Single-solute and bi-solute sorption of phenanthrene and pyrene onto pine needle cuticular fractions

To better understand interaction mechanisms of pine needles with persistent organic pollutants, single-solute and bi-solute sorption of phenanthrene and pyrene onto isolated cuticular fractions of pine needle were investigated. The structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy and solid-state ¹³C NMR. Polymeric lipids (cutin and cutan) exhibited notably higher sorption capabilities than the soluble lipids (waxes), while cellulose showed little affinity with sorbates. With the coexistence of the amorphous cellulose, the sorption of cutan (aromatic core) was completely inhibited, so the cutin components (nonpolar aliphatic moieties) dominated the sorption of bulk needle cuticle. By the consumption of the amorphous cellulose under acid hydrolysis, sorption capacities of the de-sugared fractions were dramatically enhanced, which controlled by the exposed aromatic cores and the aliphatic moieties. Furthermore, the de-sugared fractions demonstrated nonlinear and competitive sorption due to the specific interaction between aromatic cores and polycyclic aromatic hydrocarbon.     

Ecological condition of forests around the eastern part of the Gulf of Finland

The effects of air pollutants on forests around the eastern part of the Gulf of Finland were studied by measurement of the sulphur and calcium content of pine needles and evaluation of the ecological conditions of pine forests. Several parameters for pine trees and their needles were chosen as well as the species composition and condition of epiphytic lichens. Very high pine needle S- and Ca-contents were measured in the vicinity of the Narva and Slantsy plants. In this region both the acid and basic pollutant load is massive, partly neutralizing each other. It is suggested that the total load will, sooner or later, cause unexpected environmental damage. Wide 'lichen desert' areas were detected around Narva and Slantsy. Near the margins of these areas extraordinary epiphytes on pines were observed namely Xanthoria parietina (L.) Th.Fr. and red-coloured green alga Trentepohlia umbrina. They are regarded as indicators of alkaline pollution. The lowest pine needle S- and Ca-contents of the study area were measured in south-eastern Finland. The condition of pine forests and their needles was, however, better on the neighbouring Karelian Isthmus although the species number of epiphytic lichens was very low and the condition of the lichens was poor. It is suggested that these most sensitive indicators of air pollutants are damaged by pollutants from St Petersburg and Narva. Vast virgin forests of the Karelian Isthmus act as pollutant sinks reducing the effect of pollutants on trees. On the Finnish side intensive forest management has been carried on for many decades making forests and trees more sensitive to pollutants.     

Scots pine needle surfaces on radial transects across the north boreal area of Finnish Lapland and the Kola Peninsula of Russia

To gain an understanding of the characteristics of the needle surfaces of naturally regenerated Scots pine (Pinus sylvestris L.) and their geographical distribution, eight physicochemical variables were investigated within the north boreal forest area. The visibly undamaged needles were collected in autumn 1990 from 114 plots (3-5 pines per plot) along radial transects from the Monchegorsk and Nikel smelters, emitting SO2 and heavy metals, on the Kola Peninsula, Russia, to Finnish Lapland. The needles were examined by scanning electron microscopy (SEM) and measured for surface wettability using the droplet contact angle (DCA) method. Significant geographical south-north and west-east patterns could be observed in needle surface characteristics, correlating with emissions from the smelters and to climate. Despite the slightly higher initial DCAs (61.4-87.6 degrees) towards the north, the pine needle surfaces of the northernmost transects exhibited higher annual needle wettability change (ANWC) and wax erosion rate (AWER), expressed as the reduction in DCAs and epistomatal wax tube distribution (WTD) during one year, respectively, but a lower occurrence of particles and fungal hyphae than those of more southern transects. The higher ANWC was related to higher atmospheric SO2 concentration, and to the lower long-term temperature sum, but not clearly to annual precipitation. In the Monchegorsk smelter area, the current needles exhibited, on average, a 15% higher WTD and seven degree larger DCA, resulting in more hydrophobic needle surfaces than in Finnish Lapland, but during their first year, both the AWER and ANWC, were greatly increased. In Finnish Lapland, 30%, of all the epistomatal wax tubes disappeared from the needle surface during the first year, the value being 70% for the pines located 8 km from the smelter. The mineral composition of the particles deposited on the needle surfaces mirrored that of the minerals being produced by the smelters (e.g. FexSx, CuFeS2, NixSx, FexOx). Stomatal densities were in the range of 71.1-141.7 stomata mm(-2). The lower densities of stomata on needles close to the smelters correlated with reduced number of needle age classes of the pines, higher dry weights, higher pollutant accumulation and lower Mn and Zn concentrations in the needles. The AWER and ANWC were able to indicate the most seriously deteriorated needle surfaces on a regional scale, e.g. including the surroundings of both smelters, although the plot-specific relationships between 'needle surface variables' and 'pollution variables' were generally weak. The present study showed that the exposure of pine needles to the combined effects of ambient pollutants and harsh climate led to a deterioration in the physicochemical characteristics of the epicuticular wax, which may have serious ecophysiological consequences in the long term.     

