Chlorinated short chain aliphatic hydrocarbons in pine needles by purge and trap gas chromatography/mass spectrometry

The concentrations of volatile chlorinated short chain aliphatic hydrocarbons in pine needles have been measured using purge and trap GC/MS. The concentrations of dichloromethane, chloroform, dichloroethene and tetrachloroethene in the needles were calculated. The concentrations of dichloromethane and tetrachloroethene were highest. As a rule the concentrations were higher in the older needles. The needle samples were collected from five sampling points in an area situated in the Southern Finland in the vicinity of a metal scrab plant. Reference needles were collected in the Central Finland. Needles originated from years 1991, 1992 and 1993.     

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.     

Monitoring environmental pollution in Poland by chemical analysis of Scots pine (Pinus sylvestris L.) needles

Maps of the distribution of environmental pollution by sulfur (S), zinc (Zn), cadmium (Cd), lead (Pb), copper (Cu), and arsenic (As) for the territory of Poland and the Warsaw (Warszawa) district were developed on the basis of chemical analysis of Scots pine (Pinus sylvestris L.) needles collected from randomly selected sampling points during 1983-1985. The maps show deposition zones for the studied elements and can help in identification of sources and directions of air pollution dispersion. This study indicated that vegetation in Poland is greatly endangered by sulfur dioxide (SO(2)) and other sulfurous air pollutants, whereas Zn, Cd, Pb, and As do not pose an immediate threat to vegetation in most of the country's territory. However, in the urban-industrial agglomeration of Katowice-Cracow, very high pollution with Z, Cd, Pb and As could limit growth and development of some sensitive plant species. Higher than normal levels of As in some areas of Poland (Upper Silesia, Glogow-Lubin Copper Region, and areas close to the Russian border near Braniewo) might affect the health of humans and animals. Results of this study indicated that Poland's environment was not contaminated with Cu.     

UV-absorbing compounds and waxes of Scots pine needles during a third growing season of supplemental UV-B

Methanol-extractable UV-absorbing compounds, wax tube distribution and the chloroform-soluble waxes of the needles of mature Scots pines were studied in a UV-B field experiment in Oulu (65 degrees N). Throughout the experiment, UV-B lamp banks were placed over the same selected branch and each year needle samples were taken from the same branch. In the third exposure year, needle samples were taken twice a month from 3-day-old needles (18 June) to fully developed needles (13 August). On 28 September, the previous year's needles (c + 1, c + 2) were also collected. There was a significant negative correlation between the amount of waxes and UV-absorbing compounds. A high amount of UV-absorbing compounds was observed early and late in the season when the amount of waxes was low and epicuticular waxes were undeveloped (youngest needles) or already eroded (c + 2 needles). The amount of UV-absorbing compounds (A310/cm2 and A320/cm2) was significantly (30-day-old needles) or slightly (all the other needle ages) higher in the ambient needles compared to the needles under supplemental UV-B. This possibly indicated the already inhibited pigment synthesis in the UV-B-treated needles during the third year of supplemental UV-B. This observation could mean that the protective mechanisms may not be effective under accumulated UV-B dose.     

Airborne lipophilic pollutants in pine needles

Many environmental contaminants known today are semivolatile organic compounds (SOC) and are present in the atmosphere. Airborne SOC are taken up and enriched by the epicuticular wax that covers leaves of higher plants. The purpose of the present work was to use pine needles 1) to map the distribution of airborne SOC in Europe, 2) to identify source regions, and 3) to identify hitherto unknown anthropogenic and/or natural substances. Some of the results were a confirmation of a suspected release of DDT in the former East Germany, high levels of pentachlorophenol were noted in Scandinavia, hexachlorocyclohexanes were higher in southern than in northern Europe, whereas PCB and hexachlorbenzene were rather evenly distributed throughout Europe. Elemental sulphur was identified as a previously unknown natural substance in higher plants.     

Influence of solar UV radiation on the nitrogen metabolism in needles of Scots pine (Pinus sylvestris L.)

Needles of 20-year-old Scots pine (Pinus sylvestris L.) saplings were studied in an ultraviolet (UV) exclusion field experiment (from 2000 to 2002) in northern Finland (67 °N). The chambers held filters that excluded both UV-B and UV-A, excluded UV-B only, transmitted all UV (control), or lacked filters (ambient). UV-B/UV-A exclusion decreased nitrate reductase (NR) activity of 1-year-old needles of Scots pines compared to the controls. The proportion of free amino acids varied in the range 1.08-1.94% of total proteins, and was significantly higher in needles of saplings grown under UV-B/UV-A exclusion compared to the controls or UV-B exclusion. NR activity correlated with air temperature, indicating a “chamber effect”. The study showed that both UV irradiance and increasing temperature are significant modulators of nitrogen (N) metabolism in Scots pine needles.     

