AIR POLLUTION MONITORING IN

Presentation of results from the second measuring campaign in the region zone

Report elaborated by reVite, SHMU

Analyses performed by Vito - Belgium and SHMU - Bratislava

Project coordinator SHMU: Lubor Kozakovic

April 2005

Cooperation project between the Slovak Hydrometeorological Institute (SHMU-Slovak Republic), the Flemish Environmental Agency (VMM-Belgium), the Flemish Institution for Technological Research (Vito-Belgium) and Environmental Data Processing Company (reVite-Slovak Republic)

CONTENT

1. SUMMARY ...... 3

2. INTRODUCTION...... 3

3. METHOD...... 6

4. PROCESSING THE RESULTS ...... 7

4.1 Evaluation of the correspondence between passive and active measurements ...... 8

4.2 Evaluation of the spatial and temporal representativeness of the data for the sampling period...... 11

4.3 Meteorological condition within the period from the climatological point of view...... 14

5. EVALUATION OF THE RESULTS...... 15

6. CONCLUSION ...... 16

7. ANNEXES ...... 21

2 1. SUMMARY

In January 2003, the bilateral project between the Flemish Environmental Agency (VMM) and The Flemish Institute for technological research (VITO) on one side and the Slovak Hydrometeorological Institute (SHMU) and the reVite company on the other side was started. This report presents the results obtained during the second monitoring campaign in the zone in November 2004.

The main objective was to obtain information on spatial distribution of NO2, SO2 and benzene concentrations in the Bratislava region zone where only a little information on Air Quality (AQ) was available, mostly from model calculations. Preliminary results from the measuring campaign showed that this area does not belong to very high polluted ones and with regards to the measured components none of the areas belong to the category of ‘air quality management area’. In addition to modelling, the presented results also provide objective information and indicate spatial distribution of SO2, NO2 and benzene concentration throughout the whole zone. In this way, the study helps the regional policy maker to assess the impact on air quality in different places from new potential emission sources. Moreover, the photo documentation and the classification according to the EoI criterion represent additional information, which is helpful for deeper analyses of relations between emissions and AQ. All this information and other documentation related to this project are available at the website: http://www.shmu.sk/?page=28.

2. INTRODUCTION

The Air Quality Project in the Slovak Republic - Monitoring of air pollution and audit of quality system, is being realised in the frame of a bilateral programme between the governments of Flanders and the Slovak Republic. The main objective of the project is to help the Slovak Republic in the process of harmonization with the EU air quality legislation requirements. According to the Framework Directive “Council Directive 96/62/EC on Air Quality Management and Assessment”, the Member States are obliged to provide an assessment of ambient air quality throughout the territories of the Member States. General requirements concerning AQ are aimed to ensure implementation of necessary measures in order to comply with the limit values. Since January 1st 2003, the Slovak Republic has fully transposed the EU AQ legislation, which came into force under the Clean Air Act No. 478/2002 Coll. and the Decree No. 705 about Air Quality.

3 Regular measurements are carried out at 28 automated monitoring stations. This network is called the National Urban AQ Monitoring Network and the following pollutants were monitored at most stations in the year 2004: SO2, NOx, NO2, CO, O3, PM10, Pb, Benzene,

PM2.5, As, Ni, Cd. The AQ assessment performed on the basis of automated measurements could be understood as fundamental for the assessment of areas where the AQ level exceeds the limit values or the limit values plus the margin of tolerance. Passive long scale measurements, such as those that were performed in this campaign, provide supplementary information that is valuable mainly because it indicates spatial distribution of particular pollutants in the whole area. As a result, regular and supplementary measurements of SO2,

NO2 and benzene are very important for complex AQ assessment in the zones and agglomerations and for delimitation of areas where the appropriate measures have to be applied. There is a little bit different situation with the evaluation of air pollution by PM10 because of various sources of PM10 (traffic, industry, agriculture, etc.), mixture of different types of sources (points, mobile and area sources) and the uncertainty regarding quantification of their emissions. Therefore, in many cases it is the expert’s assessment and the model interpolations that play a more significant role. Similar to other parts in Europe, the

PM10 is nowadays the most discussed pollutant. The aim is to better understand and quantify different sources, such as long-range transport, local background and local hot spot sources, such as traffic. Apportionment and quantification of PM10 sources is crucial for the application of effective measures at particular locations that are necessary for improving the AQ. The reason why it is mentioned here is that the pollution by PM10 represents a major problem in the whole country and the issue is much more complicated than, for example, the pollution by NO2.