Fluoranthene fumigation and exogenous scavenging of reactive oxygen intermediates (ROI) in evergreen Japanese red pine seedlings (Pinus densiflora Sieb. et. Zucc.)

Generation of reactive oxygen intermediates (ROI) such as O(2)(-), H(2)O(2), and *OH is known to be a major mechanism of damage in biological systems. This study investigated and compared effectiveness of scavenging ROI generated in fluoranthene (FLU) pre-fumigated Japanese red pine seedlings. Three kinds of eco-physiological assessments were used to express the impact of the different fumigants used inside the green house. Gas exchange measurements showed negative changes induced by 10 microM FLU on Japanese pine seedlings during a 10 d exposure period whilst no negative change was found during a 5 d exposure period. Moreover, during a 14 d FLU exposure incorporating ROI scavengers, results revealed that chlorophyll fluorescence, needle chemical contents and needle dry mass per unit area of the seedlings were affected. The negative effects of FLU on the conifer were dependent on both the dose and period of FLU fumigation. Peroxidase (PERO), superoxide dismutase (SOD) and mannitol (MANN) were all effective scavengers of ROI. MANN scavenged *OH, the most lethal of the ROI. For practicable use, MANN is more economical, and may be the best ROI scavenger among the three considered. It can be concluded that efficient scavenging of ROI in biological systems is important to mitigate the negative effects of FLU on Japanese red pine trees.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.     

Phytoremediation of cadmium-contaminated soil by Bidens pilosa L.: impact of pine needle biochar amendment

Environmental Science and Pollution Research - The objective of the present study was to evaluate the feasibility of pine needle biochar as a soil amendment to promote the growth of Bidens pilosa...     

Height growth of different European Scots pine Pinus sylvestris L. Provenances in a heavily polluted and a control environment

Results are presented of height measurements and degree of needle injury on five-year-old plants of Scots pine (Pinus sylvestris L.) growing near a phosphate fertiliser plant that emits SO(2) and fluorides. The populations of Scots pine represented in this experiment originate from 11 countries and were substantially differentiated in height growth and extent of needle necroses. Those populations which grew most rapidly were found to be the most sensitive to pollutant injury. The least productive provenances from the north of the range (Sweden, USSR) are at the same time characterized by lowest decline in height growth, lowest mortality and least extensive necroses. It is proposed that gene banks be established for the best genotypes likely to be eliminated in the heavily polluted conditions of Poland today.     

Ozone Injury to Pinus Strobus

In a study of the ozone-induced needle blight of eastern white pine in central New York, acute injuries naturally induced on field trees during a year of relatively low ozone concentrations (1 966) were compared with injuries induced during a year of higher concentrations (1967). Injuries were more frequent and severe and were associated with higher mean ozone concentrations in 1967 than in 1966. Characteristic symptoms were induced on foliage of pine branches exposed to controlled doses of ozone as low as 7 ± 1 pphm for four hours or 3 ± 1 pphm for 48 hours. Such doses were equalled or exceeded two and four times, respectively, in the field during the 1 967 season. Ozone sensitivity of pine needle tissue was increased by fumigation in atmospheres containing water mist. High concentrations of ozone (40-60 pphm) caused general injury of foliage of both ozone-susceptible and resistant trees; the symptoms were unlike those found in the field or caused by fumigation with low concentrations of ozone.     