Growth, respiration and nitrogen content in needles of Scots pine exposed to elevated ozone and carbon dioxide in the field

Single Scots pine (Pinus sylvestris L.) trees, aged 30 years, were grown in open-top chambers and exposed to two atmospheric concentrations of ozone (O3; ambient and elevation) and carbon dioxide (CO2) as single variables or in combination for 3 years (1994-1996). Needle growth, respiration and nitrogen content were measured simultaneously over the period of needle expansion. Compared to ambient treatment (33 nmol mol(-1) O3 and 350 micromol mol(-1) CO2) doubled ambient O3 (69 nmol mol(-1)) significantly reduced the specific growth rates (SGRs) of the needles in the early stage of needle expansion and needle nitrogen concentration (N1) in the late stage, but increased apparent respiration rates (ARRs) in the late stage. Doubled ambient CO2 (about 650 micromol mol(-1)) significantly increased maximum SGR but reduced ARR and N1 in the late stage of needle expansion. The changes in ARR induced by the different treatments may be associated with treatment-induced changes in needle growth, metabolic activities and turnover of nitrogenous compounds. When ARR was partitioned into its two functional components, growth and maintenance respiration, the results showed that neither doubled ambient O3 nor doubled ambient CO2 influenced the growth respiration coefficients (Rg). However, doubled ambient O3 significantly increased the maintenance respiration coefficients (Rm) regardless of the needle development stage, while doubled ambient CO2 significantly reduced Rm only in the late stage of needle expansion. The increase in Rm under doubled ambient O3 conditions appeared to be related to an increase in metabolic activities, whereas the decrease in Rm under doubled ambient CO2 conditions may be attributed to the reduced N1 and turnover rate of nitrogenous compounds per unit. The combination of elevated O3 and CO2 had very similar effects on growth, respiration and N1 to doubled ambient O3 alone, but the interactive mechanism of the two gases is still not clear.     

Effect of simulated acid rain on quantity of epiphytic microfungi on Scots pine (Pinus sylvestris L.) needles

The effects of simulated acid rain on the phyllosphere microflora of pine (Pinus sylvestris L.) were studied experimentally in northern Finland during the summer of 1988. Trees were irrigated with artificial acid rain of pH4 and pH3 (H(2)SO(4) and HNO(3), weight ratio of S:N=2.86:1). Untreated trees and trees irrigated with spring water (pH6) were used as controls. Two sampling heights (0.5m and 2m) were used. The needles were colonized exclusively by epiphytic fungi, mainly Aureobasidium pullulans (de Bary) Arnaud. The lower branches had significantly more epiphytic fungi than the upper branches. Compared to the control trees, the numbers of epiphytic fungi were significantly decreased on the needles of trees irrigated with acid rain. Acid rain affected the number of epiphytic fungi equally at both sampling heights. The species composition of the epiphytic fungi was not affected by the acid treatments.     

The effect of simulated acid rain on the biochemical composition of Scots pine (Pinus sylvestris L.) needles

The effects of prolonged simulated acid rain on the biochemistry of Scots pine needles were studied in Finnish Lapland. Pine trees were exposed by spraying the foliage and soil with either clean water or simulated acid rain (SAR; both sulphuric and nitric acids) over the period 1985-1991. The concentrations of carbohydrates (starch, glucose, fructose, sucrose) in one-year-old pine needles were not affected by SAR-treatments. The SAR-treatments did not have significant effects on protein bound amino acids, which was true also for most of the free amino acids. However, the citrulline concentration was over three-fold greater in the foliage of pines exposed to SAR of pH 3 compared to irrigated controls. The concentrations of total phenolics, individual low molecular weight phenolics and soluble proanthocyanidins were not affected by the treatments, but insoluble proanthocyanidins had increased in acid-treated trees. Some of the studied biochemical compounds showed significant differences between two sub-areas (similar treatments) only 120 m apart.     

Accumulation of chlorinated hydrocarbon vapours in pine needles

Needles with different ages from four pines have been analysed for PCB's, HCB, α- and γ-HCH, p,p'DDT and DDE. The accumulation found has been discussed and provisional accumulation rates under actual background conditions have been calculated.     

