ppmv at 33 km altitude, and the altitude of the maximum VMR increases from the tropics to the Arctic. The N₂O VMRs show the largest value of 325 ppbv in the lower stratosphere, indicating their tropospheric origin, and they decrease with increasing altitude and latitude due to photolysis. The sub-tropical and polar mixing barriers are well represented in the N₂O measurements. The most striking seasonal difference found in the measurements is the large polar descent in February–March. The observed features are interpreted with the help of SLIMCAT and Bremen Chemical Transport Model (CTMB) simulations. The SLIMCAT simulations are in good agreement with the measured O₃ and N₂O values, where the differences are within 1 ppmv for O₃ and 15 ppbv for N₂O. However, the CTMB simulations underestimate the tropical middle stratospheric O₃ (1–1.5 ppmv) and the tropical lower stratospheric N₂O (15–30 ppbv) measurements. A detailed analysis with various measurements and model simulations suggests that the biases in the CTMB simulations are related to its parameterised chemistry schemes.     

Comparison of the EMEP, RADM2 and RACM Mechanisms

A comparison of the atmospheric chemistry mechanisms EMEP (Co-operative Programme for Monitoring and Evaluation of the Long-Range Transmission of Air Pollutants in Europe), RADM2 (Regional Acid Deposition Model, version 2) and RACM (Regional Atmospheric Chemistry Mechanism) has been conducted. Each mechanism was used to simulate the PLUME case of Kuhn et al. (1998) and to simulate an additional 150 and 81 scenarios with and without emissions, respectively. These simulations covered scenarios that ranged from relatively clean, through rural and polluted urban conditions. Ozone isopleths and scatter plots were generated from the simulations. The mechanisms were compared primarily on the basis of calculated ozone and ozone precursor concentrations. For the gas-phase ozone precursors the differences between the mechanisms were rather small under clean conditions and more significant under polluted conditions. The differences were especially significant for the concentrations of NO₂ and organic peroxy radicals. In general the EMEP mechanism yielded the most ozone and the RADM2 mechanism yielded the least. Furthermore the results suggest that a broad range simulation conditions should be used to compare mechanisms and not just a few selected scenarios.     

Simulation of surface energy fluxes using high-resolution non-hydrostatic simulations and comparisons with measurements for the LITFASS-2003 experiment

Land-surface heterogeneity effects on the subgrid scale of regional climate and numerical weather prediction models are of vital interest for the energy and mass exchange between the surface and the atmospheric boundary layer. High-resolution numerical model simulations can be used to quantify these effects, and are a tool used to obtain area-averaged surface fluxes over heterogeneous land surfaces. We present high-resolution model simulations for the LITFASS area near Berlin during the LITFASS-2003 experiment, which were carried out using the non-hydrostatic model FOOT3DK of the University of Köln with horizontal resolutions of 1 km and 250 m. The LITFASS-2003 experimental dataset is used for comparison. The screen level quantities show good quality for the simulated pressure, temperature, humidity and wind speed and direction. Averaged over the four week experimental period, simulated surface energy fluxes at land stations show a small bias for the turbulent heat fluxes and an underestimation of the net radiation caused by excessive cloudiness in the simulations. For eight selected days with low cloud amounts, the net radiation bias is close to zero, but the sensible heat flux shows a strong positive bias. Large differences are found for latent heat fluxes over a lake, which are partly due to local effects on the measurements, but an additional problem seems to be the overestimation of the turbulent exchange under stable conditions in the daytime internal boundary layer over the lake. In the area average over the LITFASS area of 20 ×  20 km², again a strong positive bias of 70 W m^?2 for the sensible heat is present. For the low soil moisture conditions during June 2003, the simulation of the turbulent heat fluxes is sensitive to variations in the soil type and its hydrological properties. Under these conditions, the supply of ground water to the lowest soil layer should be accounted for. Different area-averaging methods are tested. The experimental set-up of the LITFASS-2003 experiment is found to be well suited for the computation of area-averaged turbulent heat fluxes.