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.     

The effects of sulphur gas and elemental sulphur dust deposition on Pinus contorta x Pinus banksiana: cell walls and water relations

The bulk modulus of elasticity (E) for Pinus contorta (lodgepole pine) x Pinus banksiana (jack pine) hybrids was compared between a site (AI) close to a sour gas processing plant and a control site (AV). The mean bulk modulus of elasticity for branches from AI was 47.5 MPa vs 18.5 MPa for the control site (AV). Site AI had been exposed to S-gas emissions and large amounts of elemental S deposition and had an acidic soil (pH 4.0 at 10 cm depth). During 1981 the needles at AI had more aluminum and iron compared to those at AV (900 ppm vs 390 ppm AI in the 3-year-old needles). Mean leader growth was measured over a 3-year period and was observed to be greater at AI than AV (46+/-7 cm vs 29+/-9 cm for 1988). Histochemically, the needles at AI had higher phenol and lignin content than AV. These results suggest that the S-gas fumigation, S-dust deposition, plus increased concentrations of soluble aluminum and iron had altered the cell wall elastic properties resulting in altered water relations. The implications of this on leaf diffusive resistance and photosynthesis are discussed.     

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.     

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.     

Foliar injury symptoms of Saskatoon serviceberry (Amelanchier alnifolia Nutt.) as a biological indicator of ambient sulfur dioxide exposures

Saskatoon serviceberry or Saskatoon (Amelanchier alnifolia Nutt. cv. Smoky) seedlings were planted at five study sites within a 35,000 km(2) airshed, that is influenced by a number of isolated stationary sources of sulfur dioxide (SO(2)), oxides of nitrogen and hydrocarbons, among others. The locations of the five sites were based on the results of a meteorological dry deposition model for the oxides of sulfur and nitrogen. Visible foliar injury responses of Saskatoon were used as a biological indicator of SO(2) exposures, through monthly field surveys. During late July 1998, unifacial, interveinal chlorosis was observed on some 12% of the seedlings at one study site. By September, the chlorosis had become more severe (necrosis) on some 70% of the plants at that site. Site specific ambient SO(2) levels were relatively low (maximum 5-min concentration of 52.8 ppb). Similar data were unavailable for all, but one other site. Therefore, foliar total S and SO(4)(2-)-S concentrations were analyzed in September at four of the five study sites. Previously soil SO(4)(2-)-S at these sites had been analyzed. There were spatial variabilities among these parameters. Based on the overall examination of these data, it is concluded that the observed visible injury symptoms were due to chronic SO(2) exposures, exacerbated by the presence of ozone (O(3)). Independent of this literature based speculation, visible foliar injury responses of Saskatoon can be used as a biological indicator for acute or chronic ambient SO(2) exposures, in the presence of other phytotoxic air pollutants.     

Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO4(2-)/Cl-) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO4(2-)/Cl-) and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO4(2-)/Cl-) which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9 per thousand in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO3-) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO3- is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.     

Sulphur status in some Swedish podzols as influenced by acidic deposition and extractable organic carbon

To evaluate the changes in sulphur pools in response to acidic deposition, two studies were made-one in southwest Sweden where podzolic B horizons originally sampled in 1951 were resampled in 1989. At the Norrliden site, northern Sweden, sulphur pools in control plots were compared to plots that had been subjected to H(2)SO(4) application between 1971 and 1976. The results show that in southwest Sweden neither organic S nor extractable SO(4)(2-) increased significantly over the 38-year period, despite a decreasing pH and a high S deposition. At Norrliden, about 37% of the applied S was still remaining in the upper and central parts of the Bs horizon, most of which was inorganic sulphate. These contrasting results are explained by intrinsic differences in the soil organic carbon status between the sites-in southwest Sweden, organic carbon concentrations were high which inhibited SO(4)(2-) adsorption. Low organic carbon concentrations and high extractable Fe/Al concentrations promoted SO(4)(2-) adsorption and caused a low subsequent SO(4)(2-) desorption rate at the Norrliden site. The results suggest that sulphate adsorption may be an important mechanism which delays the response in soil chemistry to H(2)SO(4) deposition, provided that soil organic carbon concentrations are low. Organic S retention was not shown to be an important S retention mechanism in any of the sites studied.     

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.     