From all 8 zones in the Slovak Republic, “the Bratislava region zone” is the only one where the air pollution level has not exceeded the limit values for PM10. On the other hand, the spatial distribution of PM10, NO2 and SO2 concentrations were mainly evaluated on the basis of model calculations. This campaign fully complies with the requirement of the FW Directive to perform the AQ assessment throughout the zone, and it also provides broader applications related to the possibility of tuning model estimations. It enables the municipalities and monitoring managers to select proper sites for installing new automated monitoring stations, which should be done in this zone by the end of year 2005.

Delimitation of the zones in Slovakia was performed on an administration principle. The zones are identical with the higher territorial units, regions. According to the new Clean Air Act, the municipal policy makers are responsible for the elaboration of action plans and programmes and for the implementation of necessary measures to ensure that the air

4 pollution achieves acceptable levels, meaning that it will not exceed the limit values. The Table 1a (Annex 1) provides the general overview of AQ management areas in SR for each zone/agglomeration and the pollutants for which the action plans have already been or will have to be elaborated. So far, we have not been able to quantify the contribution of natural

PM10 sources, winter sanding, or the particulates that are reemitted from the ground.

Correction factor 1.3 is applied to all automated PM10 measurements in the whole Slovakia. The second measuring campaign was focused primarily on the evaluation of spatial distribution of NO2, SO2 and benzene concentrations, mainly at most frequented roads in different towns and villages in the Bratislava region zone.

Bratislava Region zone

Bratislava region zone spreads over an area of 1685 km2 and the number of inhabitants is approximately 1,65 million. Little Carpathian Mountains extend from Bratislava in the north east direction dividing the lowland into the Plain and the Bor Lowlands across the whole area at the altitude of 130-514 meters. Wind patterns in this area are affected mainly by these slopes, which are located perpendicularly to the generally prevailing North West wind direction.

So far, the industrial sources, the traffic and/ or other specific local emission sources have not affected this zone very much. That is why this is still the only zone in the Slovak Republic, where the regular measurements have not been carried out by the SHMU yet. The only automated monitoring station in this area is operated by the Slovnaft refinery in a small village located close to the city Bratislava (appr. 5 km). For comparison of passive and automated measurements, the mobile stations Slovnaft and Poddunajske Biskupice, which are located in Bratislava city but very close to this zone, were also taken into account (at maps they are numbered as points 1 and 2). Because all of these stations are operated by petrochemical refinery Slovnaft, Ltd., for some statistical analyses it was useful to consider also the measurements from the city stations.

5 3. METHOD

In total, 78 sites were selected for the location of passive samplers. The measurements of

SO2 were carried out at 70 sites and the NO2 and benzene were measured at 71 locations. Parallel measurements were carried out at several sites and the analyses were performed at VITO and SHMU simultaneously. Only few samples have been marked by red colour - as questionable, where unexpected concentrations occurred without any reasonable relation to the known emission sources. Most of the samplers were located close to the traffic and in such places, as to be representative for several metres of the measured site. The concentrations of NO2, SO2 and benzene were assessed at all locations by diffusive samplers during the two-week long measuring campaign in November 2004. In the first step, the shelters were mounted before the installation of diffusive samplers at each site. Then meta data, such as the names of the streets, the locations, the geographical coordinations and the photo documentation were assigned to each measuring site.

All of this information was compiled together with the results of measurements and it is complexly presented in the BA zone 10-24/11/2004 report at the web site: http://www.shmu.sk/?page=28. The map is constructed in such a way that when the mouse pointer hits the measuring point, the basic information appears, such as the concentrations measured at that point, see Fig. 1. As the title on the Fig. 1 shows, more information is available by clicking on any particular point where such examples of documentation of particular locations are shown, see the Annex 2. The main objective of this approach is to extend, as much as possible, the availability of information for both the experts dealing with the air pollution and the general public. Subsequently, the concentrations were also measured at the monitoring station in Rovinka and at various automated stations in this zone’s vicinity. From the statistical viewpoint, comparisons between the active and the passive measurements could not be made on any serious level because of lack of sufficient number of regular measurements in this area.

