Are N and S deposition altering the mineral composition of Norway spruce and Scots pine needles in Finland?

Data from a large-scale foliar survey were used to calculate the extent to which N and S deposition determined the mineral composition of Scots pine and Norway spruce needles in Finland. Foliar data were available from 367 needle samples collected on 36 plots sampled almost annually between 1987 and 2000. A literature study of controlled experiments revealed that acidifying deposition mediates increasing N and S concentrations, and decreasing Mg:N and Ca:Al ratios in the needles. When this fingerprint for N and S elevated deposition on tree foliage was observed simultaneously with increased N and S inputs, it was considered sufficient evidence for assuming that acidifying deposition had altered the mineral composition of tree needles on that plot in the given year. Evidence for deposition-induced changes in the mineral composition of tree foliage was calculated on the basis of a simple frequency model. In the late eighties the evidence was found on 43% of the Norway spruce and 27% of Scots pine plots. The proportion of changed needle mineral composition decreased to below 8% for both species in the late nineties.     

Effects of acid rain on growth and nutrient concentrations in Scots pine and Norway spruce seedlings grown in a nutrient-rich soil

The effects of artificially applied acid precipitation on growth and nutrient concentrations of Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst.) seedlings were investigated in a long-term acid irrigation experiment in field conditions. Seedlings of northern and southern origin were planted in boxes containing peat and composted soil rich in nutrients, and sprinkler irrigated with water acidified with nitric and sulphuric acids to pH 3 or pH 4 for periods varying from two to three and a half growing seasons during 1986-1989. Water irrigated (pH 5.4-7.6) and non-irrigated groups of seedlings were also included in the experiment. At the end of the experiment needles, main and lateral shoots and roots were collected from the seedlings for the determination of height growth and biomass partitioning, and for the analysis of S, N, Mg, P, K, Ca, Mn and Fe concentrations. The treatment effects compared to the irrigated control were studied using multivariate analyses of variance and covariance. In the pine seedlings the total dry matter production increased by 25-70% compared with the irrigated controls when the total wet deposition to the seedlings exceeded 67 kg S ha(-1) and 36 kg N ha(-1) (e.g. after two growing seasons' exposure of the pH 3 treatment). The increase was mainly due to an increase in needle dry weight (54-72% greater at pH 3) and root weight (20-65% greater at pH 3), whereas the height growth or shoot weight growth were less affected. The northern provenance pine seedlings responded more clearly to the pH 3 irrigation than the southern ones. The treatments had no consistent effects on any of the growth variables studied in the spruce seedlings, however. The pines had higher root and foliage Ca concentrations as a result of the acid irrigation, whereas in spruce, acid rain decreased the Ca concentration in needles and shoots. Root Mn and Fe concentrations were higher in both species as a result of the pH 3 treatment. A higher soil conductivity and Ca concentration resulted from the prolonged pH 3 treatment. The results strongly support the hypothesis that the long-term growth and nutrient allocation response of conifers to acid precipitation is dependent both on the tree species and on the nutritional status of the soil.     

Atmospheric input of elements to forest ecosystems: a method of estimation using artificial foliage placed above rain collectors

Usefulness of a method of artificial foliage was tested for estimation of total ionic inputs from the atmosphere to forest ecosystems, as well as of processes relevant to ionic fluxes through tree canopies: uptake, leaching, passive flow. The studies were performed in Norway spruce and European beech stands in Karkonosze Mountains (Poland), in 1995-97. Artificial leaves of increasing leaf area index: 0, 2, 6 and 12 m(2) m(-2 )were placed above standard rain collectors. It has been found that total atmospheric fluxes of H(+), NH(4)(+), Ca(2+), Mg(2+), Pb(2+), NO(3)(-) and SO(4)(2-) rose as surface area of the foliage increased. This was especially true for nitrate, sulphate and ammonium. No such relationship was found for K(+), Na(+), Zn(2+), Cd(2+), Cu(2+) and PO(4)(3-). The increase in anion fluxes exceeded that in neutralising cations (NH(4)(+), Na(+), K(+), Mg(2+), Ca(2+)) and led to progressive rainwater acidification with the increase in the foliage area. An analysis of net canopy exchange (atmospheric input-throughfall flux) has shown that SO(4)(2-), PO(4)(3-), Na(+), Ca(2+) and Cu(2+) flowed passively through the tree crowns; NH(4)(+), NO(3)(-), Zn(2+), Cd(2+) and occasionally Pb(2+) were efficiently absorbed, whereas K(+) was leached from the canopies. Beech was more effective in modifying ionic pool from the atmosphere than spruce. This related to H(+) (greater absorption) and Mg(2+) (greater leaching). It has been demonstrated that the results concerning trends in net canopy exchange and produced by the simple method of artificial foliage are comparable to more sophisticated techniques of the measurements. This proves the method to be useful.     

