Evaluation of SO2 and NO2-related degradation of coniferous forest stands in Poland

The Science of the Total Environment 241 Ž1999. 1]15

Evaluation of SO 2 and NO 2-related degradation of coniferous forest stands in Poland a,U Małgorzata Grodzinska-Jurczak , Grazyna ´ ˙ Szarek-Łukaszewskab a

En¨ ironmental Biology Department, Jagiellonian Uni¨ ersity, Ingardena 6, 30-060 Krakow, ´ Poland b Institute of Botany, Polish Academy of Sciences, Lubicz 46, 31-512 Krakow, ´ Poland Received 30 March 1999; accepted 2 June 1999

Abstract Poland has been for many years under the strong influence of air pollutants Žmainly SO 2 , NO 2 and heavy metals. which have inflicted significant damage on Polish forests. A 3-year study on the degradation of coniferous stands assessment as opposed to the level of acidic air pollutants was carried out in various regions of Poland. Concentrations of SO 2 and NO 2 in the atmosphere showed significant seasonal variation Žmonthly range from 0 to 95 and 0.5 to 22 mg my3 considerably for SO 2 and NO 2 ., reaching the highest levels in winter. Their concentrations varied between the sites. Sulphur and nitrogen concentrations in the needles of Norway spruce Ž Picea abies ŽL.. Karst. Ž666]2511 mg gy1 . and Scots pine Ž Pinus syl¨ estris L.. Ž900]2438 mg gy1 . were high and exceeded the levels considered normal from 100 to 400%. Levels of S and N varied seasonally, between the years and sites. All analysed needles from all stations were damaged identifying the beginning to more severe degradation of epicuticular wax structure. Stage of epicuticular wax structures showed a relationship with S content in the needles. Both levels of S and N concentration and erosion of the needle surface wax were in most cases connected to the concentrations of acidic gas in the air. Q 1999 Elsevier Science B.V. All rights reserved. Keywords: Forest decline; Norway spruce; Scots pine; Sulphur; Nitrogen; Needles; SEM

1. Introduction In terms of air pollution, Poland has been for many years one of the most polluted countries in

U

Corresponding author.

Europe. Even though significant decreases in the emissions of principal industrial air pollutants ŽSO 2 , NO 2 and heavy metals. have been registered throughout the last decade, their concentrations in air have still remained at fairly high levels. The effects of SO 2 , NO 2 and heavy metals,

0048-9697r99r$ - see front matter Q 1999 Elsevier Science B.V. All rights reserved. PII: S 0 0 4 8 - 9 6 9 7 Ž 9 9 . 0 0 3 0 5 - 8

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

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persisting for many years, have inflicted significant damage on Polish forests ŽGrodzinski ´ et al., 1990; Dmuchowski and Wawrzoniak, 1994; Jadczyk, 1995; Matzner and Murach, 1995.. The most affected forests are those in the mountains and most affected species are coniferous trees which consist of approximately 77.6% of the total forested area of Poland ŽBiałobok, 1989; Głowny ´ Urza ˛d Statystyczny, 1996; Grodzinska ´ and SzarekŁukaszewska, 1997; Wawrzoniak et al., 1997; Boratynski ´ et al., 1998; Karolewski, 1998.. An evaluation of the level of damage in Polish forests is done mainly by assessing the level of defoliation and discoloration of the photosynthetic tissue ŽWawrzoniak et al., 1997.. Also used to quantify the damage were measurements of macro- and microelements Žsulphur, heavy metals. mainly in the needles of the Scots pine Ž Pinus syl¨ estris L.. and on a smaller scale other conifer species Žspruce. ŽMolski and Dmuchowski, 1984; Grodzinski ´ et al., 1990; Stachurski et al., 1994;

Dmuchowski and Bytnerowicz, 1995; Manninen and Huttunen, 1995; Godzik et al., 1996; Zimka and Stachurski, 1996.. Some changes in the structure of the epicuticular waxes covering without a plants’ surface are considered early indicators of damage to trees ŽTurunen and Huttunen, 1990; Wozny, ´ 1991; Helloqvist et al., 1991; Bermadinger-Stabentheiner and Grill, 1995; Werner, 1998; Cape and Percy, 1998.. These changes are determined by a sensitive method of scanning electron microscopy ŽSEM.. SEM enables the evaluation of wax morphology changes at a very early stage, before visible symptoms have occurred ŽGodzik, 1982; Bermadinger-Stabentheiner, 1995; Turunen and Huttunen, 1996.. SEM has been considerably helpful in the examination of low tolerant species Žmainly conifers. either from highly polluted areas or exposed to various chemical substances under experimental conditions ŽGodzik, 1982; Hanisch and Kilz, 1990; Turunen and Huttunen,

Table 1 Characteristics of the investigated sites Site

Coordinates and altitude of the site Ža.s.l..

Deposition S and Na Žg my2 .

Soil

Forest stands

Ž1. Karkonosze Mts.

