Ceilometer observations of aerosol layer structure above the Petit Lubéron during ESCOMPTE's IOP 2

A modified ceilometer has been used during the second Intensive Observation Period (IOP) of the “Expérience sur Site pour COntraindre les Modèles de Pollution atmosphériques et de Transport d'Émission” (ESCOMPTE) to perform continuous remote observations of aerosol accumulations in the first 3 km of the atmosphere. These observations encompassed an episode of intense particulate and photochemical pollution. The submicronic particles density, measured at an altitude of 600 m, went from a very low point of a few tens of particles per cubic centimeter (at the end of a Mistral episode in the free atmosphere) to a high point of more than 4500 particles per cubic centimeter (when pollutants were trapped by thermal inversions).The main result is that this instrument enables a fine documentation of the mixing layer height and of aerosol particles stratifications and circulation. Airborne aerosol measurements have been made above the mountainous region of Mérindol in order to validate in situ the remote sensing measurements. Ozone measurements near the summit of the mountains as well as in the valley were performed in order to correlate aerosol accumulation and ozone concentration. As a notable example, the two-layer aerosol stratification seen in the first 2 days of IOP 2b in that part of the ESCOMPTE domain confirms the results of another team which used backtrajectories. The low-altitude pollution for this timeframe had a local origin (the Fos industrial area), whereas above 500 m, the air masses had undergone regional-scale transport (from north-eastern Spain).The second major result is the highlighting of a pattern, in sea breeze conditions and in this part of the ESCOMPTE experiment zone, of nocturnal aerosol accumulation at an altitude of between 500 and 2000 m, followed by high ozone concentration the next day.     

The ESCOMPTE program: an overview

In this paper, the “Expérience sur Site pour COntraindre les Modèles de Pollution atmosphérique et de Transport d'Emissions” (ESCOMPTE) program is presented. The ESCOMPTE program is used to produce a relevant set of data for testing and evaluating regional pollution models. It includes high-resolution (in space and time) atmospheric emission inventories and field experiments, and covers an area of 120×120 km, centered over the Marseilles-Berre area in the southeast of France during Summer 2001. This region presents a high occurrence of photochemical pollution events, which result from numerous industrial and urban sources of primary pollutants. From the dynamical characteristics of the area, sea-breeze circulation and channeling effects due to terrain features highly influence the location of the pollutant plumes. ESCOMPTE will provide a highly documented framework for dynamics and chemistry studies.Campaign strategies and experimental set up are described. During the planning phase, existing modeling results helped defining the experimental design. The campaign involved surface measurement networks, remote sensing, ship-borne, balloon-borne, and airplane measurements. Mean standard meteorological parameters and turbulent fluxes, ozone, ozone precursors, photochemically active trace gases, and aerosols were measured. Five intensive observation periods (IOPs) were documented using a wide spectrum of instruments, involving aircraft (7) (one of them equipped with a Doppler lidar, the others for in situ meteorological and chemical measurements), constant volume balloons (33), ozone lidars (5), wind profilers (15 sodars and radars), Doppler scanning lidar (1), radiosonde systems (at 4 locations), instrumented ships (2). In addition to the air quality networks from environmental agencies, 15 supplementary ground stations equipped for chemistry and/or meteorology and/or surface flux measurements, were operational. All instruments were calibrated and compared during a Quality Control/Quality Assurance (QC/QA) week, at the very beginning of the campaign.Fifteen days were intensively documented during five IOPs, referenced as 1, 2a, 2b, 3, and 4. High pollution levels were encountered during sea-breeze conditions observed during IOPs 2b and 3, whereas IOPs 2a and 4 corresponded to moderate wind, and channeled plume regimes. In addition, hourly emissions inventories for all IOPs were established to complete data sets and to finalize the ESCOMPTE database (EDB).Two other projects were associated to ESCOMPTE: urban boundary layer (UBL) and tropospheric water vapor content by GPS tomography (GPS/H₂O). They took advantage of the scientific environment provided by ESCOMPTE.     

An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m³ during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.     