Air Pollution Impacts to Some Important Species of Pine

In the past, many species of pine have been severely damaged by acute forms of air pollution associated with ore smelting. More recently, damage to ponderosa pine in the state of Washington has been associated with atmospheric fluoride, and this species in particular has also suffered smog damage in southern California. In the East, white pine has been declining in the vicinity of certain soft-coal-burning power plants, and in one case downwind from an oil-burning power plant: also, throughout the East, an atmospheric oxidant of unknown source has caused a type of needle blight on white pine. Trash burners and city dump combustion have led to the hilling of certain pine species, leaving other intermixed pine species unharmed. Localized damage to white pine from automobile exhaust has been observed. Differences in the susceptibility of neighboring trees of the same species to a given air pollutant have been observed repeatedly.     

Damage to Eastern White Pine by Sulfur Dioxide,Semimature-Tissue Needle Blight,and Ozone

Eastern white pine (Pinus strobus L.) forests were severely damaged by atmospheric sulfur dioxide up to distances of 25 miles northeast of large smelters located in the Sudbury mining district of Ontario. Damage to white pine was measured in terms of foliage, bark, and biological injuries, radial and volume growth decrement, and tree mortality. The foliar symptoms of sulfur dioxide injury on white pine trees sometimes resembles those caused by a physiogenic disease, semimature-tissue needle blight (abbreviated to SNB). Studies on the nature and etiology of SNB were conducted in white pine forests in the Upper Ottawa Valley, which are remote from smelter operations which might pollute the atmosphere. These studies included the determination of the role that naturallyoccurring atmospheric ozone plays in the occurrence of SNB. Differences between the symptoms of sulfur dioxide injury, SNB, and ozone damage are outlined.     

Relations between Scots pine needle element concentrations and decreased needle longevity along pollution gradients

Scots pine (Pinus sylvestris L.) shoots were sampled along transects near one urban pollution source and two smelters. Needle Mg, P and K concentrations decreased from the second to the fourth age class linearly with needle survival along the urban pollution gradient. Still, over 80% of the average concentration of these nutrients remained in the fourth needle age class. Decreased needle longevity was closely related to the increased heavy metal concentrations near the smelters. Near the urban pollution source, it was related to the increased annual needle mass and the increased needle nutrient concentrations. Decreased Mn accumulation along with needle age was detected near all pollution sources. Leaching of Mn from needles and especially from soil as a cause of decreased needle concentrations is discussed.     

Phytotoxicities of fluoranthene and phenanthrene deposited on needle surfaces of the evergreen conifer, Japanese red pine (Pinus densiflora Sieb. et Zucc.)

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied with respect to their carcinogenic and mutagenic effects on animals and human cells. Phenanthrene (PHE) and fluoranthene (FLU) effects on the needle photosynthetic traits of 2-year-old Japanese red pine (Pinus densiflora Sieb. et. Zucc.) seedlings were investigated. Three months after fumigation of foliage with solutions containing these PAHs (10 microM each), FLU had negative effects on net photosynthesis at near-saturating irradiance, stomatal conductance, initial chlorophyll fluorescence, and the contents of total chlorophyll, magnesium, and ribulose 1,5-bisphosphate carboxylase (rubisco) of current-year needles. PHE had similar negative effects to FLU but in lesser magnitude. The effects of the PAHs were mitigated by the addition of an OH-radical scavenger (mannitol) into the PAH solutions. PAHs deposited on the surface of pine needles may induce the generation of reactive oxygen species in the photosynthetic apparatus, a manner closely resembling the action of the herbicide paraquat.     

Variation in CO2 assimilation rate induced by simulated dew waters with different sources of hydroxyl radical (*OH) on the needle surfaces of Japanese red pine (Pinus densifora Sieb. et Zucc.)

The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.     

