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SURFACE OZONE MODELLING for Kiev city ( in the frame of the program Eurotrac-2) Kiev city program
A.V. Shavrina(1), Veles A.A.(1), Dyachuk V.A.(2),, Nochvay V.(3), O.B. Blum(4), Sosonkin M.G(1), Eremenko N.A.(1), MikulskayaI.A.(5), Below V.M. (5)

(1)Main Astronomical Observatory of National Academy of Sciences, Ukraine, (2) Institute of Hydrometeorology, Ukraine (3) National University of Kyiv-Mogyla Academy (now- in MAUP) (4) Botanical Garden of National Academy of Sciences, Ukraine (5) International Scientific-Educational Center of the Information Technologies and Systems of National Academy of Sciences of Ukraine


ABSTRACT

The modelling of ozone episode of August 2000 for Kiev city is discussed. For simulation of ozone concentrations, the Prognostic Meteorological Model (PMM) and Urban Airshed Model (UAM-V) (SAI of USA) are used. The episode of Urban Model (UAM used The enhanced ozone concentrations for 17-21 August 2000 from monitoring data of Kiev Botanic Garden was selected for modelling. A rather high ozone concentrations exceeding Ukrainian and European limit values were predicted for ti di Uk li it di north-east part of city. The results of model calculations show an importance of more detailed temporal results of more detailed temporal modulation of emission data, in particular hourly NO, NO2 and VOC data, and the necessity of taking into account night time heterogeneous chemistry.


INTRODUCTION It is common knowledge that the stratospheric ozone layer (in the upper atmosphere) is very important for sustaining life on Earth - the ozone layer protects life on Earth from the harmful and damaging ultraviolet solar radiation. Ozone in the lower atmosphere, or troposphere, acts as a pollutant but is also an important greenhouse gas. Ozone is not emitted directly by any natural source. However, tropospheric ozone is formed under high ultraviolet radiation flux conditions from natural and anthropogenic emissions of nitrogen oxides (NOx) and volatile organic compounds (VOCs). and While in European region the monitoring of surface ozone is carried out at more than 1700 site stations, in Ukraine the ozone concentrations were not measured before a recent time. Only from 1996 the permanent automatic time. permanent automatic registrations of ozone concentrations were organized in National Botanic Garden (Kiev) with the help of ultraviolet ozone analyzer TECO 49. The same analyzer was installed at the Main Astronomical Observatory of National installed Main Astronomical Observatory of National Academy of Sciences in summer 2006. Preliminary results of analysis of O3 measured data, air quality state stations measurements and first steps of modeling permit to do some main conclusions relative to formation of surface permit relative to formation ozone in Kiev city.


Why ground-based ozone monitoring and modelling are important? · Now satellite observations are available for total ozone and tropospheric columns, nevertheless ground based columns monitoring and modelling is needed to validate and complement space-based measurements and to clarify local/regional specific sources and sinks of ozone and each l/ greenhouse gas. These data can help to study the dynamical behavior of air pollution from space and ground-based observations and to check compliance to the pollutants transport models. · They will also serve to development of an environmental to development of an environmental policy, greenhouse gases policy in particular, in a local and regional scale.


Figure 1.

Average for year 2000/01 and averaged for seasons hourly ozone concentrations, ppb


The analysis of surface ozone measurements in National Botanic Garden (Kiev) with the help of ultraviolet ozone analyzer help of ultraviolet analyzer TECO 49 for 2000 year (Sosonkin et al. 2002) permit to do some main conclusions relative to surface ozone levels in Kiev city. The average annual concentrations of surface ozone are near to 19.5 parts per billion (ppb) , which exceed average daily limited concentration for Ukraine, 30 mkg m(-3)or 15 ppb, as it is given in for m( ) or in the Guide (Rukovodstvo po kontrolyu zagryazneniya atmosfery. Leningrad: Hydrometizdat, 1979, 448 p. (Atmosphere pollution control's quide)) Seasonal variations of ozone concentration are presented in Fig.1, maximum of this value was observed in July-August, minimum - in winter.


