Air Pollution in the Base Stations of the Environmental Integrated Monitoring System in Poland

Air Pollution XIII 465

Air pollution in the base stations of the environmental integrated monitoring system in Poland

K. Sawicka-Kapusta, M. Zakrzewska, J. Gdula-Argasińska & G. Bydłoń Department of Environmental Monitoring, Institute of Environmental Sciences, Jagiellonian University, Poland

Abstract

Air pollution by heavy metals and sulphur dioxide in the Base Station of the Integrated Monitoring of the Environment was estimated using lichen Hypogymnia physodes (L.) Nyl. as a bioindicator. In July 2001 lichen samples from the natural environment were collected in all seven Base Stations (Szymbark, Św.Krzyż, Pożary, Storkow, Koniczynka, Puszcza Borecka, Wigry). The concentration of heavy metals (Cd, Pb, Cu, Zn, Fe) and S were determined in the lichen samples. The global pollution Index and Sulphur Index showed different air contamination of the studied Base Stations. During the winter season 2002/2003 and the summer season 2003 Hypogymnia physodes were transplanted to three Base Stations (Szymbark, Św. Krzyż, Koniczynka). The results confirmed air contamination by heavy metals and sulphur dioxide of the investigated Base Stations. The sources of emissions which caused contamination are different in the cases of these three areas. Keywords: air pollution, heavy metals, sulphur dioxide, Hypogymnia physodes, biomonitoring, transplantation.

1 Introduction

Poland was one of the most polluted country in the Eastern Europe. For a long time Poland took the third place in sulphur dioxide emission and second place in the dust emission after former Soviet Union and East Germany [1]. The situation has improved considerably during last fifteen years, but still most of the natural

WIT Transactions on Ecology and the Environment, Vol 82, © 2005 WIT Press www.witpress.com, ISSN 1743-3541 (on-line) 466 Air Pollution XIII environment is contaminated. The State Environmental Monitoring has been implemented based on the Act on the Establishment of the State Inspection for Environmental Protection of 1991. The new Environmental Protection Law of 27 April 2001 strengthened and broadened the scope of tasks conducted within the State Environmental Monitoring. According to these Acts, the State Environmental Monitoring is a system of the measurements, assessments and prognoses concerning the environment’s status. It is carried out by the units of the state administration self-governments as well as by institutes, universities and economic enterprises [2]. Integrated Monitoring of the Environment is one of the programme within the State Environmental Monitoring. It was created to control the condition and changes of natural ecosystems in Poland. Several geographical and biological parameters have measured in seven Base Stations located in different part of the country [3]. Lichen Hypogymnia physodes (L.) Nyl. was used to estimate the air pollution in Base Station of the Integrated Monitoring of the Environment. Biological monitoring is known to be very useful method in assessment of environmental contamination [4, 5]. Lichens the symbiotic association between fungus and alga have been shown to be highly sensitive to air pollution. They absorb substances for growth and survival through the exposed surface of the thallus making them intolerant to air pollution. Epiphytic lichens growing on the tree stems and branches use them only as substrate. Instead lichens get nutrients from rainwater and deposited dust. Along with the essential nutrients, they absorb many nonessential or harmful substances as well [6]. Lichens show the concentrations of metals and sulphur as a function of the amount of atmospheric deposition. Thus it makes lichens widely used in monitoring of air pollution [7, 8, 9]. The aim of this study was to estimate air contamination in Base Station of the Integrated Monitoring of the Environment using lichen Hypogymnia physodes as bioindicator.