508539N 158319E 1306 m

4.8]8.0 S ) 2.8 N

Poorly developed podsols

Spruce forest

Ž2. Tatra Mts.

498169N 208039E 1500 m

1.6]3.2 S 1.4]2.1 N

Poorly developed podsols

Spruce forest

Ž3. Ratanica

498519N 208029E ; 350 m

3.2]4.8 S 2.1]2.8 N

Podsols

Beech]pine forest

Ž4. Cze ˛stochowa

508489N 198269E ; 300 m

3.2]4.8 S 2.1]2.8 N

Podsols

Scots pine forest

Ž5. Kampinoska Primeval Forest

528179N 208279E ; 50 m

1.6]3.2 S 2.1]2.8 N

Sand soils

Scots pine forest

Ž6. Białowieska Primeval Forest

528449N 238529E ; 160 m

0]16 S 1.4]2.1 N

Podsols

Decidous and coniferous Žpine] spruce forest.

a

According to Mill et al. Ž1994..

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

1990, 1996; Bermadinger-Stabentheiner, 1994; Grodzinska-Jurczak, 1994, 1996; Huttunen, 1994; ´ Bermadinger-Stabentheiner, 1995., especially when it is combined with other methods Že.g. determination of S, N and heavy metals concentrations. for assessment of forest degradation. The aim of this study was to conduct an assessment of the degradation of coniferous stands in various regions of Poland as opposed to the level of environmental degradation, relative to levels of acidic air pollutants ŽSO 2 and NO 2 .. It was intended that this goal would be achieved by determining: Ž1. concentrations of sulphur and nitrogen dioxides in the air along a transect running from south-west to north-east Poland; Ž2. concentrations of sulphur and nitrogen in pine and spruce needles; and Ž3. assessing damage to the structure of epicuticular wax in epistomal regions in needles of both the Norway spruce Ž Picea abies ŽL.. Karst. and the Scots pine Ž Pinus syl¨ estris L...

2. Material and methods 2.1. Study area The investigation was conducted at six stations ŽFig. 1, Table 1.. Two stations were located in the mountains Žthe Karkonosze Mts., Szrenica Mt. 1362 m a.s.l. } station 1, the High Tatra Mts., Psia Trawka, 1500 m a.s.l. } station 2.. Station 3 was located in the Carpathian foothills ŽRatanica area, approximately 350 m a.s.l., 40 km south of Cracow., station 4 was on the Krakow-Cze ˛sto´ chowa Upland, a 15-km distance of Cze ˛stochowa, within the Orle Gniazda Landscape Park, two stations were set at lowland locations: the station 5 Kampinoska Primeval Forest, approximately 50 m a.s.l., station 6-the Białowieska Primeval Forest, approximately 160 m a.s.l. The stations in the current study were selected in order to determine the level of damage to coniferous trees, both in areas exhibiting different pollution levels Žthe Karkonosze Mts., Krakow ´ and Cze ˛stochowa regions, Kampinoska Primeval Forest. and also in relatively unpolluted sites ŽBiałowieska Primeval Forest. ŽTable 1.. Among

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the stations used in this study, the Białowieska Primeval Forest site located in the north-eastern part of Poland is a non-industrialised region affected only by local low emissions Žfrom home furnaces . and thus regarded as one of the most environmentally clean regions in Poland. Cze ˛stochowa is located in the region of Poland suffering under the highest impact of various industrial emissions Žacidic pollutants, dusts.. This region also had the most congested roads Žplied mainly with heavy vehicles.. At the same time the level of sulphur and nitrogen accumulation could be mitigated Žlowered. by high emissions of alkaline dusts Žcontaining Mg and Ca.; the emissions in the Cze ˛stochowa province Žvoivodeship. were 6000 t yeary1 in 1995, including 1300 t yeary1 from cement factories and the refractory materials industry, as well as by occurrence of soils with a high buffer capacity Žbrown rendzinas originating from Jurassic limestones ŽKrolikowski et al., 1986; ´ . Głowny Urza ˛ d Statystyczny, 1996 . ´ The spruce forests of the Karkonosze Mts. were the most liable to accumulate large quantities of sulphur whilst at the same time showing the highest extent of degradation, having been for many years subjected to very high levels of acidic emissions. Input of sulphur in this area has been very high in recent years Žapprox. 20 kg yeary1 ., exceeding seven fold the concentrations regarded as critical, while the deposition of alkaline dusts was very low ŽZimka and Stachurski, 1996.. The reaction of soils, already acidic by their own virtue, dropped recently by 0.5]1.0 in pH scale, reaching 3.0 in some parts of the Karkonosze Mts. The high levels of soil acidification have been deemed to be the main cause of decline among spruce stands in these Mts. ŽBoratynski ´ et al., 1998.. The damage has in the main been sustained by older trees and the degree of damage increases with altitude above sea level Žapprox. 30 and 60% of reduction in photosynthesis-related tissues for 500 and 1200]1300 m a.s.l. ŽJohnson et al., 1989; Borecki et al., 1995.. 2.2. Sampling and analysis procedure 2.2.1. Passi¨ e samplers At each station air concentrations of SO 2 and

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M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

Fig. 1. The study sites: Ž1. Karkonosze Mts.; Ž2. Tatra Mts.; Ž3. Ratanica; Ž4. Cze ˛stochowa; Ž5. Kampinoska Primeval Forest; and Ž6. Białowieza ˙ Primeval Forest.