Meteorology and wind field fi ld The synoptic situation at 18-21 August was characterized by synoptic at 18 was predominance of small-gradient high pressure field with a mild cold arctic front, slowly moving above Ukraine area. Near the earth surface, it was dominant the west wind of 1-3 m/sec, at altitudes up to 1000 m south and south-west winds (2-15 m/sec), the temperature was changed from 18-20є C up to 30-35є C around-the-clock, the temperature 18 th inversion with intensity of 0.5-2.01є C was formed during each night. This type of synoptic processes was favorable for significant was significant accumulation of ozone precursors, primary from area sources (traffic predominantly), and subsequent intensive ozone production in city's area under weak mechanism of natural self-cleaning of the atmosphere, that was satisfied by the results of primary calculations.


Figure 3: Ozone time series for entire episode (19-21 Aug 2000).


The Prognostic Meteorological Model SAIMM Prognostic Meteorological
The Prognostic Meteorological Model (PMM SAIMM) was used as (PMM preprocessor for meteorological data needed for modelling of ozone concentrations. The coarse grid for PMM was consisted of 18x18 cells of 4x4 km and corresponded to most part of Kiev region. The measurements co esponded to most pa egion meas ements of temperature, pressure, humidity and wind parameters - velocities and directions of wind on ground level at 6 weather stations of Kiev region and balloon measurements (up to 10 km of altitude) at one station (Kiev), to 10 km of altitude) station twice a day, were used for wind and temperature fields simulation. In the process of simulation with PMM the background fields were reconstructed, adjusting wind fields to local topography. Finally PMM model provides 3D wind and temperature fields as well as turbulence provides 3D wind and fields as well as turbulence parameters for input to Urban Airshed Model UAM-V.




Input Data Required by the UAM-V Model The UAM-V derived pollutant concentrations are calculated from the emissions, advection, and dispersion of precursors and the formation and dispersion of pr and formation deposition of pollutants within every grid cell of the modeling domain. To adequately replicate the full three-dimensional structure of the atmosphere during an ozone episode, the UAM-V program requires an hourly and dayan ozone pr require an hourly and specific database for input preparation. Several preprocessing steps to translate raw emissions, meteorological, air quality, and grid-specific data are required the develop final UAM-V input files. develop input The new features of the UAM-V model necessitate the provision of more extensive input data compared to the earlier version. Observed air quality data input earlier version Observed data are used to evaluate model predictions. These data may also be used to estimate the initial concentrations and boundary conditions for ozone, NOx , and volatile organic compounds (VOC). The UAM-V model is usually used to The model simulate a multiday episode, and the simulation is started during the early morning hours one to three days before the start of episode. Use of start-up days limits the influence of the initial concentrations (which are not wellthe of the concentrations not known) on the simulation of the primary episode days.


Emissions inventory
Evaluation of emission rates due to various sources of pollution for Kiev city in August Ki it 2000 were carried out according to statistical emission data for separate industrial plants. Among the point-source emission species we took into account the next ones: point-source nitrogen oxides, saturated and unsaturated hydrocarbons, and formaldehyde. From the anthropogenic and biogenic sources distributed on grid cells, the emissions of carbon oxide and main components of Volatile Organic Compounds (VOC), 22 compounds altogether, were estimated additionally. Emissions of specified species from traffic were estimated according relative composition of exhaust gas of automobile cars. Pollution by stationary sources is due to more than 700 plants of different branch of industry, on which there are 24 thousands of organized emission points of atmosphere pollution. The most contribution in city's atmosphere pollution from industry is due to The in city atmosphere industry is combined heat and power (CHP) plants, emissions from which in year 2000 are composed 19,386 ton (60% of pollutions from stationary sources). For today the road traffic in Kiev, like to number of other towns of Ukraine, is one of main sources of in Kiev to of other of Ukraine atmosphere pollution. Our estimates for NOx and VOC due traffic are 3,348 and 10,460 ton accordingly. Total VOC amount was split into individual compounds7 and than lumped into the emission classes needed by the photochemical mechanism CB-IV-TOX CB implemented in the UAM-V model. UAM-V