2 Material and methods

In July 2001 samples of Hypogymnia physodes (L.) Nyl. were collected in all seven Base Station of the Integrated Monitoring of the Environment: Storkowo in Zachodniopomorskie district, Puszcza Borecka, Wigry located in Warmińsko- mazurskie district, Koniczynka in Kujawsko-pomorskie district, Pożary in Mazowieckie district, Święty Krzyż in Świętokrzyskie district and Szymbark situated in Małopolska, fig. 1. In the middle of October 2002 and middle of April 2003 Hypogymnia physodes from unpolluted area (Borecka Forest, north-eastern Poland) were transplanted to three Base Station (Szymbark, Św. Krzyż, Koniczynka). The transplants were exposed for 6-months long periods of winter season 2002/2003 (15th October 2002 – 15th April 2003) and of summer season 2003 (15th April – 15th October 2003). Unwashed lichens collected from natural environment and after transplantation were dried to constant weight (at 60-70˚ C) and digested in a 4:1 nitric and perchloric acid. Concentration of heavy metals Cd, Pb, Cu, Zn, Fe were determined using IL 250 flame AAS [10, 11]. Sulphur concentrations in lichens were determined using turbidimetric Butters-Chenry’s method. Reference materials (SRM 1573) were also analysed. Data are presented

WIT Transactions on Ecology and the Environment, Vol 82, © 2005 WIT Press www.witpress.com, ISSN 1743-3541 (on-line) Air Pollution XIII 467 in µg·g-1 dry weight. One way ANOVA and post hoc Tukey’s test were used to determine the statistical differences [12]. In case of transplanted lichens’ accumulation of metals and S after 6 month period of exposition were calculated as subtraction of the control values in lichens from Borecka Forest before transplantation.

Figure 1: Location of Base Stations of Integrated Monitoring of Environment.

Table 1: Cadmium and lead concentration (µg·g-1 d.w.) in lichen Hypogymnia physodes collected from Base Stations of Integrated Monitoring of the Environment in 2001.

Base Station Mean values ±SE min-max Cd Pb 0,75 ab ± 0,13 17,93 ab ± 3,05 P. Borecka N = 6 0,37 - 1,29 9,98 - 28,73 0,47 ab ± 0,07 8,51 a ± 1,84 Wigry N = 8 0,19 - 0,78 3,87 - 19,38 0,36 a ± 0,03 9,78 a ± 2,54 Storkowo N = 18 0,19 - 0,60 3,84 - 46,02 0,89 25,17 Koniczynka N = 2 0,85 - 0,92 15,28 - 35,07 0,50 ab ± 0,11 13,18 ab ± 1,33 Pożary N = 5 0,20 - 0,78 9,86 - 17,47 0,77 b ± 0,08 22,36 b ± 3,30 Św. Krzyż N = 7 0,53 - 1,12 5,93 - 32,76 0,95 ab ± 0,30 22,83 ab ± 0,77 Szymbark N = 3 0,37 - 1,39 21,93 - 24,37 a,b – different letters indicate statistical differences between Base Stations.

Table 2: Copper, zinc, iron and sulphur in (µg·g-1 d.w.) in lichen Hypogymnia physodes collected from Base Stations of Integrated Monitoring of the Environment in 2001.

Base Stations Mean values ±SE min-max Cu Zn Fe S 4,0a 56b ± 9 404ab ± 23 1200a ± 76 P. Borecka N = 6 ±0,3 26 - 92 328 - 495 1040 - 1502 3,3 - 5,0 5,2b ± 70bc ± 3 571ab ± 55 1380a ± 145 Wigry N = 8 0,3 60 - 86 378 - 787 714 - 2005 3,6 - 6,4 5,2b ± 62bc ± 4 422b ± 27 1329a ± 51 Storkowo N = 18 0,2 39 - 109 249 - 733 1033 - 1822 3,6 - 6,4 11,8 91 733 2889 Koniczynka N = 2 9,2 - 86 - 96 646 - 820 2791 - 2987 14,4 6,2bc ± 92 c ± 12 578ab ± 93 1531a ± 1841 Pożary N = 5 0,6 59 - 121 403 - 924 1076 - 2188 4,7 - 8,3 6,7 c ± 150a ± 10 715a ± 127 1483a ± 76 Św. Krzyż N = 7 0,3 122 - 193 453 - 1457 1215 - 1722 5,6 - 7,7 N = 3 7,0bc ± 105ac ± 17 898ab ± 329 1858a ± 1651 Szymbark 0,2 81-137 552 - 1556 1650 - 2184 6,8 - 7,3 a,b,c – different letters indicate statistical differences between Base Stations