Compensation processes of Aleppo pine (Pinus halepensis Mill.) to ozone exposure and drought stress

A long-term experiment was performed to study the effects of O3 and drought-stress (DS) on Aleppo pine seedlings (Pinus halepensis Mill.) exposed in open-top chambers. Ozone reduced gas exchange rates, ribulose-1,5-biphosphate carboxylase/oxygenase activity (Rubisco), aboveground C and needle N concentrations and C/N ratio and Ca concentrations of the twigs under 3 mm (twigs<3) and the aerial biomass. Also it increased phosphoenolpyruvate carboxylase (PEPc) and N and K concentrations of the twigs<3. Water stress decreased gas exchange rates, predawn needle water potential (PsiPd), C/N ratio, twigs<3 Ca, plant growth, aerial biomass and increased N, twigs with a diameter above 3 mm P and Mg concentrations. The combined exposure to both stresses increased N concentrations of twigs<3 and roots and aboveground biomass K content and decreased root C, maximum daily assimilation rate and instantaneous water use efficiency. The sensitivity of Aleppo pine to both stresses is determined by plant internal resource allocation and compensation mechanisms to cope with stress.     

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.     

Biomonitoring airborne parent and alkylated three-ring PAHs in the Greater Cologne Conurbation I: Temporal accumulation patterns

Polycyclic aromatic hydrocarbons (PAHs) comprise an important group of air pollutants, with three-ring components (PAH-3) often dominating. Spatiotemporal variation in atmospheric PAH-3 can be analyzed by biomonitoring but high vapour pressure and low octanol-air-partitioning of PAH-3 cause dynamic accumulation on plant surfaces. This study for the first time shows that PAH-3 exhibit systematic accumulation trends on pine needles of 3-48 months of exposure time at six sites in Germany. Correlation of needle exposure time with PAH-3 concentration was r² = 0.83 for phenanthrene and methylphenanthrenes, r² = 0.77 for cyclopenta[def]phenanthrene, r² = 0.60 for dibenzothiophene, r² = 0.57 for dimethylphenanthrenes and r² = 0.32 for retene. Variations in PAH-3 for summer and winter collected needles emphasize vegetation-air-partitioning influence on cumulative PAH-3 loads. PAH-3 ratios calculated for needle cohorts indicate persistence of original PAH patterns thus demonstrating the source-diagnostic potential of pine needle biomonitoring, which is utilized in part II of this study where spatial distribution of PAH-3 is investigated and related to emission sources.     

Sulphur dioxide adsorption in Scots pine canopies exposed to high ammonia emissions near a Cu-Ni smelter in SW Finland

Since 1994 the nickel-processing plant at the Cu-Ni smelter at Harjavalta, south-west Finland, has emitted considerable amounts of NH(3) into the atmosphere. The effects of NH(3) emissions on nitrogen and sulphur deposition in throughfall and the foliar nutrient status were investigated in a Scots pine stand at 0.5 km distance. Bulk deposition, stand throughfall and percolation water (20 cm depth) samples were collected at 4-week intervals during 1992-1998. pH and the Ca, Mg, K, NH(4) and SO(4) concentrations were determined on the samples. NH(3) emissions have strongly increased the scavenging of SO(2) from the air in the pine stand, and the increased levels of N and S deposition were clearly evident as increased foliar N and S concentrations and larger needle size. The increased input of SO(4) into the forest floor was not associated with an increase in the leaching of Ca and Mg from the surface soil layers.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

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.     

Response of needle sulphur and nitrogen concentrations of Scots pine versus Norway spruce to SO2 and NO2

The results of two field studies and an open-top chamber fumigation experiment showed that the response of mature Scots pine to SO(2) and NO(2) differed from that of mature Norway spruce. Moreover, the response of pine seedlings to SO(2) and NO(2) differed from that of mature trees. The greater increase in the needle total S concentrations of pine suggested more abundant stomatal uptake of SO(2) compared to spruce. Both pine seedlings and mature trees also seemed to absorb more N from atmospheric deposition. Mature pine was able to assimilate SO(4)(2-) derived from SO(2) into organic S more effectively than mature spruce at the high S and N deposition sites, whereas both pine and spruce seedlings accumulated SO(4)-S under NO(2)+SO(2) exposure. Spruce, in turn, accumulated SO(4)-S even when well supplied with N. Net assimilation of SO(4)(2-) in conifer seedlings was enhanced markedly by elevated temperature. To protect the northern coniferous forests against the harmful effects of S and N deposition, it is recommended that the critical level for SO(2) as a growing season mean be set at 5-10 microg m(-3) and NO(2) at 10-15 microg m(-3), depending on the 'effective temperature sum' and/or whether SO(2) and NO(2) occur alone or in combination.