Throughfall chemistry in a spruce chronosequence in southern Poland

The chemical composition of throughfall and canopy leaching, as well as the acid neutralizing capacity and alkalinity depended on the age of Norway spruce (Picea abies Karst) stands and season of the year. A higher amount of sulphur and strong acids was deposited to the soil in the older age classes. Concentrations of SO(4)(2)(-), K(+), H(+), Mn(2+), Fe(2+) and Zn(2+) in throughfall were higher than in bulk precipitation in any season. This suggests that these ions were washed out or washed from the surface of needles and/or barks. The other ions NO(3)(-), NH(4)(+), Ca(2+) and Mg(2+) were retained by the canopy, in particular Ca(2+) and Mg(2+) during the growing season in young stands. Principal component analysis identified five factors responsible for the data structure and suggested the major anthropogenic emission sources were acidic emission (SO(4)(2)(-)+NO(3)(-)), heavy metals-dust particles (Fe(2+)+Mn(2+)+Zn(2+)), ammonium (NH(4)(+)) and H(+), while the natural-origin emission was mineral dust (Na(+)+K(+)+Ca(2+)+Mg(2+)).     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd) and Al concentrations as well as values of Ca/Al in the tip, middle, base sections and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Forest health status in the Carpathian Mountains over the period 1997-2001

The results of forest health status assessments in the Carpathian Mountains from the monitoring networks developed by the European Union Scheme on the Protection of Forest Against Atmospheric Pollution (EU Scheme) and International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP-Forests), have led to a better understanding of the impact of air pollution and other stressors on forests at the regional scale. During the period 1997-2001, forests in the Carpathian Mountains were severely affected by air pollution and natural stresses with 29.7-34.9% of the trees included in defoliation classes 2-4. The broadleaves were slightly healthier than the conifers, and European beech (Fagus sylvatica) was the least affected species. Norway spruce (Picea abies) has poor health status, with 42.9-46.6% of the trees damaged (2-4% defoliation classes). Silver fir (Abies alba) damage was also high, with 46.0-50.9% in defoliation classes 2-4. Pines (primarily Pinus sylvestris) were the least affected of the conifers, with 24.9-33.8% in defoliation classes 2-4. The results from the transnational networks (16 x 16 km) show that the Carpathian forests are slightly more damaged than the average for the entire Europe. The correlative studies performed in individual European countries show the relationships between air pollution stressors with trends in defoliation and a possible effect of natural stresses at each site. More specific, effects of tree age, drought, ozone and acid deposition critical level exceedances were demonstrated to affect crown condition.     

Visible injury responses

During a five year experiment on the causes of forest disease, symptoms of visible injury and pest infestations in trees treated with various air pollutants in open-top chambers were observed. Though the long-term experiment was originally not intended to include such investigations, insect infestation and some discoloration of the trees (Beech, Fagus sylvatica; Fir, Abies alba; Spruce, Picea abies) could not be avoided. Abundance and size of some of the insects were measured after two years and at the end of the experiment. Because it was unknown when the first infestation in the chambers occurred, quantitative investigations of the population size provided little information. Visible injury on leaves and needles was infrequent in general. When it occurred, it appeared to be caused by at least three stress factors. However, three different types of symptoms on beech and fir could be attributed mainly to air pollutants. These symptoms consisted of two types of foliar necrosis and browning in beech and needle tip chlorosis in fir. These symptoms have been observed under certain conditions in the German forests. The spruce clone used, however, developed no injuries which could be connected definitely to treatment effects.     

Analyses of enzyme activities and other metabolic criteria after five years of fumigation