3 Results

Cadmium concentration ranged from 0.36 µg·g-1 in lichens collected in Storkowo to 0.95 µg·g-1 in Szymbark Base Station (Table 1). In Hypogymnia physodes collected from Base Station Koniczynka cadmium concentration was also very high (0.89 µg·g-1). The highest lead concentrations ranged from 22 do 25 µg·g-1 were found in three Base Stations: Koniczynka, Św. Krzyż and Szymbark. The lowest lead concentrations (below 10 µg·g-1) were noticed in northern Base Stations: Storkowo and Wigry (Table 1). Copper amount was similar in almost all Base Stations (ranged from 4.0 to 7.0 µg·g-1) with exception of Koniczynka were copper concentration was twice higher – 11.8 µg·g-1. Zinc concentration in collected lichens was lowest in Puszcza Borecka and Storkowo Base Stations - about 60 µg·g-1 and highest in Św. Krzyż - 150 µg·g-1. Level of iron in Hypogymnia physodes ranged from 404 µg g-1 in Puszcza Borecka to 898 µg·g-1 in Szymbark. Only two among seven

Base Stations meet the iron value which normally is expected in clean area (about 400 µg·g-1). Sulphur concentration in thallus of Hypogymnia physodes collected in Base Stations ranged from 1200 µg·g-1 in Puszcza Borecka to 2889 µg·g-1 in Koniczynka. Also the high sulphur concentration - 1858 µg·g-1 was found in Szymbark (Table 2). To compare the air contamination of Base Stations of the Integrated Monitoring of the Environment by heavy metals and sulphur dioxide a global pollution index (GI) was calculated. It represents the sum of the indexes calculated for all metals and sulphur for each Base Station. The index shows how many times the concentration of a given metal or sulphur in Hypogymnia physodes from each Base Stations exceeds the level of this element in lichen from clean area. None of the investigated Base Stations had least of amounts for all five heavy metals. Therefore ‘a control’ area was constructed on the basis of the smallest concentrations of particular metals from different Base Stations. The lowest concentration of cadmium (0.36 µg·g-1) was found in Storkowo, the lowest concentration of lead (8.51 µg·g-1) was found in Wigry, the lowest concentration of copper (4.0 µg·g-1), zinc (56 µg·g-1) and iron (404 µg·g-1) were found in Hypogymnia physodes from Puszcza Borecka (Table 1, 2).

Table 3: Global Pollution Index (GI) of the Base Stations of Integrated Monitoring of the Environment for metals and sulphur.

Index Base Station Cd Pb Cu Zn Fe GI GI metals sulphur

P. Borecka 2,1 2,1 1,0 1,0 1,0 7,2 1,5

Wigry 1,3 1,0 1,3 1,3 1,4 6,3 1,7

Storkowo 1,0 1,1 1,3 1,1 1,0 5,5 1,7

Koniczynka 2,5 3,0 3,0 1,6 1,8 11,9 3,6

Pożary 1,4 1,5 1,5 1,6 1,4 7,4 1,9

Św. Krzyż 2,1 2,6 1,7 2,7 1,8 10,9 1,9

Szymbark 2,6 2,7 1,8 1,9 2,2 11,2 2,3

Regarding heavy metals global index of Base Stations Storkowo (GI=5.5), Wigry (GI=6.3), Puszcza Borecka (GI =7.2) and Pożary (GI=7.4) were classified as relatively clean with index value below 10. To moderately contaminated belong Św. Krzyż (GI=10.9), Szymbark (GI=11.2) and Koniczynka (GI=11.9). According to pollution index for sulphur to clean area belong Puszcza Borecka (GI=1.5). Moderately contaminated were Wigry, Storkowo, Pożary and Św.