NO 2 were determined, as well as concentrations of S and N and damage to epicuticular wax at Scots pine and Norway spruce needles. The measurements of a monthly average concentration of NO 2 and SO 2 in the air were carried out in the period April 1996]March 1998 using a passive, modified Amay]Sugiur method ŽKrochmal and Gorski, 1991a,b.. Passive samplers ´ were hung approximately 3 m above ground level, far from potential sources of air pollution Žbig agglomeration, industrial centres or highways.. The co-workers living in the six study regions,

exchanged samplers on the same day at each point and returned them in air-tight bags to the Krakow ´ laboratory. Samplers absorbed NO 2 and SO 2 from the air, where gas was absorbed by the material impregnated with an absorbant triethanolamine aqueous solution. After collection, content of nitrate ions was analysed spectrophotometrically following reactions with Saltzman reagent. SO 2 absorbed in the samplers was converted into sulphates and determined using ion chromatography ŽKrochmal and Gorski, 1991a,b; Krochmal and Kalina, 1997.. ´

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

2.2.2. Spruce and pine needles Needles of the Norway spruce and Scots pine were collected in June and September over two consecutive years Ž1996 and 1997.. At each site the needle samples Ž5]10 shoots per tree f 100 needles. were taken from the middle or upper canopy Ž3]4 m. of 10]20]30-years-old spruce and pine trees. Branches were collected from west and east facing sides of the trees and analysed as one mixed sample, separately for each season. Plant material was than segregated according to the age class into: 1- and 2-year-old needles Ž12]24-month-old consequently. and stored in polyethylene bags. A part of the needles were air dried for 2 days, ground, and analysed separately for sulphur ŽS. and nitrogen ŽN. concentrations, separately for each age class within each year of sampling. For S concentrations the Butters] Chenery nephelometric method was used, while nitrogen concentration in the needles was determined by the Kjeldahl method ŽNowosielski, 1968.. SrN ratio was calculated on a gram-atom basis. Rest of the collected needles for SEM were obtained from the same trees Žusing the same criteria } number of trees, needles per each site and age class. as for S and N content determina-

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tion. In the laboratory two to three macroscopically undamaged needles per needle age class per tree were chosen and investigated by scanning electron microscopy ŽSEM.. They were placed on aluminium stubs covered with double-sided tape, and then cut with a razor from the middle of the needle to obtain a 5]8-mm piece. Samples were coated with gold Ž20 nm. in a SEM-coating Unit E 5100 and examined under a JEOL JSM-35 scanning microscope using 15 kV. Forty stomatas per needle were viewed and analysed under the SEM at 1000]2000 = magnification. The stomatas of Norway spruce were classified into four stages depending on the degradation of wax crystalloids in the epistomatal chambers as follows: stage I } without visible degradation or aggregation of the wax rodlets; stage II } beginning aggregation of the wax rodlets but less than 1r3 of the stomatal antechamber covered with a flat layer of structurally degraded wax; stage III } medium strong aggregation of wax rodlets on more than approximately 1r3 up to 8r10 of the surface of the epistomatal chamber with formation of a flat layer of wax; stage IV } most severe aggregation and degradation of the formerly structural wax and formation of a continuous wax layer on 9r10 or more of the episto-

Fig. 2. Average 1-month concentrations of SO 2 Žmg my3 . in the air at the following stations in 1996 and 1997.

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M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

matal chamber ŽSauter and Voss, 1986.. The Scots pine classification comprised five stages based on the distribution of wax tubes in the epistomatal area. Stage I represents distribution of wax tubes 100%, stage II 70]100%, stage III 30]70%, stage IV 0]30% and stage V 0%. Stage I a well-preserved structure with intact wax tubes and stage V a seriously damaged structure with no remaining wax tubes ŽTurunen and Huttunen, 1996.. 2.3. Statistical analysis Variations of the sulphur and nitrogen dioxide concentrations in the atmosphere between months were shown in Figs. 2 and 3. Additionally differences in gas concentrations between the sites were determined by the Freedman test ŽByrkit, 1987.. In order to explain whether there was any statistically significant difference in sulphur, nitrogen content and SrN in the Norway spruce and Scots pine needles between the following seasons and years the Freedman test was used ŽByrkit, 1987.. Differences between the sites were determined using analysis of variance ŽTuckey test.. A comparison of wax crystalloids of 1- and 2-year-old needles and needle age and season,

from both conifer species selected from all sites, is presented in Table 4. The number of stomatas of 1- and 2-year-old needles of both species were classified to the following damage stages Žsee Section 2.2.2.. Classification was made separately for each needle investigated under SEM. An indication of needle damage was finally given in percentage Žas a mean values of all investigated needles for each damage stage..