Enzymatic activity (peroxidase, glutamate dehydrogenase, glutamine synthetase), foliage buffering capacity, soluble protein and nitrogen content were measured in current and previous year needles from young spruce (Picea abies) and fir (Abies alba). The trees were exposed to low levels of SO(2) and/or O(3) and simulated acidic precipitation (pH 4.0) in open-top chambers from 1983 through 1988. Needle samples were taken during March 1988 at the end of the five-year fumigation period. Exposure to SO(2) substantially increased sulphur content in both needle age classes of spruce and fir, and concomitantly reduced the foliage buffering capacity index (BCI), whereas the combined fumigation with SO(2) and O(3) had no effect on BCI. Peroxidase activity was markedly higher in year-old needles compared to current-year needles. However, trees from the SO(2) and SO(2) + O(3) treatments exhibited statistically significant stimulated peroxidase activities. Similarly, changes in the activities of the nitrogen-metabolizing enzymes indicated an altered cellular function of the trees after the long-term pollution stress. Levels of activity of both glutamate dehydrogenase and glutamine synthetase were increased by exposure to SO(2), especially in spruce. Although glutamate dehydrogenase in spruce was affected by all treatments, such changes in activity were found in fir only with the SO(2) treatment. The highest activity of glutamine synthetase, however, occurred in the older needles of trees exposed to SO(2) + O(3). Total nitrogen concentration was either unaffected by the pollutant treatments or decreased in spruce compared to the controls. No statistically significant changes due to the fumigation were found in soluble protein concentrations. Results indicated that chronic exposure to air pollutants lead to alterations in metabolic processes in conifer needles, detectable either by changes in typical stress indicating values or by increases in ammonium assimilation capacity.     

Mineral content in the soil and tree foliage

Seedlings of fir (Abies alba Mill.) and spruce (Picea abies L. Karst.) were fumigated with SO(2), O(3) and SO(2) + O(3) in open-top chambers (OTCs) for almost 5 vegetation periods. As background stress, simulated rain of pH 4.0 was applied. Nutrient content of soil, soil solutions, and trees was investigated and balanced. In the upper partition of the soil high concentrations of exchangeable Ca(2+) were found in all chambers. The SO(2) and SO(2) + O(3) treatments led to increased Ca(2+), Mg(2+) and Mn(2+) concentrations in soil solution and the pool of exchangeable protons increased. This response was most evident in the SO(2) and SO(2) + O(3) chambers and less clear in the filtered pH 5.0 control chamber. In the SO(2) treatment increased Mn and S levels were found in the needles. Ca content in the needles showed a decreasing trend. O(3) alone had no consistent effect on needle nutrient content.     

Fine root studies in situ and in the laboratory

The fine roots and myocorrhizae of beech, spruce and fir trees exposed to ozone, sulphur dioxide and simulated acid precipitation in open-top chambers (OTC) were examined both in situ by rhizoscopy and in the laboratory using root samples from soil cores. Prior to measurements the trees were treated for about one year. During the second year of treatment the fine root production of all three tree species was determined rhizoscopically. The OTC experiments were concluded after an additional three years at which time fine root and small root dry matter as well as the absolute and relative frequencies of mycorrhizae of spruce and fir were determined from soil cores. The vitality of spruce mycorrhizae was examined by fluorescein diacetate staining. In addition total contents of essential cations of spruce mycorrhizae were measured. Long-term exposure to SO(2), SO(2) + O(3), and simulated acid precipitation led to an increased mycorrhizal production by fir. On spruce, a decreased number of mycorrhizae was found in the chambers polluted with SO(2), but a high proportion of dead fine roots indicated an increased root production with an intensified turnover or a delayed decomposition of spruce mycorrhizae. The cation analyses showed an accumulation of Ca(2+) and Zn(2+) in the mycorrhizae of spruce exposed to ozone.     

Atmospheric deposition and ionic interactions within a beech canopy in the Karkonosze Mountains

A method, of artificial foliage placed above rain collectors, which enables to estimate total atmospheric inputs of elements, was employed to study processes related to ionic flow through a tree canopy. The investigations were conducted within a beech forest in the Karkonosze Mountains, in 1996-1997. An analysis of net canopy exchange (throughfall flux-atmospheric input) revealed that NH4+, NO3-, H+ had been retained in the canopy, Ca2+, Na+, Cl-, SO(2-)4, PO(3-)4 flowed passively, whereas K+ and Mg2- had been removed from the tree foliage. Ammonium absorption was more efficient than that of NO3- ions, because NH4+ was taken up from rain-waters and aerosol-gaseous fraction of the atmospheric input, whereas NO3- ions were captured primarily from the latter source. Retention of H+ was also related exclusively to the aerosol-gaseous input. Leaching losses of K+ and Mg2+ did not result from exchange reactions of these ions with retained H+, but from ionic exchange between NH4+ and K+ + Mg2+. At the same time, neutralisation of H+ in the canopy has been attributed to NO3- absorption, resulting most likely from HNO3 vapour penetration into the plants.     