Emission sources were grouped as point and area ones on city's domain. Among point sources, 16 high stationary sources were selected for emission modelling. 16 hi Their emission volume in the summer 2000 put together more than 80% of industrial pollution. For each point source, the next stack parameters were included as input data for modelling: stack height, diameter of stack, stack exit velocity and exit temperature for gas-air mixture. The other 20% of stationary point sources were taken into account together with mobile sources as area emission sources. The city's domain was presented as a cell grid of 17 x 15, with size of each cell of 2 x 2 km. Emission from each cell was estimated on the base of traffic volume on roads within each cell and district ll averaged emissions of stationary sources, which were not accounted as point sources.


The UAM-V species continuity equation using nested grids is solved as follows: 1. Emissions are injected into the coarse grid. 2. Transport/diffusion/deposition are integrated on the coarse grid for one coarse-grid advective (driving) time step. 3. For each fine grid: (a) If necessary, coarse-grid input data are interpolated to the fine grid. (b) A driving time step is defined for the fine grid that is an integral subdivision of the coarse-grid time step. (c) Emissions are injected. (d) Transport/diffusion/deposition are integrated. (e) Chemistry calculations are carried out.


Emission rates
Evaluation of emission rates due various sources of pollution for Kiev city in August 2000 were carried out according to statistical emission data for separate industrial plants from Minicipal Report. Among the point- source emission species it was taken into account the th it th next ones: nitrogen oxides, saturated and unsaturated hydrocarbons, and formaldehyde. From the anthropogenic and biogenic sources distributed on grid cells, the emissions of carbon oxide and main components of emissions of carbon oxide main components of Volatile Organic Compounds (VOC), 22 compounds altogether, were estimated additionally. Emissions of specified species from traffic (area sources) were estimated according relative composition of exhaust gas of automobile car cited in relative composition gas cited the book of Isidorov, 2001. Total VOC amount was split into individual compounds and than lumped into the emission classes needed by the photochemical mechanism CB-IV-TOX implemented in the UAM-V model. mechanism in the model.



uam-v modelling Two days simulation of ozone episode for 19-20 August 2000 were performed scaling emission data averaged daily and hourly on the basis emission basis of annual volumes. In the Figure 5 we show the comparison of calculated with UAM-V ozone concentrations and data of measurements in National Botanic Garden for 19-20 August 2000. One can see on Figure 3 that O3 concentrations show non-linear variation depending on average hourly NOx emission data (curves 2,3). The comparison of ozone comparison of ozone concentrations with measurements shows the necessity of temporal modulation of VOC and NOx emissions taking into account diurnal of NO traffic intensity and specific weekday variations (curve 4). It is known, that the ratio of NO and NOx is very badly determined both for industrial and traffic emissions and can change of factor up to 107), therefore we scaled their emission data separately for each species.


Fig Fi ure 5: The comparison of measured (red line) and calculated (lines 2-4) O3 Th concentrations for Aug 19-20, 2000. Lines 2 and 3 are scaled hourly average emissions, line 4 is modulated ones according diurnal traffic motion.