3. Results 3.1. SO2 and NO2 concentration in the air Average 1-month concentrations of SO 2 in the air remained within the range of non-detectable levels at 95 mg my3 Žbi-annual mean at the following stations 5.1]15.9 mg my3 ., whereas NO 2 level ranged from 0.5 to 22 mg my3 Žbi-annual mean at the following stations 1.9]10.3 mg my3 . ŽFigs. 2 and 3.. Concentrations of both gaseous pollutants showed seasonal variations, reaching their highest levels in winter ŽFigs. 2 and 3.. In the case of both gases, their concentration varied between the sites, with the lowest levels recorded

Fig. 3. Average 1-month concentrations of NO 2 Žmg my3 . in the air at the following stations in 1996 and 1997.

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

in the Tatra Mts. and Białowieza ˙ National Park and highest in Ratanica and Cze ˛stochowa Ž P0.05.. At all stations, differences in SO 2 and NO 2 concentrations were observed during the winters of 1996 and 1997.

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higher levels in 1997 Ž P- 0.05.. The same pattern was noticed for Scots pine needles. For sulphur, only the Norway spruce needles from the autumn samples showed higher values in 1997 than in 1996. In the case of the Scots pine no significant differences between the years were found. No notable variations Ž P) 0.05. in sulphur and nitrogen contents between 1- and 2-year-old needles of both conifer species could be detected. Sulphur and nitrogen content in needles of Norway spruce and Scots pine varied significantly between the seasons ŽJune]September. with the exception of 2-year-old spruce needles which were collected in 1996. S and N content in the needles of both species varied between the sites. The S needle content of Białowieza ˙ trees differed significantly Ž P- 0.05. from that in other sites, and significant differences Ž P- 0.05. in nitrogen content in the nee-

3.2. Needle S and N concentration The mean sulphur concentration in the Norway spruce needles ranged from 666 ŽBiałowieza ˙ National Park. to 2511 mg gy1 ŽCze ˛stochowa., while in the Scots pine from 900 ŽKampinos. to 2438 mg gy1 ŽCze ˛stochowa.. Nitrogen mean concentrations were recorded at 0.61 ŽCze ˛stochowa. and 1.67% range ŽTatra Mts.. in Norway spruce and from 0.80 ŽKampinos. to 1.58% ŽCze ˛stochowa. in the Scots pine ŽTable 2.. Nitrogen concentrations in the Norway spruce needles between the subsequent years reached

Table 2 The mean sulphur Žmg gy1 . and nitrogen Ž%. concentrations in the 1- and 2-year-old needles of Norway spruce Ž Picea abies ŽL.. Karst. and Scots pine Ž Pinus syl¨ estris L.. a collected at the following sites in 1996 and 1997 Site species

Needle age Žyears.

Sampling year and season Sulphur

Nitrogen

1996 JunerSeptember

1997 JunerSeptember

1996 JunerSeptember

1997 JunerSeptember

Ž1. Karkonosze Mts. Norway spruce

1 2

974 2292

1010 2053

1332 1421

1609 1582

0.75 0.68

0.70 0.95

1.47 1.53

1.17 1.53

Ž2. Tatra Mts. Norway spruce

1 2

986 1781

1021 1793

1165 1330

1220 1399

0.72 0.69

0.68 0.64

1.67 1.60

1.02 1.42

Ž3. Ratanica Norway spruce

1 2

2009 1981

1715 2257

1326 221

1317 1061

0.95 0.75

0.81 0.71

1.34 1.15

1.44 1.26

Ž4. Cze ˛stochowa Norway spruce

1 2

979 1914

1107 2195

1939 1698

2511 1719

0.61 0.71

0.66 0.75

1.05 1.09

1.06 1.07

Ž4. Cze ˛stochowa Scots pine

1 2

900 ]

917 ]

2438 1787

1777 1827

0.75 ]

0.77 ]

1.32 1.52

1.58 1.49

Ž5. Kampinoska Primeval Forest Scots pine

1 2

1171 1839

1138 1914

1349 1379

1533 1230

0.96 0.83

0.80 0.84

1.28 1.55

1.29 1.25

Ž6. Białowieza ˙ Primeval Forest Norway spruce

1 2

714 1846

666 2128

1212 1624

1225 1335

0.80 0.74

0.68 0.68

1.12 1.29

0.93 1.24

a

At each site 10 trees were investigated.