6 Fig. 1 Passive measurements from Bratislava region zone, November 10. - 24. 2004 (click on point to see details)

4. PROCESSING THE RESULTS

The results obtained within the project are presented in the tabular form in the ANNEX 3. The Table 2a shows that 23 samplers were lost. The problems with the analyses of benzene were solved after cooperation with the experts from VITO and parallel samples proved the comparability of these two principally different methods. The average of the absolute values of differences between benzene concentrations from 30 parallel samples was only 0,14

7 µg.m-3 and the correlation coefficient between the corresponding samples reached 0,87. Maximal differences of 0,56 µg.m-3 occurred at the Dunajska Luzna site, where the concentrations of benzene measured by SHMU were 2,21 µg.m-3 and by VITO 2,77 µg.m-3. At 17 sites, what represents almost 60%, the absolute differences between these two sets of samples were less than 0,1 µg.m-3. These figures underline the comparability between the liquid method with CS2 and the GC thermodesorption method and also indicate sufficient accuracy of passive measurements.

4.1 Evaluation of the correspondence between passive and active measurements

The two-week November concentrations measured by passive methods and the average values for this period taken by the automated stations at the same sites were compared. It must be emphasised that the monitoring stations in Slovnaft, Podunajské Biskupice and Rovinka are operated exclusively by the industrial company Slovnaft, Ltd., so the SHMU cannot guarantee the quality of these data. The following table shows the corresponding concentrations of NO2, SO2 and benzene at those three locations during the two-week period in November:

Table 1 Average concentrations of NO2, SO2 and benzene measured by active and passive method during the two-week period in November 2004

Active Passive Active Passive Active Passive

Location SO2 SO2 NO2 NO2 Benzene Benzene Slovnaft mobile 3,1 2,2 13,4 19,7 1,6 3,8 Pod. Biskupice 3,8 1,5 17,5 14,0 3,3 Rovinka 14,7 6,3 14,3 21,3

The SO2 concentrations measured by passive methods, as well as the value at the Slovnaft mobile station compared with the annual average of 15,7 µg.m-3 in 2004, seem to be underestimated. Annual average of SO2 concentration at Podunajske Biskupice was 7,4 -3 µg.m . The SO2 concentrations measured at all tree stations by passive method are lower than those measured by automated analyzers. When the results from the previous campaign and the results from other sites are considered, the shift between active and passive measurements seems to be significant.

In the first campaign, a linear equation was derived in order to correct the SO2 concentrations that are measured by passive methods to the concentrations that were monitored by automated stations, where the SO2* represents the corrected concentrations according to this equation:

SO2* = SO2(PASSIVE)*0.8322+8.88 [equation 1]

8 If we applied this equation for SO2 in Rovinka, the corrected concentration of SO2* would be 14,1 µg.m-3, which is very close to the measured value of 14,7 µg.m-3. As the next analyses show, neither these measurements are very reliable, but they were validated and some doubtful values were designated as non valid (the gaps can be seen in the graph). The values measured by passive method and the corrected concentrations according to the equation 1 will be therefore presented together in next considerations. There is no doubt, that the passive method provides underestimated values because at 25 locations the -3 concentrations of SO2 are lower than 1,7 µg.m (Table 2), which is the concentration measured at the Chopok station at the altitude of 2008 m. This value could be considered as the national country background concentration for SO2 resulted from the long-range transboundary transport. Although the general application of the equation 1 remains questionable, at the present time it seems to be the only one how to correct the measured values if they have to be used for further AQ assessment. According to the expert’s assessment, the corrected concentrations seem to be more realistic than the measured ones. Unfortunately, because of a limited number of parallel concentrations we are unable to make any sophisticated statistical analyses and conclusions. Modified concentrations were therefore used for the presentation of spatial distribution of sulphur dioxide concentrations in the map of the Bratislava region zone.

The behaviour of NO2 concentrations is not so unique. The NO2 concentrations measured by passive samplers were a little bit lower than those measured by automated monitors at Podunajske Biskupice, while an opposite trend was indicated at two other stations. At this time, the only one conclusion that could be generally accepted is that NO2 concentrations measured by passive samplers do not differ by more than ± 30% from those measured by active monitors.