Impact of chemical and meteorological boundary and initial conditions on air quality modeling: WRF-Chem sensitivity evaluation for a European domain

This study evaluates the impact of different chemical and meteorological boundary and initial conditions on the state-of-the-art Weather Research and Forecasting (WRF) model with its chemistry extension (WRF-Chem). The evaluation is done for July 2005 with 50 km horizontal resolution. The effect of monthly mean chemical boundary conditions derived from the chemical transport model LMDZ-INCA on WRF-Chem is evaluated against the effect of the preset idealized profiles. Likewise, the impact of different meteorological initial and boundary conditions (GFS and Reanalysis II) on the model is evaluated. Pearson correlation coefficient between these different runs range from 0.96 to 1.00. Exceptions exists for chemical boundary conditions on ozone and for meteorological boundary conditions on PM₁₀, where coefficients of 0.90 were obtained. Best results were achieved with boundary and initial conditions from LMDZ-INCA and GFS. Overall, the European simulations show encouraging results for observed air pollutant, with ozone being the most and PM₁₀ being the least satisfying.     

Study of ozone distribution over the south-eastern France (ESCOMPTE campaign): discrimination between ozone tendencies due to chemistry and to transport

Ozone tendencies due to chemistry and transport are calculated by a mesoscale model using a fine horizontal resolution (3 km × 3 km), over South-Eastern France. Over that region where the anthropogenic emissions are very strong, ozone pollution is highlighted during two intensive observations periods of the ESCOMPTE campaign, when the sea breeze penetrates far into the Durance and Rhone valleys and the up-slope breezes are developed. From a fine analysis of time series of ozone concentration at different ground stations along these valleys and from numerical results, it is possible to discriminate the tendency due to chemistry from the tendency due to dynamical processes. We can distinguish both processes, either local chemical production/loss or dynamical increase/decrease (transport, deposition) on maps of ozone budget according to the meteorological conditions. In particular, we show that the variations due to transport can be have the same order of magnitude than those due to chemistry, reaching 20 ppbv h⁻¹, whereas those due to chemistry are around 30 ppbv h⁻¹.     

Airborne measurements of turbulent trace gas fluxes and analysis of eddy structure in the convective boundary layer over complex terrain

Using the new high-frequency measurement equipment of the research aircraft DO 128, which is described in detail, turbulent vertical fluxes of ozone and nitric oxide have been calculated from data sampled during the ESCOMPTE program in the south of France. Based on airborne turbulence measurements, radiosonde data and surface energy balance measurements, the convective boundary layer (CBL) is examined under two different aspects. The analysis covers boundary-layer convection with respect to (i) the control of CBL depth by surface heating and synoptic scale influences, and (ii) the structure of convective plumes and their vertical transport of ozone and nitric oxides. The orographic structure of the terrain causes significant differences between planetary boundary layer (PBL) heights, which are found to exceed those of terrain height variations on average. A comparison of boundary-layer flux profiles as well as mean quantities over flat and complex terrain and also under different pollution situations and weather conditions shows relationships between vertical gradients and corresponding turbulent fluxes. Generally, NO_x transports are directed upward independent of the terrain, since primary emission sources are located near the ground. For ozone, negative fluxes are common in the lower CBL in accordance with the deposition of O₃ at the surface.The detailed structure of thermals, which largely carry out vertical transports in the boundary layer, are examined with a conditional sampling technique. Updrafts mostly contain warm, moist and NO_x loaded air, while the ozone transport by thermals alternates with the background ozone gradient. Evidence for handover processes of trace gases to the free atmosphere can be found in the case of existing gradients across the boundary-layer top. An analysis of the size of eddies suggests the possibility of some influence of the heterogeneous terrain in mountainous area on the length scales of eddies.     

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。     

A Review of Atmospheric Chemistry Research in China: Photochemical Smog, Haze Pollution, and Gas-Aerosol Interactions

In this paper we present a review of atmospheric chemistry research in China over the period 2006-2010, focusing on tropospheric ozone, aerosol chemistry, and the interactions between trace gases and aerosols in the polluted areas of China. Over the past decade, China has suffered severe photochemical smog and haze pollution, especially in North China, the Yangtze River Delta, and the Pearl River Delta. Much scientific work on atmospheric chemistry and physics has been done to address this large-scale, complex environmental problem. Intensive field experiments, satellite data analyses, and model simulations have shown that air pollution is significantly changing the chemical and physical characters of the natural atmosphere over these parts of China. In addition to strong emissions of primary pollutants, photochemical and heterogeneous reactions play key roles in the formation of complex pollution. More in-depth research is recommended to reveal the formation mechanism of photochemical smog and haze pollution and their climatic effects at the urban, regional, and global scales.     

