Air pollution, precipitation chemistry and forest health in the Retezat Mountains, Southern Carpathians, Romania

In the Retezat Mountains concentrations of O3, NO2 and SO2 in summer season 2000-2002 were low and below toxicity levels for forest trees. While NH3 concentrations were low in 2000, the 2001 and 2002 concentrations were elevated indicating possibility for increased N deposition to forest stands. More than 90% of the rain events were acidic with pH values <5.5, contributing to increased acidity of soils. Crown condition of Norway spruce (Picea abies) and European beech (Fagus sylvatica) was good, however, defoliation described as >25% of foliage injured increased from 9.1% in 2000 to 16.1% in 2002. Drought that occurred in the southern Carpathians between fall 2000 and summer 2002 and frequent acidic rainfalls could cause the observed decline of forest condition. Both Norway spruce and European beech with higher defoliation had lower annual radial increments compared to the trees with low defoliation. Ambient O3 levels found in the Retezat did not affect crown condition of Norway spruce or European beech.     

Seasonal patterns of ascorbate in the needles of Scots Pine (Pinus sylvestris L.) trees: correlation analyses with atmospheric O3 and NO2 gas mixing ratios and meteorological parameters

In the present field study the role of ascorbate in scavenging the harmful atmospheric trace gases O3 and NO2 was examined. For this purpose ascorbate contents were determined in needles of adult Scots pine trees (Pinus sylvestris L.) during three consecutive years. Ascorbate contents were correlated with ambient tropospheric O3 and NO2 concentrations and with meteorological parameters. The results showed a strong correlation of atmospheric O3 but not of atmospheric NO2 concentrations with the apoplastic content of ascorbate during the seasonal course. Ascorbate contents in needle extracts did not correlate with ambient trace gas concentrations. In the apoplastic space, but not in needle extracts ascorbate contents correlate highly significantly with global radiation. From these results it is assumed that apoplastic ascorbate in Scots pine needles is adapted to the actual atmospheric O3 concentration to mediate immediate detoxification of O3, while the atmospheric O3 concentration itself is largely dependent on light intensity.     

Ozone air pollution and foliar injury development on native plants of Switzerland

The objectives of this study were to examine the foliar sensitivity to ozone exposure of 12 tree, shrub, and herbaceous species native to southern Switzerland and determine the seasonal cumulative ozone exposures required to induce visible foliar injury. The study was conducted from the beginning of May through the end of August during 2000 and 2001 using an open-top chamber research facility located within the Lattecaldo Cantonal Forest Nursery in Canton Ticino, southern Switzerland (600 m asl). Plants were examined daily and dates of initial foliar injury were recorded in order to determine the cumulative AOT40 ppb h ozone exposure required to cause visible foliar injury. Plant responses to ozone varied significantly among species; 11 species exhibited visible symptoms typical of exposures to ambient ozone. The symptomatic species (from most to least sensitive) were Populus nigra, Viburnum lantana, Salix alba, Crataegus monogyna, Viburnum opulus, Tilia platyphyllos, Cornus alba, Prunus avium, Fraxinus excelsior, Ribes alpinum, and Tilia cordata; Clematis spp. did not show foliar symptoms. Of the 11 symptomatic species, five showed initial injury below the critical level AOT40 10 ppmh O3 in the 2001 season.     

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.     

Phenolic compounds content in Pinus halepensis Mill. needles: a bioindicator of air pollution

Foliar phenol concentrations (total and simple phenols) were determined in Aleppo pine (Pinus halepensis Mill.) needles collected in June 2000, from 6 sites affected by various forms of atmospheric pollutants (NO, NO(2), NO(x), O(3) and SO(2)) monitored during two months. Results show an increase in total phenol content with exposure to sulphur dioxide and a reduction with exposure to nitrogen oxide pollution. p-Coumaric acid, syringic acid and 4-hydroxybenzoic acid concentrations increase with exposure to nitrogen oxide pollution, whereas gallic acid and vanillin decrease in the presence respectively of sulphur dioxide and ozone. This in situ work confirms the major interest of using total and simple phenolic compounds of P. halepensis as biological indicators of air quality.     

Diversity and sensitivity of epiphytes to oxides of nitrogen in London

This study investigated the distribution and diversity of epiphytes in London in relation to NO(x) using fine-scale atmospheric dispersion modelling. The survey recorded over 3000 epiphytes from 334 trees (Fraxinus excelsior) representing 74 lichen, 14 moss, 7 fungal and 3 algal species. There was a significant inverse relationship between diversity and NO(x). Diversity declined where NO(x) exceeded 70 microg m(-3) and NO2 exceeded 40 microg m(-3), suggesting a phytotoxic effect. However, there was a significant positive relationship between NO(x) and lichen abundance due to the ubiquitous distribution of pollution tolerant species, mainly associated with eutrophication. A scale of lichen sensitivity to NO(x) has been derived.     