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

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dles, were detected between Cze ˛stochowa and Białowieza ˙ as well as between Cze˛stochowa and Karkonosze. In the case of the Norway spruce, the lowest SrN ratio Ž0.031. was recorded for needles from the Tatra Mts. and the highest Ž0.147. from the Karkonosze Mts. ŽTable 3.. The sulphurrnitrogen ratio for the Scots pine fell between the range between 0.039 Žautumn 1997. and 0.099 Žautumn 1996. ŽKampinos.. For the Norway spruce, significant differences in SrN ratios between the sites were detected Ž P- 0.05..

of aggregation of the wax rodlets. Less than 1r3 of the epistomatal antechamber was covered with a flat layer of structurally degraded wax Žstage II.. In many cases, however, more severe aggregation and degradation of the formerly structural wax and formation of almost continuous wax layer on 9r10 or more of the epistomatal chamber Žstage IV. were observed ŽPlate 1a]c.. In both June and September 1996 and 1997 similar percentages of stomatas’ degradation were observed but these varied between the sites. In general, the most affected needles were found Žfor both years. in the Karkonosze Mts. and Ratanica Ž31]100% and 51]87% in class IV, respectively. while the lowest degradation levels Ž4%. were observed in the June 1996 samples in Cze ˛stochowa. In both years, differences in wax injuries between the 1- and 2-year-old needles were noticed, although epistomatal wax structures showed different stages at the following sites. Also stages of epicuticular wax

3.3. Epicuticular wax degradation The degradation of wax crystalloids in the epistomatal chambers of 1- and 2-year-old needles of Scots pine and Norway spruce is illustrated in Table 4. All analysed spruce needles from all stations were damaged indicating the beginning

Table 3 The sulphurrnitrogen ratio for 1- and 2-year-old needles of Norway spruce Ž Picea abies ŽL.. Karst. and Scots pine Ž Pinus syl¨ estris L.. a collected at the following sites in 1996 and 1997 Site species

Needle age Žyears.

Ž1. Karkonosze Mts. Norway spruce

1 2

0.057 0.063

0.147 0.095

0.040 0.060

1.041 0.045

4Ž2. Tatra Mts. Norway spruce

1 2

0.060 0.066

0.113 0.123

0.031 0.052

0.036 0.043

Ž3. Ratanica Norway spruce

1 2

0.093 0.093

0.116 0.139

0.043 0.040

0.046 0.037

Ž4. Cze ˛stochowa Norway spruce

1 2

0.070 0.073

0.118 0.128

0.081 0.104

0.068 0.070

Ž4. Cze ˛stochowa Scots pine

1 2

0.053 0.052

] ]

0.081 0.049

0.051 0.054

Ž5. Kampinoska Primeval Forest Scots pine

1 2

0.053 0.062

0.097 0.099

0.046 0.052

0.039 0.043

Ž6. Białowieła Primeval Forest Norway spruce

1 2

0.039 0.043

0.109 0.137

0.047 0.058

0.055 0.047

a

At each site 10 trees were investigated.

Sampling year and season 1996 JunerSeptember

1997 JunerSeptember

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

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Table 4 The degradation of wax crystalloids in the epistomatal chambers of 1- and 2-year-old needles of Norway spruce Ž Picea abies ŽL.. Karst. and Scots pine Ž Pinus syl¨ estris L.. collected at the following sites in 1996 and 1997 a Site species

Needle age Žyears.

Stage of degradation Ž%.b

Sampling year and season 1996 JunerSeptember

1997 JunerSeptember

Ž1. Karkonosze Mts. Norway spruce

1

I II III IV I II III IV

0 21 47 31 0 0 19 81

0 0 47 52 0 0 0 100

0 0 0 100 0 0 0 100

0 0 20 80 0 0 4 36

I II III IV I II III IV

0 0 36 64 0 4 49 50

2 25 31 44 0 5 37 57

25 28 30 16 5 33 26 35

95 5 0 0 6 13 35 45

I II III IV I II III IV

0 0 30 70 0 0 12 87

0 17 31 53 0 0 12 87

10 9 9 72 7 16 11 65

1 12 27 58 0 6 37 51

I II III IV I II III IV

0 25 71 4 1 12 22 64

16 27 21 35 2 17 41 41

41 5 4 50 26 35 26 12

18 25 17 39 32 26 24 17

I II III IV V I II III IV V

0 47 10 46 1 0 10 22 46 21

0 0 44 30 26 0 1 47 35 16

2 22 30 45 0 0 1 4 64 31

9 5 14 52 20 0 0 1 45 55

2

Ž2. Tatra Mts. Norway spruce

1

2

Ž3. Ratanica Norway spruce

1

2

Ž4. Cze ˛stochowa Norway spruce

1

2

Ž5. Kampinoska Primeval forest Scots pine

1

2

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

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Table 4 Ž Continued. Site species

Needle age Žyears.