大城市气溶胶对光化辐射通量及臭氧的影响研究(Ⅱ)——数值试验分析

城市化已引起大量痕量气态污染物、气溶胶以及臭氧前体物的人为排放,从而引起区域大气化学循环的扰动变化。在分析国内外研究现状与观测实例的基础上,进一步用辐射模式与化学模式研究了气溶胶对到达地面的光化辐射通量以及臭氧形成的影响,表明气溶胶可显著减小到达地面的光化学辐射通量,减缓光化学反应进程,并进一步抑制臭氧的形成;在目前广州等大城市的污染过程中,高浓度的气溶胶可造成光化学辐射通量衰减高达70%~80%,紫外线的衰减比可见光更明显,在可见光波段随波长增大衰减幅度减小,气溶胶层的存在对短波长激发的光化学过程的影响更加显著。分析说明城市污染大气中光化学反应的生成物与反应物之间存在自抑制过程,在目前的城市群复合污染情况下,气溶胶与臭氧之间的非线性相互作用值得关注。     

Variability of Near-Ground Ozone Concentrations During Cold Front Passages – a Possible Effect of Tropopause Folding Events

The analysis of surface ozone variability requires besides chemicalstudies the consideration of meteorological conditions and dynamicprocesses. Our research focuses on the mechanisms in connection with coldfront passages. A statistical study and case studies of cold front passageswere carried out at six German ground-based sites during the year 1990.After the passage of cold fronts three typical developments of thenear-ground ozone concentrations could be identified. Usually the ozoneconcentrations decrease due to advection of clean air masses or due toenhanced cloudiness preventing the photochemical production of ozone,chemical destruction by nitrogenoxides, and heterogeneous chemistry. In somecases the concentrations increased by reason of downward mixing of ozoneenriched air intruded from the stratosphere into the troposphere bytropopause foldings. For a few cases no modification set in. The decreasewas mostly twice as strong as the increase. The latter was between 4 and 8ppb on the average. Special emphasis is given to the transport ofstratospheric ozone down to the ground. There is no direct evidence forstratospheric ozone at ground level, because it cant be distinguished fromthe tropospheric one, but from case studies circumstantial evidence is foundin favour of it. As an example of increasing ozone behind the passage ofcold fronts one case study typical of all other case studies is presented.It shows the characteristic properties of the corresponding fronts, whichare fast movement, a vertical split structure and strong convection.     

The establishment of the atmospheric emission inventories of the ESCOMPTE program

Within the frame of the ESCOMPTE program, a spatial emission inventory and an emission database aimed at tropospheric photochemistry intercomparison modeling has been developed under the scientific supervision of the LPCA with the help of the regional coordination of Air Quality network AIRMARAIX. This inventory has been established for all categories of sources (stationary, mobile and biogenic sources) over a domain of 19,600 km² centered on the cities of Marseilles–Aix-en-Provence in the southeastern part of France with a spatial resolution of 1 km². A yearly inventory for 1999 has been established, and hourly emission inventories for 23 days of June and July 2000 and 2001, corresponding to the intensive measurement periods, have been produced. The 104 chemical species in the inventory have been selected to be relevant with respect to photochemistry modeling according to available data. The entire list of species in the inventory numbers 216 which will allow other future applications of this database. This database is presently the most detailed and complete regional emission database in France. In addition, the database structure and the emission calculation modules have been designed to ensure a better sustainability and upgradeability, being provided with appropriate maintenance software. The general organization and method is summarized and the results obtained for both yearly and hourly emissions are detailed and discussed. Some comparisons have been performed with the existing results in this region to ensure the congruency of the results. This leads to confirm the relevance and the consistency of the ESCOMPTE emission inventory.     

The 15‐km version of the Canadian regional forecast system

Abstract

A new mesoscale version of the regional forecast system became operational at the Canadian Meteorological Centre on 18 May 2004. The main changes to the regional modelling system include an increase in both the horizontal and vertical resolutions (15‐km horizontal resolution and 58 vertical levels instead of 24‐km resolution and 28 levels) as well as major upgrades to the physics package. The latter consist of a new condensation package, with an improved formulation of the cloudy boundary layer, a new shallow convection scheme based on a Kuo‐type closure, and the Kain and Fritsch deep convection scheme, together with a subgrid‐scale orography parametrization scheme to represent gravity wave drag and low‐level blocking effects. The new forecast system also includes a few changes to the regional data assimilation such as additional radiance data from satellites.