Tree species effect on the redistribution of soil metals

Phytostabilization of metals using trees is often promoted although the influence of different tree species on the mobilization of metals is not yet clear. Soil and biomass were sampled 33 years after planting four tree species (Quercus robur, Fraxinus excelsior, Acer pseudoplatanus, Populus 'Robusta') in a plot experiment on dredged sediment. Poplar took up high amounts of Cd and Zn and this was associated with increased Cd and Zn concentrations in the upper soil layer. The other species contained normal concentrations of Cd, Cu, Cr, Pb and Zn in their tissues. Oak acidified the soil more than the other species and caused a decrease in the concentration of metals in the upper soil layer. The pH under poplar was lower than expected and associated with high carbon concentrations in the top soil. This might be assigned to retardation of the litter decomposition due to elevated Cd and Zn concentrations in the litter.     

Conifer aphids in an air-polluted environment. II. Host plant quality

Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) seedlings were transported to five forest sites at increasing distances from a pulp mill emitting mainly SO(2). Levels of compounds which may have nutritional or defensive value for aphids on pine and spruce seedlings were studied. Glucose and fructose concentrations were significantly increased in pine and spruce needles near the pulp mill. There were no changes in sucrose and starch concentrations. In pine shoots, total free amino acid concentration and the concentrations of ornithine, lysine, histidine and arginine were significantly negatively correlated with the distance from the pulp mill, while in spruce only the individual amino acids glycine, ornithine, lysine and histidine showed a significant negative correlation with distance. There were no changes in total phenolic, catechin, total monoterpene and total resin acid concentrations. However, in pine seedlings monoterpenes beta-pinene and sabinene and in spruce seedlings resin acid palustric acid were significantly correlated with the distance from the pulp mill. The results indicate that SO(2) disturbs carbohydrate metabolism in spruce and pine seedlings. The elevated concentrations of arginine may be the result of the combinations of SO(2), NO(3) and NH(3) emissions of the pulp mill. The emissions did not have any impact on total amounts of defensive substances in trees. Thus, the possible susceptibility of conifers to herbivores appears to be due to changes in nutritive value rather than to reduced chemical resistance.     

Modeling speciated terpenoid emissions from the European boreal forest

We present the first estimates of speciated monoterpene emissions from the North European coniferous forests. Measured emission factors and emission profiles of boreal tree species (Picea abies, Pinus sylvestris, Betula pendula, Salix phylicifolia, Populus tremula, and Alnus incana) were used together with detailed satellite land cover information and meteorological data in an emission model based on the Guenther emission algorithms. The variation of the coniferous biomass within the boreal region (60°N to 70°N) was obtained from forest inventory data, and the seasonal variability of the deciduous biomass was taken into account through simple boreal climatology parameterisation. The annual biogenic emissions in the boreal zone are dominated by coniferous species, but in the summer months, the deciduous contribution to the monoterpene and isoprene emissions is considerable. Norway spruce (Picea abies) is the most important isoprene emitter in the north European boreal forests. The biogenic emission fluxes in the South boreal zone are approximately twice as high as fluxes in the North boreal zone. α- and β-pinene, carene, and cineole are the most abundant emitted terpenes, with a strong contribution of isoprene and linalool during the summer months.     

Scots pine (Pinus sylvestris L.) growth and condition in a polluted environment: from decline to recovery

The results of long-term investigations of Scots pine (Pinus sylvestris L.) growth and condition in the impact zone of one of the biggest air pollution sources in Lithuania--mineral fertilizers plant "Achema" are presented. The main attention is laid to the recovery of damaged stands since annual emissions to air were reduced essentially. The investigations indicated, that the recovery of tree increment was mostly caused by distinct reduction of emissions of nitrogen and sulphur oxides and dust of mineral fertilizers. Despite reduced pollution, crown defoliation of investigated stands has continued to increase for a certain period. After the crown recovery of damaged stands has started, the recovery of most damaged survived trees was most intensive and convergence of defoliated to a different extend stands and trees is characteristic feature of this period. No defoliation threshold has been determined beyond of which recovery of trees would be impossible. Recovery of more than a quarter of damaged trees was registered even in the case of 90% of defoliation. Recovery of dominant trees occurs to be faster of that for suppressed trees within the same level of defoliation. The impact of stand density on the crown recovery rate is negative, the higher density (more intensive competition), the slower recovery of damaged trees. The dependence of growth rate on defoliation was found to be of logistic character: while crown defoliation consists up to 25-30%, tree increment losses are rather inconsiderable, further increase of defoliation leads to the essentially higher increment losses, however having achieved 65-70% defoliation, further increase of defoliation does not result such intensive decrease of radial increment.     