On the other hand, the measurements of benzene by passive methods indicated that they could be taken as fundamental and reliable concentration data, which was clearly proved after the results obtained at 30 locations by two different methods were compared.

9

Table 2 Locations where minimal November SO2 concentrations occurred

ID Altitude SO Locations 2 number m µg.m-3 52 Stupava 174 0.3 55 197 0.3 40 Road from the Baba mountain, bus stop 341 0.4 53 Stupava, centre 147 0.5 4 Dunajská Lužná 123 0.6 36 Limbach 205 0.6 39 Pezinská Baba 530 0.6 67 Závod, highway 164 0.6 38 181 0.6 44 , centre 166 0.7 60 Rohožník 204 0.7 64 Plavecký Mikuláš 246 0.7 12 Bernolákovo 129 0.8 25 146 0.8 57 271 0.9 56 Jablonové 232 0.9 7 140 0.9 62 Sološnica 224 0.9 65 201 1.0 72 , centre 156 1.0 68 Veľké Leváre 168 1.0 26 Báhoň 157 1.0 70 152 1.2 63 Plavecké Podhradie 219 1.3 20 Hrubý Šúr 95 1.4 17 Senec, centre 125 1.5 2 Poddunajské Biskupice, automated station 137 1.5 9 131 1.5 19 Senec, Lidl 125 1.5 51 225 1.6

10

4.2 Evaluation of the spatial and temporal representativeness of the data for the sampling period

In order to know the extent to which our conclusions are representative from a long-term viewpoint (for example one year), in the first step we analysed the annual sets of data from monitoring stations. These analyses should indicate the extent to which the differences between the two-week November concentrations and the annual ones can fluctuate. More comprehensive analyses aimed in this direction revealed further discrepancies related mainly to the insufficient quality of measurements of the basic data. For various reasons, the stations located in the Bratislava agglomeration have also been included in this analysis. It is reasonable to suppose that the character of temporary changes and general dependences at the city stations will be very similar to those stations that are operated by the Slovnaft company itself. In the Table 3, the annual concentrations of pollutants are specified as “M- Annual” and the concentrations evaluated during the two-week period in November as “M- November”. “M” means monitored. This table shows the annual averages from six automated stations in the city of Bratislava and the Bratislava region zone and the corresponding th th averages of SO2 and NO2 pollutants between November 10 and 24 , 2004.

Table 3 The annual and the two-week November averages of SO2 and NO2 concentrations measured at the automated monitoring sites

SO [µg.m-3] SO [µg.m-3] NO [µg.m-3] NO [µg.m-3] Station/ pollutant 2 2 2 2 M-Annual M-November M-Annual M-November Petrzalka1 12,4 12,5 28,1 24,6 Trnavske myto1 8,9 8,9 38,3 28,6 Stare mesto1 12,3 10,1 33,8 21,3 Slovnaft2 15,7 3,1 16,0 13,6 Podunajske Biskupice2 7,4 3,8 17,5 17,5 Rovinka2 11,8 14,7 12,5 14,3 1) Monitoring stations operated by SHMU 2) Monitoring stations operated by Slovnaft, Ltd.

There were major differences in the annual and the November averages of SO2 concentrations between the stations operated by Slovnaft and SHMU. In order to reveal the discrepancies between the SO2 concentrations in November and the annual average values, the time course of the daily patterns of SO2 concentrations was analysed. The following are the graphs of selected stations:

11 Fig. 2

SO2 daily course at Slovnaft

100

90

80

70

60 10. - 24. November -3 m

. 2004

µg 50

40

30

20

10

0 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 2 20 2 20 20 20 20 20 20 20 20 20 20 20 /20 20 /20 20 20 20 20 20 20 20 20 20 1/ 1/ 1/ 2/ 2/ 3/ 3/ 4/ 4/ 5/ 5/ 6/ 6/ 7/ 7/ 7 8/ 8 9/ 9/ 0/ 0/ 1/ 1/ 2/ 2/ 2/ /0 0 /0 0 /0 0 /0 /0 /0 /0 /0 /0 /0 /0 0 /0 0 /0 0 /0 /1 /1 /1 /1 /1 /1 /1 1 5/ 9 2/ 6 1/ 5 8 6 3 1 5/ 2/ 9/ 7 4 2 0 0 1 2 1 2 1 2 0 22 0 20 0 17 0 1 29 1 26 0 23 0 21 0 18 0 16 3

Fig. 3

SO2 daily course at Poddunajské Biskupice

50

45

40

35 10. - 24. November 30 2004 -3 m .