Stage of degradation Ž%.b

1996 JunerSeptember

1997 JunerSeptember

Ž6. Białowieza ˙ Primeval forest

1

I II III IV I II III IV

1 20 71 7 0 5 71 24

12 49 17 21 2 15 64 19

Norway spruce 2

Sampling year and season

0 1 54 45 0 16 70 14

10 34 35 21 0 22 49 29

a

At each site twice per year ŽJune and September. 10 trees were collected. Needles were of 12 and 24 months old. % } identifies proportion of crystalline waxes distribution in epistomatal area at analysed needles Žsee Section 3..

b

structures varied over the 2-years covered in the study. In the case of Scots pine in both sampling years, similar differences in needle degradation between the seasons ŽJune and September. were noticed. In June 1996 and 1997 most of the needles were classified into II, III and IV stages identifying: 70]100%, 30]70% and 0]30% of wax distribution, respectively. Needles were more damaged during both autumns, rating mainly for III, IV and V stages. The most significant damage to the wax of pine needles originated from September 1996. The stage of epicuticular wax structures varied between 1- and 2-year-old needles.

4. Discussion 4.1. SO2 and NO2 concentration in the air According to Polish standards, the annual average concentration limit of SO 2 in air in protected areas is 32 mg my3 ŽDziennik Ustaw, 1990.. In this study this standard was exceeded several fold Žmainly during winter., with the highest SO 2 concentrations found in stations in southern Poland matching those obtained by Krochmal and Kalina Ž1997. and Wawrzoniak et al. Ž1997.. Two stations were located within specially protected areas Žin national parks of the Tatra and Karkonosze Mts.. where the average annual concentration limit in the air is 11 mg my3 ŽDziennik Ustaw, 1990.. In the Tatra Mts. the standard was exceeded only

twice, while in the Karkonosze Mts. it was exceeded much more often. As regards nitrogen dioxide, the pattern of distribution found in this study followed a similar nation-wide pattern to that found in SO 2 . The highest concentrations occurred in the south of the country Žexcept for Karkonosze station.. In contrast to SO 2 , however, the NO 2 concentrations did not exceed the Polish standard limit value in any month or station, both for protected areas Ž50 mg my3 ., as well as those for specially protected areas Ž30 mg my3 . ŽDziennik Ustaw, 1990.. The results obtained in this study do not differ much from the concentrations of NO 2 recorded in Great Britain in 1992. The highest concentration of this gas measured by the same method in farmlands was 10 mg my3 in Scotland and 17 mg my3 in Wales, whereas the highest concentrations were found in urban areas, 50 mg my3 ŽLondon. ŽAshenden and Bell, 1989; Campbell et al., 1994; Ashenden and Edge, 1995.. It was found that there are significant seasonal fluctuations in the concentrations of these two gases. In the case of SO 2 these high concentrations were to be found in the winter months as in other studies ŽKrochmal and Kalina, 1997; Wawrzoniak et al., 1997.. These higher concentrations, particularly of SO 2 in autumn and winter months, should be explained by lower air temperatures and higher consumption of fossil fuels in generating heat for industrial and domestic premises. The winter seasons covered in the study period

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

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Polish energy industry, has a high sulphur content Ž4]5% S.. As the price differentials are large for fuels of different quality, cheaper coal Žwith high sulphur content. is used most frequently ŽNowicki, 1993.. 4.2. Sulphur, nitrogen concentration and S r N ratio in conifer needles

Plate 1.

were relatively cool and long, particularly in the first year. Hard coal, used as the main fuel in

The concentration of sulphur in both pine and spruce needles exceeded the levels considered ‘normal’ Ž650 mg gy1 for pine and 820 mg gy1 for spruce ŽMolski and Dmuchowski, 1984; Dmuchowski and Bytnerowicz, 1995; Boratynski ´ et al., 1998.. In the case of pine the excess above the standard ranged from approximately 200 to 400%, and for spruce, from approximately 100 to 300%. The highest S concentrations found in both years in areas of southern and south-western Poland were subject to constant impact of acidic industrial pollutants. The normal Žphysiological. sulphur concentration in needles is elevated to the increased S deposition either by chronic or acute stress ŽManninen and Huttunen, 1995.. The results at this study are similar to those conducted in Poland by Dmuchowski and Bytnerowicz Ž1995. and Godzik et al. Ž1996.. The highest concentrations of sulphur in pine needles were recorded in the Upper Silesia Coal Industrial Region Ž2200 mg gy1 ., whilst the lowest values were found in the east of Poland Ž650 mg gy1 .. For the remaining part of Poland these values fell within a 900]1300 mg gy1 range. The levels recorded in the needles in this study also match the results of the nation-wide survey of the state of forests, prepared separately for both national parks and other forests by the State Inspec´. in torate for Environmental Protection ŽPIOS 1994 and 1996. The least damaged coniferous forest stands were found in the north and the central part of Poland and more damaged forest, in the south of Poland. The most damaged forests included those in the Karkonosze Mts. and Silesia ŽBorecki et al., 1995; Wawrzoniak et al., 1997.. Over the 2 years of this study, differences were found in sulphur and nitrogen concentrations in the needles of the two coniferous species. As there is a relation between concentrations of S in