Krzyż with index value from 1.6 to 2.1. Base Stations Szymbark and Koniczynka were classified as heavily contaminated sites with GI>2.1 (Table 3). The highest concentration of all investigated metals and also the highest concentration of sulphur were found in Koniczynka Base Station located close to Toruń agglomeration. Also high concentration of cadmium, lead, zinc, iron and sulphur were noticed in lichens collected in Św. Krzyż and Szymbark Base Stations (Table 1, 2). Additionally in Koniczynka and Szymbark number of sites in which Hypogymnia physodes were collected was too small and not representative for station’s areas (N=2 and N=3). To those three Base Stations Hypogymnia physodes were transplanted twice for winter 2002/2003 and for summer 2003. After 6-month of exposition samples lichen were analysed for heavy metals and sulphur. Accumulation of cadmium in Hypogymnia physodes after winter transplantation was very high. Lichens from Koniczynka and Szymbark accumulated the same amount 1.21 µg·g-1 the value for Św. Krzyż was slightly low, fig. 2. Accumulation of lead in transplanted lichens ranged from 9 µg·g-1 in Św. Krzyż to 11.5 µg·g-1 in Szymbark, fig. 3. The highest accumulation of copper (7 µg·g-1) was noticed in Hypogymnia physodes from Koniczynka, fig. 4. Similar values for zinc were found in lichens transplanted to Św.Krzyż and Szymbark (60 µg·g-1 on average) while Hypogymnia physodes from Koniczynka accumulated 98 µg·g-1 of this element, fig. 5. Iron accumulation was higher in transplants from Koniczynka (575 µg·g-1) and Szymbark (408 µg·g-1), but much lower from Św. Krzyż (202 µg·g-1), fig. 6. During 6 months of winter transplantation very high accumulation of sulphur was noticed in Koniczynka Base Station (1876 µg·g-1) lichens from two other Base Stations accumulated half of this value, fig. 7. Generally the data for summer transplantation showed the lower accumulation of all heavy metals with exception for cadmium in Szymbark and cadmium, lead and iron in Św. Krzyż, fig. 2-6. Significantly lower accumulation was found for sulphur in lichens from all investigated Base Stations, fig. 7.

2,5 2 1,5 1 0,5 Cd [ug/g] d.w.Cd [ug/g] 0 Szymbark Koniczynka Św. Krzyż control

w inter summer

Figure 2: Cadmium content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

40 35 30 25 20 15 10

Pb [ug/g] d.w. [ug/g] Pb 5 0 Szymbark Koniczynka Św. Krzyż control

w inter s ummer

Figure 3: Lead content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

5 Cu [ug/g] d.w. Cu [ug/g] 0 Szymbark Koniczynka Św. Krzyż control

w inter s ummer

Figure 4: Copper content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

250

200

150

100

50 Zn d.w. [ug/g]

0 Szymbark Koniczynka Św. Krzyż control

w inter s ummer

Figure 5: Zinc content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

1600 1400 1200 1000 800 600 400

Fe [ug/g]d.w. 200 0 Szymbark Koniczynka Św. Krzyż control

w inter summer

Figure 6: Iron content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

3000

2500

2000

1500

1000

S [ug/g]d.w. S 500

0 Szymbark Koniczynka Św. Krzyż control

w inter s ummer

Figure 7: Sulphur content [µg·g-1d.w.] in lichens transplanted in the Base Stations.

4 Discussion

Poland is one of the main sources of heavy metal emissions in Europe [15]. In 1990, Poland emitted 91 tonnes (t) of Cd, 599 t of Cu, 1371 t of Pb and 3091 t of Zn. During 11 years emission of these metals decreased considerably and in 2001 total emissions for Cd was 52 t, for Cu 394 t, for Pb 610 t, and for Zn 1709 t. [16]. The main sources of heavy metals are industry and coal combustion so the higher emissions were restricted to industrial and urban areas. Additional sources of metals and sulphur dioxide in Poland are local sources and long distance transport which are difficult to estimate. Sulphur dioxide emission also decreased during last eleven years from 3210 thousands tonnes in 1990 to 1564 thousands tonnes in 2001 [16]. Air contamination in Base Stations of the Integrated Monitoring of the Environment was on average level mainly because of elevated cadmium concentration and high concentration of lead and sulphur in some of the Stations.