µg 25

20

15

10

5

0 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 /20 /2 /20 1 1 1 2 2 3 3 4 4 5 5 6 6 7 7 7 8 8 9 9 0 0 1 1 2 2 2 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /1 /1 /1 /1 /1 /1 /1 1 2 5 6 7 9 9 1 2 0 15 29 1 26 11 2 08 22 0 20 03 1 01 15 2 12 26 0 23 07 2 04 18 0 16 30

Fig. 4

SO2 daily course at Rovinka

160

140

120 10. - 24. November 100 2004 -3 m .

µg 80

60

40

20

0 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 /20 1/20 1/20 1/20 2/20 2/20 3/20 3/20 4/20 4/20 5/20 5/20 6/20 6/20 7/20 7/20 7/20 8/20 8/20 9/20 9/20 0/20 0/20 1/20 1/20 2/20 2/20 2 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /0 /1 /1 /1 /1 /1 /1 /1 1 5 9 2 6 1 5 8 2 6 0 3 7 1 5 9 2 6 9 3 7 1 4 8 2 6 0 1 2 1 2 1 2 0 2 0 2 0 1 0 1 2 1 2 0 2 0 2 0 1 0 1 30

12 The daily patterns at the presented stations exhibit quite a reasonable time course. A small decline in the comparison to the remaining part of the year (Slovnaft and Podunajske Biskupice) is apparent, but without any evident gaps. As a result, the following step was aimed at the analyses of basic 10-minute SO2 concentrations, but only within the period under the investigation, the Figures 5, 6 and 7. The first two figures proved that the SO2 analyzers did not function correctly at these stations. SO2 concentrations at Slovnaft and Podunajske Biskupice do not exhibit any changes for long periods of time and the analyzers remained quite often at the constant level of 1.332 µg.m-3.

Fig. 5 SO2 10-minute concentrations at the Slovnaft (Vcie Hrdlo) station (10th – 24th November 2004)

Fig. 6 SO2 10-minute concentrations at the Poddunajske Biskupice station (10th – 24th November 2004)

13 Also the time course at the Fig 7 indicates that the SO2 analyzer in Rovinka did not measure correctly during the whole time period. All these gaps point to the low quality of measurements at these stations and underline that these results could not be applied for deriving a new equation for the correction of SO2 concentration from passive measurements.

th th Fig. 7 SO2 10-minute concentrations at the Rovinka station (10 – 24 November 2004)

4.3 Meteorological condition within the period from the climatological point of view

In the time period under the investigation, the temperature did not differ very much from the previous years. The temperature could be taken as an indirect indicator of the amount of emissions mainly from family houses and other local heating sources where the emissions strongly depend on the temperature. Beside seasonal variations of the amounts of emission, the maximal values of ground level concentrations in the winter period result partly also from the adverse dispersion condition in this period of year. The main factor that influences the spatial distribution of emission from many industrial sources is the speed and the direction of wind and, of course, temporary changes in the production. On the Figure 8, the annual and two-week November wind roses are depicted from the automated meteorological observation Kuchyna. The wind roses were constructed from one hour data. This station is not representative for the whole area, which is quite large, and it is located very close to the Little Carpathian Mountains that significantly affects wind conditions. Despite this, the figures indicate large differences between the wind roses from 10th to 24th November and the annual distribution in the year 2004.