12

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

needles and air concentrations of SO 2 , it is difficult to explain the observed decrease in sulphur concentrations in needles, with a concurrent increase in air levels of SO 2 ŽMolski and Dmuchowski, 1984; Dmuchowski and Bytnerowicz, 1995.. Even though the quantities of sulphur deposited on foliage is highest in winter, the capacity of these species to accumulate is then markedly lower ŽManninen et al., 1991; Wolfenden and Mansfield, 1991.. An additional reduction in quantities of sulphur in needles could also result from high levels of atmospheric precipitation Žin spring and winter.. Wet deposition, apart from providing sulphur input in the form of S]SO4 , could also cause the partial Ž10]30%. leaching of sulphur deposited earlier ŽCape and Lightwowlers, 1988; Zimka and Stachurski, 1996.. Also climatic conditions Žtemperature, precipitation. in both the sampling year and the previous year may affect the diagnostic value of foliar analyses ŽHelmisaari, 1990.. The subsequent years of the study varied both with respect to the amounts of precipitation and average air temperatures. The year 1996 was relatively dry and cool Žlong winter with low temperatures. whilst in 1997 most of the country suffered from floods in summer ŽWawrzoniak et al., 1997.. The increasing tendency in nitrogen concentrations over the 2 years of the study could be associated with enhanced exposure of trees to NO 2 . Increase in N concentration in the needles may also result from co-deposition of S and N and suggest that the effect of increasing SO4 ]S inputs into the soil increases the availability of NO 3 ions by ion exchange. Wintertime N deposition may have an impact on N total content, because N]NO 3 is taken up by the roots during the following growing season. Additionally, the vulnerability of coniferous species to exposure to acidic precipitation depends on the stage of development of needles and the timing within the vegetation period. It has been suggested that the highest vulnerability occurs in spring and the lowest in winter ŽKarolewski, 1998.. Seasonal and annual variations in the nutrient level at the needles is also related to fluctuations in their dry weight.

The ratio between sulphur and nitrogen emphasises the biochemical relationship between those two plant nutrients in conifers. The foliar S to N ratio has been used to assess the impact of atmospheric S deposition on forests ŽCape et al., 1990.. It is both theoretically and practically a more sensitive indicator of the accumulation of S in conifer foliage exposed to S pollution stress than analyses of elemental S ŽMalcolm and Garforth, 1997; Huttunen, 1994.. For the areas not affected by polluting emissions a mean value of 0.028]0.030 Žon a gram-atom basis. for the SrN ratio in the current foliage of Scots pine and 0.046 in polluted areas have been assumed, whereas for Norway spruce, 0.042 for unpolluted Žno calculation for the polluted one. ŽMalcolm and Garforth, 1997.. The SrN ratios achieved in the present investigation also suggest increased S concentrations in both species and in the case of Scots pine from Kampinos and Cze ˛stochowa, exaggerated values were obtained for polluted regions. Significant increase in the needle SrN ratio depending on the air pollution level at the studied sites shows that the SrN index could be successfully used as an index of SO 2 deposition, even in areas where N deposition was relatively high. Moreover, in the case of Scots pine needles, the SrN ratio might be used as an indicator of SO 2 deposition, in areas with equal N deposition andror N supply from the soil. It could also show, besides the observed increase in sulphur and nitrogen concentrations in the needles, along with increasing SO 2 deposition, as a result of either possible co-deposition of S and N andror changes in the availability of N from soil ŽCape et al., 1990. suggested, however, that the SrN ratio is better used as an indicator of the relative importance of S and N compounds as components of atmospheric pollution. The ability of trees to assimilate SO 2 into organic compounds is regulated by the availability of N, the SrN ratio of conifer foliage though should be characteristic of potential needle damage by SO 2 ŽManninen, 1995.. 4.3. Epicuticular wax degradation Erosion of the needle surface wax corre-

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

sponded with its S content. It appeared to be more severe and frequent with an increasing S content in the needles and least harmful at low S foliage concentration. Badly degraded wax of Scots pine needles Žadvanced fusion of tubular waxes between stomata and in the stomatal chambers. was observed when its S content ranged from 1531 to 2003 mg gy1 , whereas changes in wax where noticed at 1268 mg gy1 of S in needles. That relationship, however, could not have been tested statistically in recent studies, since the SEM analysis material was too small. Turunen and Huttunen Ž1991. found that a relatively low SO 2 concentration Ž10]20 mg my3 . might also cause wax degradation. Needle injuries are most probable if SO 2 occurs in combination with NO x and acidic S containing wet deposition ŽTurunen and Huttunen, 1991.. In recent studies SO 2 concentration in the air amounted to much higher values with parallel Žhigh. concentrations of NO 2 . Sulphur dioxide ŽSO 2 . and NO 2 may also have an effect on needle surface waxes through their reaction with water to form acids and may induce erosion of needle surface. In this study on the impact of acidic pollutants on the state of forests, both forms of deposition Ždry and wet. should be taken into account. Many studies on the chemistry of precipitation in Poland ŽDruzkowski and Szczepanowicz, 1988; Hryniewicz ˙ and Przybylska, 1989; Dyduch and Borowska, 1994; Twarowski, 1996; Zimka and Stachurski, 1996; Turzanski ´ and Godzik, 1997. indicate that the areas with the most acidic precipitation in recent years are to a great extent, those with the highest air concentrations of SO 2 and NO 2 . In 1996 in southern Poland Žthe Carpathians. and south-western Poland ŽSudety Mts.. the average annual reaction ŽpH. of precipitation was approximately 4.3, whereas from the south-west towards the east it was slightly higher ŽpH 4.4., and 4.6 in the remaining areas ŽGodzik et al., 1996; Wawrzoniak et al., 1997.. As mentioned earlier, an analysis of the impact of acidic substances should include both forms of deposition particularly in areas of high precipitation ŽKarkonosze Mts... Acidic precipitation may be directly affected by chemical reaction between its . and the waxes or components ŽHq, SO42y, NOy 3