Lichens from Koniczynka Base Station had the highest concentrations of lead, copper and sulphur while Szymbark had the highest amount of cadmium and iron and quite high concentration of lead and sulphur. Św. Krzyż was also included to more contaminated stations (Table 1,2). Metal and sulphur accumulation in lichens after winter 2002/2003and summer 2003 transplantations confirmed air pollution in Koniczynka, Sw. Krzyż and Szymbark Base Stations. The influence of heating season (higher amount of metals and sulphur in transplanted lichens) was evident in Koniczynka and Szymbark Base Stations. Św. Krzyż showed different pattern of metals accumulation was higher after summer transplantation, it is probable results of long distance transport. Three Base Stations (Wigry, Pożary and Św. Krzyż) are located in Wigierski, Kampinoski and Świętokrzyski National Park. Assessment of air pollution in Polish National Parks using Hypogymnia physodes as a bioindicator have been done in 1998 [17]. Comparison of these data and results of our investigation are summarising in Table 4.

Table 4: Metals and sulphur concentrations [µg·g-1] in lichen Hypogymnia physodes collected in National Parks in 1998 and in lichens collected in Base Stations in 2001.

Location Concentration (µg g-1)

Cd Pb Cu Zn Fe S

P. Borecka 1998 N = 3 0,55 14,00 5,1 64 379 789 N = 10 0,67 15,11 4,6 68 488 1522 “P. Borecka”

Wigierski NP N = 20 0,80 14,87 6,4 77 633 1088 N = 20 0,45 9,76 5,2 66 632 1354 “Wigry”

Świętokrzyski N = 4 0,70 21,00 10,3 145 953 1431 NP N = 7 0,77 22,36 6,7 150 715 1483

“Św. Krzyż”

Kampinowski N = 7 0,63 13,15 9,1 115 715 1235 NP N = 8 0,59 14,51 6,1 88 550 1394

“Pożary”

It was expected that heavy metal concentration will be lower than 3 years ago because of the decreasing emissions of metals and sulphur dioxide in Poland [16]. In Wigierski National Park concentration of lead and cadmium was lower, while other investigated metals are on same level; concentration of sulphur is about 25 % higher than three years ago. Metal and sulphur concentrations in Św. Krzyż and Pożary Base Station are on the same level as in Świętokrzyski and Kampinoski National Park in 1998. Data for Puszcza Borecka from 1998 and 2001 are the same or slightly higher with exception for sulphur which increased about 50% (Table 4). Each of investigated Base Stations is located in different administration district in Poland, fig.1. In 2001 total cadmium emission ranged from 1303 kg in Swietokrzyskie district to 4033 kg in Małopolskie and 6015 kg in Mazowieckie district. Lowest amount of lead 9186 kg was emitted in Podlaskie district the highest 57687 kg in Małopolskie. Copper emissions ranged from 5675 in Świętokrzyskie to 22646 kg in Mazowieckie. The lowest zinc emission 26415 kg was noticed in Świetokrzyskie, the highest in Małopolskie 118905 kg [16]. The above data are not quite agreed with metal concentration found in Hypogymnia physodes from Base Stations located in the particular districts. Lichens from Szymbark situated in Małopolskie district with one of the highest metals emissions, accumulated high amount of metals. Explanation for highest metal concentrations in lichens from Koniczynka is their localisation close to Toruń agglomeration. Generally, metal concentrations in lichens both collected and transplanted reflected rather local sources of emissions or long distance transport then total emissions from the district. The obtained results confirmed that use of lichens to estimate air pollution by heavy metals and sulphur dioxide is sensitive and the one of the best available methods [9, 18, 19].

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