14 Fig. 8 Annual and November wind roses at meteorological station Kuchyna.

Windrose Kuchyna, Windrose Kuchyna, Year 2004 November 10-24, 2004

360 360 340 6.0% 20 340 8.0% 20 320 40 320 6.0% 40 4.0% 300 60 300 4.0% 60 2.0% 2.0% 280 80 280 80 0.0% 0.0% 260 100 260 100

240 120 240 120 220 140 220 140 200 160 200 160 180 180

5. EVALUATION OF THE RESULTS

SO2

As it was mentioned, the SO2 seems to be underestimated. The first campaign also showed that the correlation between automated and passive samplers is quite good, but the shift seems to be even several times higher then the concentration itself. This is very clear especially at low concentrations, where the passive method provides much lower concentrations than are measured at rural stations. Therefore, the correction factor was applied for sulphur dioxide concentration and the equation 1 indicates that the increase ranges from 9 µg/m3 at lowest concentrations (0.3 µg/m3) to 5.5 µg/m3 at the maximal value 3 19.7 µg/m . Both the original SO2 and the corrected SO2* concentrations are shown in the Table 2a in the ANNEX 3. The spatial distribution of SO2* concentrations is shown in the Figure 9. The highest concentration achieved the level of 25 µg/m-3 in Dubova and Jur, which is well bellow the limit value. Generally, it could be concluded that the highest concentrations occurred in the north-west direction from the Slovnaft refinery. The prevailing wind from this direction indicates that the local sources combined with the emissions of SO2 from Slovnaft probably play a certain role at the formation of this air pollution level, especially in locations that are closer to this industrial source. With the exception of these areas, which are not very -3 large and reach maximal concentrations of 20 µg.m , the concentration level of the SO2 is bellow 12 µg.m-3 in most of this particular zone.

15 NO2

-3 The highest NO2 concentrations over 26 µg.m were measured at two separate locations, at

Senec close to the Billa supermarket and at one part of town. Maximal isolines of NO2 -3 reaches 21 µg.m occurred in the similar direction as the SO2 concentrations. But when compared with the SO2 isolines, the NO2 maximums are much smaller, which points out mainly to the crucial influence of the local sources represented primarily by the emission from the traffic. The first maximum of NO2 occurs much further from the city of Bratislava and it does not extend to the agglomeration area as it is in the case of SO2. The concentrations of

NO2 are corresponding well with the size of the city population and the locations of sampling points. On the other hand, the level is low in comparison to the annual limit value and the air quality in the whole area is good. The concentrations are less than 16 µg.m-3 in appr. 95% of the area. The air pollution level in the whole zone is bellow 30 µg.m-3, which is the limit value for the protection of ecosystems.

Benzene

As it was already mentioned, the analyses of the results of benzene concentrations measured by passive samplers proved that the accuracy of this principle is sufficient. The spatial distribution presented in the Fig. 11 indicates that the major source in this area is petrochemical refinery Slovnaft, with the maximal concentration of 3.7 µg.m-3 in the village Rovinka located approximately 5 km from this source. The spatial distribution indicates that, with the exception of this site, the pollution levels by benzene do not exceed 3 µg.m-3 in any other location. The isolines in a small areas reached 2,1 µg.m-3 in surrounding of the towns Stupava, Malacky and Pezinok.

6. CONCLUSION

With regard to the pollutants under the investigation, the AQ assessment in the Bratislava region zone did not indicate any area where the air pollution level exceeded or was too close to the limit values. On the other hand, it was documented that at the location not very far from the refinery Slovnaft, the contribution of both the SO2 and the benzene has to be taken into account. The statistical analyzes showed that this period was not representative for a long-term period, because the prevailing wind was not typical for the annual wind frequency distribution.

16 Practically this was the first time we used passive samplers for a large scale air quality assessment of benzene by GC thermodesoption method. The experience we have gained during the second campaign will help us to recognize how and to what extent these results can be generalized and further applied in the air quality assessment and in the preparation of action plans and integrated programmes.

17 * -3 Fig. 9 SO2 in µg.m in zone Bratislava, November 2004

18 -3 Fig. 10 NO2 in µg.m in zone Bratislava, November 2004

19 Fig. 11 Benzene in µg.m-3 in zone Bratislava, November 2004

20 7. ANNEXES

Annex 1

Table 1a Zones and agglomerations in the Slovak Republic

Banska BRATISLAVA Bratislava KOSICE Kosice Trnava Nitra Trencin Presov Zilina Bystrica Zone/ AGGLOMERATION AGGLOM. Zone AGGLOM zone zone zone zone zone zone Zone

Area 368 km2 1685 km2 245 km2 6508 km2 4148 km2 9455 km2 6343 km2 4502 km2 8993 km2 6788 km2

population 452053 164818 240915 512934 547173 664072 718358 608990 763911 682983 >LV +MoT * * * * * * * * * * Pollutant in NO2, PM10 NA PM10 PM10 PM10 PM10 PM10 PM10 , SO2 PM10 PM10 2003/2004

1) PM10* = PM10 x 1.3

2) NA – regular measurements are not available to the sufficient extent yet

3) Ozone is not considered in this table, because is regarded to be a rather global problem.