Organohalogenated compounds in pine needles from Beijing city, China

Pine needles collected from 22 sites of six areas in Beijing city, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic extraction for extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The concentrations of EOX (EOX = ECl + EOBr + EOI) were in the order of EOCl > EOBr > EOI. About 1.6-34% of EOCl remained as extractable persistent organochlorine (EPOCl) after treatment with concentrated sulfuric acid, which suggested that major fractions of EOCl in pine needles were an acid-liable or acid-soluble fraction. The fact that pine needle contained higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, HCB and PCBs) to total EOCl and EPOCl were 0.32-0.76% and 2.5-11.4%, respectively, which implied that a major portion of the EOCl and EPOCl measured in pine needles was unknown. The organochlorinated pesticides (OCPs) and PCBs concentrations in six areas were as follows: sigma HCH (sigma HCH = alpha- + beta- + gamma- + delta-HCH), 11.7-20.8 ng/g; sigma DDT (p,p'-DDT + p,p'-DDE + p,p'-DDD), 12.5-113.3 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigma chlordane (cis-chlordane + trans-chlordane + heptachlor), 1.7-9.5 ng/g, sigma PCB, 41.8-270.5 ng/g, on dry weight basis. The samples from chemical industrial area and residential area nearby chemical industries contained the highest concentrations of sigma DDT, HCB, sigma chlordane and sigma PCB, while the contamination levels of most OCPs and PCBs in iron-steel industrial area were the lowest. The ratios of alpha/gamma-HCH (ranged from 0.9-1.5) and p,p'-DDT/DDTs (ranged from 72.1% to 91.0%) revealed the presence of the recent use of lindane and DDTs or impure dicofol in Beijing.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Assessing the critical level of SO2 for Scots pine in situ

A field survey was performed in eastern Finland, where measured ambient SO2 concentrations were 1.4-3.8 microg m(-3) a(-1) and bulk S deposition 0.17-0.32 g m(-2) a(-1) in 1991-1993. The accumulation of sulphur (S) in needles of Scots pine (Pinus sylvestris L.) was studied with XRF, IC and FESEM analyses and the needle damage examined under a light microscope and by SEM. Foliar N concentrations were also measured. Foliar total S concentrations were observed to be above the normal S level (500-700 microg g(-1)) over almost the whole area. Slight chlorosis and/or necrosis of the needle tips and stomatal areas, changes in the needle surface waxes and localization of S into needle tips and mesophyll cells around the stomata suggested the impact of S deposition, as did the calculations of St/Nt, and 'predicted' and 'excess' S. A concentration of about 900 microg g(-1) may be considered a critical level for foliar St in areas with low N supply.     

Chlorinated hydrocarbons in sediments of the Elbe River and the Elbe Estuary

Eight sediment samples collected between Hamburg and Cuxhaven were analysed for organic micropollutants. Using three different methods the following compounds were determined: α-HCH, γ-HCH, HCB, PCB, DDT-family, pentachlorobenzene and octachlorostyrene.     

Environmental distribution of PAHs in pine needles,soils, and sediments

Introduction  

The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale.     

Ozone-induced free polyamine response in scots pine in northern Finland

The study aimed to assess the ozone-induced response in Scots pine (Pinus sylvestris L.) needles by measuring free polyamine concentrations. An open-top chamber experiment with realistically elevated ozone concentrations was carried out in northern Finland. A carry-over effect was detected: the concentrations of free polyamines, especially putrescine, were decreased at the beginning of the next growing season in the ozone-exposed trees. This indicates that the free polyamine pathway was not activated by ozone stress in Scots pines in northern conditions.     

Chlorinated hydrocarbons in plant foliage: An indication of the tropospheric contamination level

Levels of some chlorinated hydrocarbons in foliage from the Italian peninsula and other countries of the world are reported. The use of plant leaves in monitoring and for the prediction of potential environmental distribution of persistent hydrophobic pollutants is discussed.     

Interactions between precipitation and Scots pine canopies along a heavy-metal pollution gradient

Bulk precipitation and stand throughfall were collected during 1992-96 at distances of 0.5, 4 and 8 km from the Harjavalta Cu-Ni smelter, southwestern Finland. The amounts of heavy metals (Cu, Ni, Zn, Fe) and mineral nutrients in bulk precipitation and throughfall were highest at 0.5 km. Although the canopy coverage was low at 0.5 km, the amounts of heavy metals intercepted by the canopy were extremely high. The proportion of foliar leaching relative to the wash-off of dry deposition from the needle surfaces decreased on moving towards the smelter for all elements, except for K. The high rate of K leaching from the needle tissues close to the smelter demonstrated that the K throughfall flux has been greatly altered by the heavy pollution load.     

Organochlorine pollutants in Scots pine needles--biological and site related variation within a forest stand

To study the biological variation in the content of some persistent organic pollutants, viz hexachlorobenzene (HCB), alpha- and gamma-hexachlorocyclohexane (alpha- and gamma-HCH), and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (DDT) were analysed in needles from Scots pine trees growing at an isolated peninsula south of Stockholm, Sweden. The concentration variations of each compound was evaluated by a nested analysis of variance (ANOVA) with sampling site specific compass direction, individual tree, and sampling height as factors. Two pair-wise post hoc tests were used to test significant results from the ANOVA. The hexachlorocyclohexanes showed no significant differences between sampling site, trees or sampling height. DDT concentration was significantly lower at the sampling site with the densest vegetation compared to at least three of the other sampling sites. HCB was significantly lower at the lowest sampling height (0.5 m).