Objective verifications using a series of cases and parallel runs, along with subjective evaluations by CMC meteorologists, indicate significantly improved performance using the new 15‐km resolution forecast system. We can conclude from these verifications that the model exhibits a marked reduction in errors, improved predictability by about 12 hours, better forecasts of precipitation, a significant reduction in the spin‐up time, and a different implicit‐explicit partitioning of precipitation. A number of other features include: sharper precipitation patterns, better representation of trace precipitation, and general improvements of deepening lows and hurricanes. In mountainous regions, several aspects are better represented due to combined higher‐resolution orography and the low‐level blocking term.     

A complete dynamical ozone budget measured in the tropical marine boundary layer during PASE

The Pacific Atmospheric Sulfur Experiment (PASE) was a field mission that took place aboard the NCAR C-130 airborne laboratory over the equatorial Pacific Ocean near Christmas Island (Kirimati, Republic of Kiribati) during August?CSeptember, 2007. Eddy covariance measurements of the ozone fluxes at various altitudes above the ocean surface, along with simultaneous mapping of the horizontal gradients provided a unique opportunity to observe all of the dynamical components of the ozone budget in this remote marine environment. The results of six daytime and two sunrise flights indicate that vertical transport into the marine boundary layer from above and horizontal advection by the tradewinds are both important source terms, while photochemical destruction consisting of 82% photolysis (leading to OH production), 11% reaction with HO₂, and 7% reaction with OH provides the main sink. The overall photochemical lifetime of ozone in the marine boundary layer was found to be 6.5 days. Ocean uptake of ozone was observed to be fairly slow (mean deposition velocity of 0.024?±?0.014 cm s^?1) accounting for a diurnally averaged loss rate that was ??30% as large as the net photochemical destruction. From the measurement of deposition velocity an ozone reactivity of ??50 s^?1 in seawater is inferred. Due to the unprecedented measurement accuracy of the dynamical budget terms, unobserved photochemistry was able to be deduced, leading to the conclusion that 3.9?±?3.0 ppt (parts per trillion by volume) of NO is present on average in the daytime tropical marine boundary layer, broadly consistent with several previous studies in similar environments. It is estimated, however, that each ppt of BrO hypothetically present would counter each ppt of NO above the requisite 3.9 ppt needed for budget closure. The long-term budget of ozone is further analyzed in the buffer layer, between the boundary layer and free troposphere, and used to derive an entrainment velocity across the trade wind inversion of 0.51 ± 0.38 cm s^?1.     

The urban boundary-layer field campaign in marseille (ubl/clu-escompte): set-up and first results

The UBL/CLU (urban boundary layer/couche limite urbaine) observation and modelling campaign is a side-project of the regional photochemistry campaign ESCOMPTE. UBL/CLU focuses on the dynamics and thermodynamics of the urban boundary layer of Marseille, on the Mediterranean coast of France. The objective of UBL/CLU is to document the four-dimensional structure of the urban boundary layer and its relation to the heat and moisture exchanges between the urban canopy and the atmosphere during periods of low wind conditions, from June 4 to July 16, 2001. The project took advantage of the comprehensive observational set-up of the ESCOMPTE campaign over the Berre–Marseille area, especially the ground-based remote sensing, airborne measurements, and the intensive documentation of the regional meteorology. Additional instrumentation was installed as part of UBL/CLU. Analysis objectives focus on (i) validation of several energy balance computational schemes such as LUMPS, TEB and SM2-U, (ii) ground truth and urban canopy signatures suitable for the estimation of urban albedos and aerodynamic surface temperatures from satellite data, (iii) high resolution mapping of urban land cover, land-use and aerodynamic parameters used in UBL models, and (iv) testing the ability of high resolution atmospheric models to simulate the structure of the UBL during land and sea breezes, and the related transport and diffusion of pollutants over different districts of the city. This paper presents initial results from such analyses and details of the overall experimental set-up.     

区域对流层光化学过程研究

将 MM5和 RADM耦合 ,建立了一个区域大气光化学模式。用此模式来研究区域大气光化学过程。分析了大气光化学过程中前体物、自由基以及主要产物的时空分布及其随时间的变化情况。得到了大气光化学过程各主要成分的分布及其演变特征。在此基础上 ,分析了水平平流、垂直扩散及沉降以及化学转化等物理、化学过程在大气光化学过程中的相对重要性 ,结果表明 ,水平平流和垂直扩散及沉降等物理过程对大气光化学过程中各种成分的浓度分布及其随时间的变化有重要的作用。     

Variability of NO2 in different environments at a moderately polluted island over the southwestern Indian Ocean