13

their precursors, or indirectly via the soil and root systems ŽCape, 1988; Turunen and Huttunen, 1990, 1991, 1996; Turunen et al., 1995, 1997.. In the current studies most affected epicuticular wax of the needles was found in sites where the S concentration in needles and SO 2 in the air was one of the highest. Least degraded needle wax was observed in Cze ˛stochowa and although it was one of the areas most polluted by both SO 2 and NO 2 , S concentration in foliage was surprisingly low. Dry and wet deposited S- and N-induced changes to the wax surface may be accelerated or increased by extreme climatic conditions. Karkonosze Mts. and Tatra Mts. are the highest of the investigated sites. Karkonosze Mts. and Ratanica are simultaneously located in highly polluted regions, whereas the Tatra Mts. are in a relatively clean area. The harsh mountainous climate with low temperatures, prolonged winter seasons, poor summers, high frequency of precipitation, exposure to snow, ice crystals and fog affected, to a greater extent, the epicuticular wax structure of pine needles Žerosions and a delayed cuticle development. ŽTurunen and Huttunen, 1991; Huttunen, 1994; Turunen et al., 1997.. Interactions between the effects of acidic pollutants and low temperature stress was suggested by Wolfenden and Mansfield Ž1991.. Tolerance of Sitka spruce to low temperature increased after exposure to SO 2 and NO 2 alone or in combination ŽWolfenden and Mansfield, 1991.. Damages to spruce and dwarf pine wax increased with altitude; the higher the elevation the more significant the erosion of wax ŽGrodzinska-Jurczak, ´ 1994.. Wax injuries differed between the 1- and 2year-old needles, more noticeably in the case of spruce. Sensitivity of plants to acidic substances depends on the age and phenology stage of the plant. In most cases, current-year needles were more affected by acid rain than 1- or 2-year-old ones ŽGrodzinska-Jurczak, 1994.. Least tolerant ´ are needles with a low quantity of wax: Ž1. young, elongating with undeveloped cuticle; and Ž2. old, eroded needles containing less wax than well-developed trees ŽTurunen and Huttunen, 1991..

14

M. Grodzinska-Jurczak, G. Szarek-Łukaszewska r The Science of the Total En¨ ironment 241 (1999) 1]15 ´

5. Conclusion The health of Polish forests has been strongly influenced for many years by high levels of air pollution, mainly SO 2 and NO 2 . The increased concentrations of these two gases in the atmosphere correlate with concentrations in needles which exceed standard limit values by two to four times. It is mainly the areas located in the southwest ŽKarkonosze. and west of Poland ŽCze ˛stochowa, Ratanica. which have higher concentrations of gaseous air pollutants, particularly in the winter months. In the last 5 years there has been a significant improvement recorded in the health of Polish forests. In 1996, the defoliation index for spruce and fir was among the lowest for 5 years. There was also an increase in proportion of undamaged trees Žclass 0. of these species, and a reduction in the proportion of less damaged trees Žclasses 2 and 3.. These changes were not, however, evident in spruce stands where the overall level of damage remains high and particularly in the Sudety Mts. where increases have been recorded ŽWawrzoniak et al., 1997.. The improved condition of some of the forest stands could be attributable to reduced levels of SO 2 emissions and higher precipitation in recent years. Because of an expected increase in atmospheric concentrations of NO 2 resulting from an increase in the number of motor vehicles nitrogen deposition should rise in forest areas. An increase in N contents in needles may reduce the resistance of trees to fungal infections as well as making them more sensitive to low temperatures ŽWolfenden and Mansfield, 1991.. Particularly vulnerable are the forest stands in areas exposed to the impact of industrial air pollution and those stands growing on poor sandy soil with low nutrient availability and shortage of water Žlow precipitation during the growing season. ŽWawrzoniak et al., 1997..

Acknowledgements We are grateful to J.K. Holopainen and Sirpa-

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