Relevance of element content of bark for the distribution of epiphytic lichens in a montane spruce forest affected by forest dieback

Element content in the bark on Norway spruce (Picea abies) was measured in a montane forest heavily affected by forest dieback and compared to that in a nearby intact stand. Bark contained less S, K, Fe, Mn, Pb, Cu, and H+ and more N, Ca, Mg, and Zn in the dieback-affected stand than in the intact one. Diversity of epiphytic lichen vegetation was higher in the dieback-affected stand than in the intact one. Cover of the foliose lichen Hypogymnia physodes was negatively correlated with Mn and Cu content of bark. Cover of the extremely acidophytic species Lecanora conizaeoides decreased with increasing Mg and increased with increasing Cu content of bark. The measurements support the hypothesis that chemical site factors are decisive for the high lichen diversity in dieback-affected montane spruce forests.     

Studies on leaching from spruce twigs and beech leaves

Leaching, depending on the acidity of the eluent, was investigated for K, Mg and Mn. The curves for the leachate concentration versus time could be described by a power function. Leaching from old needles exceeded leaching from young needles to a high degree, but the ratios of the leached elements were almost equal. A method for continuous measurements of pH change in solutions contacting plant materials was developed. The results were in agreement with data on acidity changes in water falling through spruce or beech canopies.     

Total vs. internal element concentrations in Scots pine needles along a sulphur and metal pollution gradient

Analysis of foliar elements is a commonly used method for studying tree nutrition and for monitoring the impacts of air pollutants on forest ecosystems. Interpretations based on the results of foliar element analysis may, however, be different in nutrition vs. monitoring studies. We studied the impacts of severe sulphur and metal (mainly Cu and Ni) pollution on the element concentrations (Al, Ca, Cu, Fe, K, Mg, Mn, Ni, P, Pb, S and Zn) in Scots pine (Pinus sylvestris L.) foliage along an airborne sulphur and metal pollution gradient. Emphasis was put on determining the contribution of air-borne particles that have accumulated on needle surfaces to the total foliage concentrations. A comparison of two soil extraction methods was carried out in order to obtain a reliable estimate of plant-available element concentrations in the soil. Element concentrations in the soil showed only a weak relationship with internal foliar concentrations. There were no clear differences between the total and internal needle S concentrations along the gradient, whereas at the plot closest to the metal smelter complex the total Cu concentrations in the youngest needles were 1.3-fold and Ni concentrations over 1.6-fold higher than the internal needle concentrations. Chloroform-extracted surface wax was found to have Ni and Cu concentrations of as high as 3000 and 600 microg/g of wax, respectively. Our results suggest that bioindicator studies (e.g. monitoring studies) may require different foliar analysis techniques from those used in studies on the nutritional status of trees.     

Responses of spruce seedlings (Picea abies) to exhaust gas under laboratory conditions--II. Ultrastructural changes and stomatal behaviour

This study examines the effects of exhaust gas exposure on the epistomatal wax structure and mesophyll ultrastructure in needles of Norway spruce (Picea abies (L.) Karst.) seedlings. Stomatal diffusive resistance was also measured. Two independent exhaust gas fumigations were performed: 100 and 200 ppb measured as NO(x), for 10 days and 50, 100 and 200 ppb NO(x) for 19 days. The obstructive effect of exhaust gas exposure on epistomatal wax tubules was apparent. The stomata became covered by flat and solid wax resulting from the structural degradation of the wax crystalloids. Increasing the exhaust gas concentration in the chamber atmosphere exacerbated the degradation of the wax structure. Exhaust gas exposure induced aggregation and electron translucence of plastoglobuli, swelling of thylakoids, increase of cytoplasmic lipids and slight increase of vesiculation of cytoplasm in mesophyll cells of current and previous year needles. These changes were exemplified in current year needles. Damage to the epicuticular waxes and mesophyll ultrastructure of spruce needles most likely reflects the NO(x) and volatile hydrocarbon fraction. The alterations in epicuticular waxes and mesophyll ultrastructure can be related to accelerated senescence of the youngest, photosynthetically active, needle generation. The exhaust gas also resulted in decreased diffusive stomatal resistance at night which indicates that the exhaust gas exposure disturbed the gas exchange of spruce seedlings. The results show that even relatively short-term exposure to realistic concentrations of exhaust gas in the atmosphere can induce rather severe injuries to the needle surface structure as well as ultrastructure at the cellular level.     