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.     

Nitrate reductase activity of needles of Norway spruce fumigated with different mixtures of ozone, sulfur dioxide, and nitrogen dioxide

Four-year-old spruce clones (Picea abies (L.) Karst.) cultivated in sand and provided with a complete nutrient solution, or a solution deficient in magnesium and calcium, were exposed to the pollutant mixtures SO(2)/NO(2), O(3)/NO(2), and O(3)/SO(2)/NO(2), at realistic concentrations for 32 weeks. Fumigation caused a slight increase of total N contents in current year needles, whereas in one-year-old needles N concentrations did not change. The response of nitrate reductase activity to pollutant stress depended on needle age and nutrient supply, respectively. In one-year-old needles fumigation resulted in a significant inhibition of enzyme activity, particularly in Mg and Ca deficient trees. The combination of all three components proved to be most effective in causing a decrease by 60% compared to the control. In contrast, nitrate reductase activity was stimulated in current year needles, especially by O(3)/NO(2) and O(3)/SO(2)/NO(2). Changes in the activity of nitrate and nitrite reductases are considered as a factor contributing to the high phytotoxic potential of pollutant combinations with NO(2).     

Effect of vegetation type on throughfall deposition and seepage flux

This paper compares different vegetation types (coniferous and deciduous forest, grassed and pure heathland) in terms of input (throughfall deposition) and output (seepage flux) in a region with intermediate nitrogen load (+/-20kg Nha(-1)y(-1) via bulk precipitation) in comparable conditions in north Belgium. Coniferous forest (two plots Pinus sylvestris and two plots Pinus nigra) received significantly higher nitrogen and sulphur throughfall deposition than deciduous forest and heathland. Grassed and pure heathland had significantly highest throughfall quantities of Ca(2+) and Mg(2+), respectively. The observed differences in throughfall deposition between the different vegetation types were not univocally reflected in the ion seepage flux. Considerable seepage fluxes of NO(3)(-), SO(4)(2-), Ca(2+) and Al(III) were only found under the P. nigra plots. We discuss our hypothesis that the P. nigra forests already evolved to a situation of N saturation, while the other vegetation types did not.     

Ozone sensitivity of Fagus sylvatica and Fraxinus excelsior young trees in relation to leaf structure and foliar ozone uptake

During the summer of 2001, 2-year-old Fraxinus excelsior and Fagus sylvatica plants were subjected to ozone-rich environmental conditions at the Regional Forest Nursery at Curno (Northern Italy). Atmospheric ozone concentrations and stomatal conductance were measured, in order to calculate the foliar fluxes by means of a one-dimensional model. The foliar structure of both species was examined (thickness of the lamina and of the individual tissues, leaf mass per area, leaf density) and chlorophyll a fluorescence was determined as a response parameter. Stomatal conductance was always greater in Fraxinus excelsior, as was ozone uptake, although the highest absorption peaks did not match the peaks of ozone concentration in the atmosphere. The foliar structure can help explain this phenomenon: Fraxinus excelsior has a thicker mesophyll than Fagus sylvatica (indicating a greater photosynthesis potential) and a reduced foliar density. This last parameter, related to the apoplastic fraction, suggests a greater ability to disseminate the gases within the leaf as well as a greater potential detoxifying capacity. As foliar symptoms spread, the parameters relating to chlorophyll a fluorescence also change. PI (Performance Index, Strasser, A., Srivastava, A., Tsimilli-Michael, M., 2000. The fluorescence transient as a tool to characterize and screen photosynthetic samples. In: Yunus, M., Pathre, U., Mohanty, P., (Eds.) Probing Photosynthesis: Mechanisms, Regulation and Adaptation. Taylor & Francis, London, UK, pp. 445-483.) has proved to be a more suitable index than Fv/Fm (Quantum Yield Efficiency) to record the onset of stress conditions.     