This work presents the temporal evolution and spatial distribution of nitrogen dioxide (NO₂) measured with the help of passive diffusion tubes in different environments: rural, sub-urban, urban, at La Réunion Island in December 1997 and November 2000 (austral spring), respectively. NO₂ concentration exhibits notable enhancement from 1997 to 2000. For instance, its mean concentration was 16 and 20 μg/m³ in December 1997 and November 2000, respectively, at La Réunion Island, especially in inhabited regions due to increase of local anthropogenic activities, mainly traffic circulation, in the absence of house heating and biomass burning. We also observe a net increase of pollutant levels by a factor two in rural/remote areas within 3 years, which is tied to the extension of inhabited areas and air-flows from enhanced local sources. The increase of atmospheric pollutants is mainly due to enhancement of anthropogenic activities (traffic) since the 1990s at La Réunion Island, which results from a constant increase of population and consequently, from a higher number of vehicles in circulation. Importantly, in cities like Saint-Denis, where traffic network has been subject to notable improvement (e.g. single to double lanes, etc.), pollutant levels exhibit little variability as in temperate continental latitudes. Semi-continuous NO₂ concentration measured in parallel with ozone in November 2000 also showed that daytime photochemical ozone production is influenced by pollutant and precursor (NO₂) levels at Saint-Denis, while nighttime ozone increase is mainly tied to dynamical processes. The November 2000 ozone diurnal pattern is notably different from that observed in September 1995, during which a daytime ozone loss was observed, pointing out that atmospheric conditions have been subject to notable changes, i.e., clean to moderately polluted, within a few years at La Réunion Island. The results presented here point out that the ‘source enhancement effect’ is superimposed on dynamical and photochemical processes to influence pollutants variability and hence atmospheric chemistry, in a quite ‘pristine’ tropical oceanic region.     

Modelling chemistry in the nocturnal boundary layer above tropical rainforest and a generalised effective nocturnal ozone deposition velocity for sub-ppbv NOx conditions

Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O₃], but relatively low observed [NO₂]. It is shown that a one-dimensional (1-D) column model with simple O₃-NO_x chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NO_x] conditions (NO_x?<?1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NO_x and O₃. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ substantially if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following days peak ozone concentration. However under medium to high [NO_x] conditions (NO_x > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate coefficients.     

WRF ARW and CHIMERE models for numerical forecasting of surface ozone concentration

Results of joint calculations with meteorological WRF ARW model and chemistry transport CHIMERE model are considered as a basis of the modern system of the air quality assessment and forecasting. The system was designed in the Russian Hydrometeorological Center and Institute of Applied Physics of the Russian Academy of Sciences. Detailed prognostic information about the atmosphere state provided by the WRF ARW was used in the CHIMERE model for describing the air mass transport processes, chemical transformation, and pollution deposition. Results of retrieval and forecast of surface ozone concentration as one of main air quality indicators are under consideration. Calculations of ozone concentrations for different configurations of a prognostic system differ in resolution of model grid and in the way the boundary conditions are prescribed.     

Preliminary results From a partial LRTAP model based on an existing meteorological forecast model

Abstract

An existing state‐of‐the‐art regional meteorological model is coupled through appropriate constituent mass conservation equations to model the long‐range transport of atmospheric pollutants (LRTAP) under restrictive constraints on atmospheric chemistry and deposition. Particular emphasis is given to the importance of a good representation of turbulence and other sub grid‐scale processes in the planetary boundary layer (PBL), both in the formulation and in the interpretation of the results. The regional meteorological model provides not only forecasts of wind velocity and temperature, but also vertical diffusion profiles consistent with the evolution of its PBL. The transport in the LRTAP model is handled by computationally stable algorithms such that the time step may be chosen on the basis of accuracy rather than stability, and the chemistry is described by a simple four‐species model of the oxidation of sulphur dioxide and nitrogen dioxide. Results are presented of a sample 48‐h summer simulation over central and eastern North America, using real meteorological data and time‐averaged emission inventory data; parameters of the integration include a one‐hour time step, a horizontal resolution of 100 km and 15 variably spaced vertical levels, 10 of which are contained in the lower one third of the atmosphere. It is argued that despite the simplicity of the chemistry, the results are qualitatively realistic and the high impact of the PBL processes on LRTAP is evident. For this particular simulation, it is interesting to note the existence of a region over Nova Scotia where the deposition of sulphates is significantly greater than that which could be expected from local sources. This is interpreted as being due to the confluence of two flows that pass over two different centres of high emission ofSC>2, andas being evidence of the model's ability to qualitatively model LRTAP.