Effects of ozone on foliar leaching in Norway spruce (Picea abies L. Karst): confounding factors due to NOx production during ozone generation

Previous experiments with conifers fumigated with O(3), produced by air-operated electric discharge ozonators, have provided evidence that O(3) increases the leaching of NO(3)(-), NH(4)(+), K(+), Ca(2+), Mg(2+) and some other cations from needles, when the trees are treated with acid mist. This evidence has provided the foundation of the ozone-acid mist hypothesis of spruce decline. We report experiments with Norway spruce saplings fumigated with purified and unpurified O(3). The results show that the accumulation of NO(3)(-) in the needles arises from the rapid deposition of N(2)O(5) and HNO(3) formed from N(2) in the ozonator. An increase in removal of NH(4)(+), Na(+), Ca(2+), Mg(2+), Zn(2+) and Mn(2+) from the needles during soaking in H(2)SO(4), pH3, was also observed, which was related to the increase in NO(3)(-) but was independent of O(3) concentration. It is concluded that results of previous experiments cited in support of the ozone-acid mist hypothesis arose from effects which were at least partly caused by N(2)O(5) produced as a contaminant, and were incorrectly attributed to ozone. Other effects, such as growth stimulations, visible symptons, enhanced frost sensitivity, and infestation by pests or pathogens, which have been attributed to O(3) generated by electric discharge in air, should be interpreted with caution. Future experiments with ozone must eliminate this problem by either using O(2)-driven ozonators, or by purifying the output from air-driven ozonators using cold and/or water traps.     

Genetic effects of air pollution on forest tree species of the Carpathian Mountains

The effects of air pollution on the genetic structure of Norway spruce, European silver fir and European beech were studied at four polluted sites in Slovakia, Romania and Czech Republic. In order to reduce potential effects of site heterogeneity on the health condition, pair-wise sampling of pollution-tolerant and sensitive trees was applied. Genotypes of sampled trees were determined at 21 isozyme gene loci of spruce, 18 loci of fir and 15 loci of beech. In comparison with Norway spruce, fewer genetic differences were revealed in beech and almost no differentiation between pollution-tolerant and sensitive trees was observed in fir. In adult stands of Norway spruce, sensitive trees exhibited higher genetic multiplicity and diversity. The decline of pollution-sensitive trees may result thus in a gradual genetic depletion of pollution-exposed populations of Norway spruce through the loss of less frequent alleles with potential adaptive significance to altered stressing regimes in the future. Comparison of the subsets of sensitive and tolerant Norway spruce individuals as determined by presence or absence of discolorations ("spruce yellowing") revealed different heterozygosity at 3 out of 11 polymorphic loci.     

Investigation of influence of tungsten mine wastes on the elemental composition of some alpine and subalpine plants on Mount Uludağ, Bursa,Turkey

In this study, the effect of mine work wastes on elemental composition (N, P, Ca, K, Mg, Fe, Mn, Cu, Zn) of some alpine and subalpine plant species and in soils were investigated in the surroundings of the Etibank Wolfram Mine Work in Uludag mountain. Soils and plant parts belonging to Thymus praecox Opiz., Acinos alpinus (L.) Moench, Plantago holosteum Scop and Festuca punctoria Sm species collected from three directions around Wolfram Mine Work were used for our investigations. All samples were analysed by flame atomic absorption spectrophotometer (FAAS) for Ca, K, Mg, Mn, Fe, Zn, and Cu. The significant differences among sample sites were in terms of pH, % CaCO3, % C, % N and % P contents of soil. The changes of Ca, Mg, Fe, Mn, Fe, Zn, and Cu contents in soil were determined to be due to mining activity. Of the four species examined, an important change was determined in concentrations of Mg, Mn, Fe and Zn although P. holosteum and F. punctoria were different in above- and below-ground parts, showing that plant element content is specific to species.     

Thermal degradation products of spruce needles

Spruce needles are analysed by in-source pyrolysis (Py)-field ionization (FI) mass spectrography and Curie-point Py-gas chromatography/electron ionization mass spectrometry. The identified thermal degradation products allow the interpretation of the FI mass signals. It could be shown that Py-FI mass spectra of plant materials are representative fingerprints which consist primarily of molecular ions of Py products derived from the thermal degradation of the main constituents of spruce needles such as carbohydrates, lignin, lipids and proteins. Primary building blocks of these biopolymers form characteristic Py products of spruce needles. Furthermore, over 500 different molecular ion species of volatilized, thermostable plant constituents are recorded using FI as soft ionization method. The present study shows that Py-FIMS is suitable for the rapid and comprehensive characterization of complex biological materials, without pretreatment of the sample except of drying and milling. The presented results contribute to the basic knowledge for the evaluation of the causes of the present tree damage.