Ozone exposure thresholds and foliar injury on forest plants in Switzerland

Canton Ticino in southern Switzerland is exposed to some of the highest concentrations of tropospheric ozone in Europe. During recent field surveys in Canton Ticino, foliar symptoms identical to those caused by ozone have been documented on native tree and shrub species. In Europe, the critical ozone level for forest trees has been defined at an AOT40 of 10 ppm.h O3 (10 ppm.h accumulated exposure of ozone over a threshold of 40 ppb) during daylight hours over a six-month growing season. The objective of this study was to determine the amount of ambient ozone required to induce visible foliar symptoms on various forest plant species in southern Switzerland. Species were grown within eight open-top chambers and four open plots at the Vivaio Lattecaldo Cantonal Forest Nursery in Ticino, Switzerland. Species differed significantly in terms of the ppb.h exposures needed to cause visible symptoms. The most to least symptomatic species grown within open-plots in this study rank as Prunus serotina, Salix viminalis, Vibrnum lantana, Rhamnus cathartica, Betula pendula, Rumex obtusifolius, Sambucus racemosa, Morus nigra, Prunus avium, Fraxinus excelsior, Rhamnus frangula, Alnus viridis, Fagus sylvatica and Acer pseudoplatanus. Similar rankings were obtained in the non-filtered chamber plots. The ranking of species sensitivity closely follows AOT values for the occurrence of initial symptoms and symptom progression across the remainder of the exposure season. Species that first showed evidence of foliar injury also demonstrated the most sensitivity throughout the growing season, with symptoms rapidly advancing over ca. 25-30% of the total plant leaf surfaces by the end of the observation period. Conversely, those species that developed symptoms later in the season had far less total injury to plant foliage by the end of the observation period (1.5 to < 5% total leaf area injured). The current European ambient ozone standard may be insufficient to protect native plant species from visible foliar injury, and many more native species may be sensitive to ozone-induced foliar injury than are currently known.     

Alfalfa nutritive quality for ruminant livestock as influenced by ambient air quality in west-central Alberta

Alfalfa (Medicago sativa) nutritive quality response to ambient ozone (O(3)), sulfur dioxide (SO(2)) and oxides of nitrogen (NO(x)) were assessed at three locations in west-central Alberta, Canada (1998-2002). Yield data were segregated into high and low relative to overall median yield. Ozone concentrations (hourly median and 95th-percentile) and precipitation (P) contributed 69 and 29%, respectively, to the variability in crude protein (CP) concentration in low-yielding alfalfa, whereas mean temperature (T) and relative humidity (RH) collectively influenced 98% of the variation in CP in high-yielding alfalfa. Three-fourths of the accounted variation in relative feed value (RFV) of low-yielding alfalfa was attributable to P, T and RH, whereas median and 95th-percentile hourly O(3) concentrations and SO(2) and NO(x) exposure integrals contributed 25%. In contrast, air quality, (mainly O(3)) influenced 86% of the accounted variation in RFV of high-yielding alfalfa, and T and P collectively contributed 14%.     

Acid neutralization of precipitation in Northern China

There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.     

Multivariate space analysis of the major precipitation ions over Europe, 1986-1997

The annual average concentrations (1986-1997) of the major ions SO4(2-), NO3-, Cl-, NH4+, Na+, Mg2+, Ca2+, and K+ in precipitation are analyzed for selected EMEP stations. The objective is to determine the ion patterns or typologies in precipitation by principal component analysis (PCA) combined with a cluster analysis. SO4(2-) and NO3- ions are predominant in central and eastern Europe. This area corresponds to high emissions of SO2 and NO2. Sea spray ions are predominant in coastal sites. The soil components show an important contribution in southern Europe, possibly due to the soil dust transported from northern Africa.     

Defining the photochemical contribution to particulate matter in urban areas using time-series analysis

The objective of this project is to demonstrate how the ambient air measurement record can be used to define the relationship between O3 (as a surrogate for photochemistry) and secondary particulate matter (PM) in urban air. The approach used is to develop a time-series transfer-function model describing the daily PM10 (PM with less than 10 microm aerodynamic diameter) concentration as a function of lagged PM and current and lagged O3, NO or NO2, CO, and SO2. Approximately 3 years of daily average PM10, daily maximum 8-hr average O3 and CO, daily 24-hr average SO2 and NO2, and daily 6:00 a.m.-9:00 a.m. average NO from the Aerometric Information Retrieval System (AIRS) air quality subsystem are used for this analysis. Urban areas modeled are Chicago, IL; Los Angeles, CA; Phoenix, AZ; Philadelphia, PA; Sacramento, CA; and Detroit, MI. Time-series analysis identified significant autocorrelation in the O3, PM10, NO, NO2, CO, and SO2 series. Cross correlations between PM10 (dependent variable) and gaseous pollutants (independent variables) show that all of the gases are significantly correlated with PM10 and that O3 is also significantly correlated lagged up to two previous days. Once a transfer-function model of current PM10 is defined for an urban location, the effect of an O3-control strategy on PM concentrations is estimated by calculating daily PM10 concentrations with reduced O3 concentrations. Forecasted summertime PM10 reductions resulting from a 5 percent decrease in ambient O3 range from 1.2 microg/m3 (3.03%) in Chicago to 3.9 microg/m3 (7.65%) in Phoenix.     

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.