OZONE modelling results and Human Health risks ASSESSMENT The modeled ozone distribution (for 19 Aug 2000, 14 h) demonstrates that the area of the National Botanic Garden is possibly not the most polluted (1-hour average ozone concentration about 60 ppb). Other parts of Kiev (north-east) can be characterized about 60 parts (Figure 4) by more enhanced ozone concentrations (predicted up to 104 ppb), which exceed European threshold (1hour average) for population information (90 ppb). Note, that 98.7 ppb was observed in National Botanic Garden in August 2007. 98 ti It is important task to evaluate possible damage for ecosystems and for population. For human population, a wide variety of physiological responses to ozone have to be considered. The responses are both individually differing, and similar in some population groups. Groups with similarities in their reactions are important to identify, as they may represent those individuals more sensitive to elevated exposures. Population groups that are often mentioned as more sensitive include younger children, child and adult asthmatics, exercising individuals, or individuals exposed to higher temperature and/or humidity. The layers of map of Kiev city and its nearest surroundings in GIS can be used for estimating of exposures of the city population to ozone.


Figure 5. The map of calculated ozone concentration exceeded 60 ppb (red area) for ozone episode in Kiev on 19 August 2000 during 8 hours.



· Value of linked to such parameters as population density, residential and recreation areas and concentrations of others pollutants; L depend of exposure time. Risks levels for Kiev depend of Risks Kiev population, estimated for the ozone episode of August 2000, are presented in the figure 6. Risk level in each cell was calculated relating to population exposure. Higher risk levels are observed to exposure Higher risk levels are in the central part of the city.

· There are two ways to reduce risk level: the first is to restrict exposure (for example by information of the example of the population) and another one is to reduce ozone concentration using anthropogenic emission optimization.


Figure 6. The local risk levels of surface ozone exposure estimated for the population of the city during modeling episode. Higher risk levels are correspondent to darker cell color. Risk level in each cell was calculated relating to population exposure. Higher risk levels are observed in the central part of the city.


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Results
Two days simulation of ozone episode for 19-20 August 2000 were performed scaling emission data averaged daily and hourly on the basis of annual volumes. Preliminary results of analysis of the first steps of modelling permit to do some main conclusions relative to formation of surface ozone in Kiev city. The comparison of calculated with UAM-V Ki Th UAM ozone concentrations (ppb) and data of measurements in Botanic Garden shows non-linear variations of O3 concentrations depending on average hourly NOx emission data. A rather high ozone concentrations exceeding Ukrainian and European limit values were predicted for north-east part of city. The results of model calculations show an importance of more detailed temporal modulation of emission data, in particular hourly NO, NO2 and VOC data, and the necessity of taking into account night time data and necessity time heterogeneous chemistry.


CONCLUSIONS

As a rule, minimum ozone values are observed in the morning, about 8 hour, rule minimum ar morning maximum - at noonday, 13-15 hours. It was revealed that situations of nocturnal decrease of O to minimum value (about zero) were almost not observed. Contrary, at night it is often observed the second maximum of ht it ft th surface ozone. One of possible explanations of this phenomenon -sinking of ozone from boundary level and specific location of monitoring station - Botanic Garden. The first results of ozone concentration modelling justify the existence of two type of ozone forming areas for Kiev city, NO and VOC sensitive. For Botanic forming for VOC Botanic Garden measured ozone concentration at 19-20 August 2000 we reveal nonlinear sensitivity to NOx both increase and reduction of NO emission data result in decreasing of O3 maximum values. Maximal ozone concentrations can ti be observed in the residential suburbs. Two-step night lowering could be simulated by additional night rejection of lowering be simulated ejection of NO, for example, by industrial stack in weekend or biomass firing, which can be expected in second half of August. The night time heterogeneous reactions must be also considered, especially the processes of ozone uptake and oxidation processes of ozone and on the surfaces of condensing water drops or particles of soot. The relevant module of heterogeneous chemistry should be implemented in UAM-V model.


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(Advection - The transfer of a property of the atmosphere, such as heat, cold, or humidity, by the horizontal movement of an air mass)






















An investigation of ozone and planetary boundary layer dynamics over the complex topography of Grenoble combining measurements and modeling
O. Couach et al., 2003 (Atmos.Chem.Phys. 3, 549-562)