21 ANNEX 2 Samples of sampling sites Measuring campaign, Bratislava region zone, November 10. – 24. 2004

General information Number of point 3 Name of street/area Village Rovinka, monit. station of Slovnaft Monitoring objectives Preliminary assessment Longitude 17º 13' 34,4'' Latitude 48º 06' 05,5'' Altitude 129 m Characterization of the location Village, family houses Classification of the station Type of area Suburban, next to main road to Bratislava Type of station Background Daily traffic volume High Heavy duty fraction of traffic Middle Traffic speed High Type of street Concentration measured [µg.m-3] NO2 21,0 * SO2/SO2 6,3/14,1 Benzene 3,7 Comments: Main source of emissions are traffic and petrochemical refinery Slovnaft, Ltd..

22 Measuring campaign, zone Bratislava region, November 10. – 24. 2004

General information Number of point 12 Name of street/area Village Bernolákovo Monitoring objectives Preliminary assessment Longitude 17º 17' 59,9'' Latitude 48º 11' 58,4'' Altitude 129 m Characterization of the location Open area, surrounded by trees Classification of the station Type of area Suburban Type of station Background Daily traffic volume Heavy duty fraction of traffic Traffic speed Type of street Concentration measured [µg.m-3] NO2 11,1 * SO2/SO2 0,8/9,5 Benzene 1,3 Comments:

23 Measuring campaign, zone Bratislava region, November 10. – 24. 2004

General information Number of point 62 Name of street/area Village Sološnica Monitoring objectives Preliminary assessment Longitude 17º 13' 51,5'' Latitude 48º 27' 54,6'' Altitude 224 m Characterization of the location Centre, partly built up area, family houses Classification of the station Type of area Suburban, first class street Type of station Traffic Daily traffic volume Low Heavy duty fraction of traffic Low Traffic speed Middle Type of street Wide Concentration measured [µg.m-3] NO2 9,7 * SO2/SO2 0,9/9,7 Benzene 1,7 Comments: Main source of emissions are traffic and local heating units.

24 Measuring campaign, zone Bratislava region, November 10. – 24. 2004

General information Number of point 56 Name of street/area Village Jabloňové Monitoring objectives Preliminary assessment Longitude 17º 05' 50,9'' Latitude 48º 20' 53,0'' Altitude 232 m Characterization of the location Centre, built up area with family houses Classification of the station Type of area Urban, first class street Type of station Traffic Daily traffic volume Low Heavy duty fraction of traffic Low Traffic speed Middle Type of street Wide, relative open Concentration measured [µg.m-3] NO2 11,0 * SO2/SO2 0,9/9,6 Benzene 1,5 Comments: Main source of emissions are traffic and local heating units.

25 ANNEX 3

Table 2a Results of measurement – zone Bratislava region 2004

ID Altitude Location SO2 SO2* NO2 C6H6 number M µg.m-3 µg.m-3 µg.m-3 µg.m-3 1 Slovnaft mobile station 131 2.9 11.3 19.0 3.8 2 Podunajské Biskupice, automated station 137 1.5 10.1 14.0 3.3 3 Rovinka 129 6.3 14.1 21.0 3.7 4 Dunajská Lužná 123 0.6 9.3 20.3 2.8 5 119 X X 1.8 6 137 6.2 14.0 16.6 0.1 7 Miloslavov 140 0.9 9.7 15.3 1.5 8 Tomášov 128 8.3 15.8 17.9 1.5 9 Most pri Bratislave 131 1.5 10.1 18.5 1.9 10 129 4.7 12.8 18.2 2.1 11 Metro 124 14.6 21.0 16.7 1.9 12 Bernolákovo 129 0.8 9.5 11.1 1.3 13 Bernolákovo, highway 141 5.3 13.3 15.6 0.2 14 Veľký Biel 128 3.9 12.1 15.0 1.5 15 Senec, highway 124 14.4 20.9 18.8 1.6 16 Senec, BILLA 117 16.4 22.6 26.2 2.3 17 Senec, centre 125 1.5 10.1 14.4 1.6 18 Senec, walking zone 97 5.1 13.1 12.9 1.7 19 Senec, Lídl 125 1.5 10.1 17.7 0.0 20 Hrubý Šúr 95 1.4 10.1 11.2 1.6 21 Kráľová pri Senci 122 2.2 10.7 11.4 1.7 22 Nový Svet 116 X X 1.3 23 Čataj 139 3.2 11.5 11.6 1.3 24 Čataj, highway 144 X X X 1.1 25 Igram 146 0.8 9.6 9.7 0.9 26 Báhoň 157 1.0 9.7 11.6 1.0 27 151 12.2 19.0 22.5 2.2 28 Doľany 233 12.1 18.9 13.5 X 29 Častá 241 X X 1.6 30 Dubová 225 19.7 25.2 15.8 1.5 31 Modra – Kráľová 230 14.8 21.2 12.2 X 32 Modra, centre 161 4.4 12.6 19.2 X 33 Modra, periphery 172 10.2 17.4 28.6 2.2 34 Jur 135 19.3 24.9 12.5 1.3 35 Pezinok, part Myslenice 142 3.2 11.6 18.2 1.8 36 Limbach 205 0.6 9.4 6.9 1.4 37 Pezinok 155 14.0 20.5 19.8 2.4 38 Vinosady 181 0.6 9.4 13.1 1.5 39 Pezinská Baba 530 0.6 9.4 10.0 0.5 40 Road of Baba mountain, bus stop 341 0.4 9.2 4.6 X 41 Pezinok, hospital 211 10.5 17.6 14.2 1.1 42 Pezinok, bus stop 189 13.8 20.3 22.8 2.3 43 Pezinok, castle 163 7.1 14.7 27.3 2.6 44 Pezinok, centre 166 0.7 9.4 18.5 2.8

26 Continuation of Table 2a

45 Šenkvice 153 3.7 12.0 19.1 1.6 46 Pezinok, Hypernova 167 15.0 21.4 23.0 1.9 47 Viničné 139 3.8 12.1 21.9 1.7 48 Slovenský Grob, centre 140 1.9 10.5 12.6 1.9 49 Chorvátsky Grob 141 15.3 21.6 17.7 1.8 50 Chorvátsky Grob, highway 143 X X X 51 Marianka 225 1.6 10.2 10.0 3.2 52 Stupava 174 0.3 9.1 22.0 1.7 53 Stupava, centre 147 0.5 9.3 19.1 3.1 54 244 5.9 13.8 14.0 1.5 55 Lozorno 197 0.3 9.2 12.0 1.8 56 Jablonové 232 0.9 9.6 11.0 1.5 57 Pernek 271 0.9 9.6 18.0 1.9 58 Kuchyňa 244 2.3 10.8 11.0 1.6 59 Rohožník, periphery 200 2.9 11.3 9.7 1.6 60 Rohožník 204 0.7 9.4 11.0 2.0 61 Rohožník, cement factory 197 3.6 11.9 7.1 1.0 62 Sološnica 224 0.9 9.7 9.7 1.7 63 Plavecké Podhradie 219 1.3 10.0 13.2 1.6 64 Plavecký Mikuláš 246 0.7 9.4 6.7 1.2 65 Studienka 201 1.0 9.7 9.7 1.7 66 Závod 165 2.2 10.7 11.9 1.8 67 Závod, highway 164 0.6 9.4 23.0 1.9 68 Veľké Leváre 168 1.0 9.7 13.4 1.1 69 Malé Leváre 159 2.8 11.2 6.2 1.1 70 Gajary 152 1.2 9.9 8.8 X 71 Kostolište 159 11.6 18.5 11.3 1.7 72 Malacky, centre 156 1.0 9.7 16.6 2.6 73 Malacky, periphery 161 2.5 11.0 17.3 2.5 74 Malacky, highway 178 X X X 75 Plavecký štvrtok 158 9.4 16.7 17.0 1.9 76 Záhorská Ves 143 X X X 77 Vysoká pri Morave 130 X X 1.8 78 143 10.4 17.5 17.1 1.9

Explanation: 1.) X missing, 2.) SO2* corrected concentrations

27