Effects of nitrogen with and without acidified sulphur on an ectomycorrhizal community in a Sitka spruce (Picea sitchensis Bong. Carr) forest

This preliminary study investigated the effects of enhanced nitrogen (NH4NO3 at 48 kg ha(-1) y(-1)), sulphur (Na2SO4 at 50 kg ha(-1) y(-1)), acidified nitrogen and sulphur (H2SO4 + NH4NO3) at pre-stated doses (pH 2.5), and acidified nitrogen and sulphur deposition at double these doses on the ectomycorrhizal community associated with a 13-year-old Sitka spruce (Picea sitchensis) forest. Sulphur deposition had little impact on below ground ectomycorrhizal diversity, but stimulated sporocarp production. Nitrogen inputs increased below ground colonisation compared to acidified nitrogen and sulphur, largely due to an increase in Tylospora fibrillosa colonisation. Sporocarp production and ectomycorrhizal root colonisation by Lactarius rufus were reduced in the nitrogen treated plots. These observations suggest that nitrogen deposition to a young plantation may suppress ectomycorrhizal fungi producing large sporocarps. It is proposed that enhanced nitrogen deposition increases ectomycorrhizal nitrogen assimilation, consuming more carbon and leaving less for extrametrical mycelium and sporocarp development.     

Soil acidification and foliar nutrient status of Ontario's deciduous forest in 1986 and 2005

To assess the impacts of the decline in sulphur (S) deposition over the past 20 years in Ontario, soil chemistry and sugar maple (Acer saccharum Marsh) foliar chemistry were measured at 17 sites in south and central Ontario in 2005 and compared with archived samples collected in 1986. Foliar S concentrations were lower in 2005, reflecting the decline in S deposition whereas foliar N remained unchanged, reflecting the lack of change in N deposition in Ontario. Mineral soil pH, exchangeable base cations were lower in 2005 whereas total S, N and cation exchange capacity (CEC) were unchanged. Foliar concentrations of Ca were positively related to soil Ca levels in the A-horizon and were lower in 2005. Despite evidence of increasing soil acidity and losses of calcium, foliar base cation concentrations at most sites were adequate for sugar maple and forest health in terms of canopy appearance (Decline Index) improved.     

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.     

The effects of excess nitrogen deposition on young Norway spruce trees. Part II the vegetation

The effects of wet-deposited nitrogen on soil acidification and the health of Norway spruce were investigated in a pot experiment using an open-air spray/drip system. Nitrogen was applied as ammonium ((NH(4))(2)SO(4)) or nitrate (HNO(3)/NaNO(3)) in simulated rain to either the soil or the foliage. Symptoms of forest decline as observed in the field were not reproduced, and there was no evidence of direct toxicity. Treatments did, however, have significant effects on tree nutrition. Both NH(+)(4) and NO(-)(3) treatment applied to the foliage lowered foliar K concentrations. NH(+)(4) to a greater extent. Soil-applied NH(+)(4) reduced foliar Mg concentrations and increased foliar Al and Fe. Soil-applied NO(-)(3) significantly reduced foliar P concentrations, and at high doses prevented the alleviation of P deficiency by fertiliser. These effects could be important in some field situations. Ammonium deposition is predicted to be more damaging than nitrate deposition, although the latter may be critical for forests where P status is marginal, such as in parts of the British uplands.     

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.     

In situ assessment of microbial sulfate reduction in a petroleum-contaminated aquifer using push-pull tests and stable sulfur isotope analyses

Anaerobic microbial activities such as sulfate reduction are important for the degradation of petroleum hydrocarbons (PHC) in contaminated aquifers. The objective of this study was to evaluate the feasibility of single-well push-pull tests in combination with stable sulfur isotope analyses for the in situ quantification of microbial sulfate reduction. A series of push-pull tests was performed in an existing monitoring well of a PHC-contaminated aquifer in Studen (Switzerland). Sulfate transport behavior was evaluated in a first test. In three subsequent tests, we injected anoxic test solutions (up to 1000 l), which contained 0.5 mM bromide (Br-) as conservative tracer and 1 mM sulfate (SO4(2-)) as reactant. After an initial incubation period of 42.5 to 67.9 h, up to 1100 l of test solution/groundwater mixture was extracted in each test from the same location. During the extraction phases, we measured concentrations of relevant species including Br-, SO4(2-) and sulfide (S(-II)), as well as stable sulfur isotope ratios (delta 34S) of extracted, unconsumed SO4(2-) and extracted S(-II). Results indicated sulfate reduction activity in the vicinity of the test well. Computed first-order rate coefficients for sulfate reduction ranged from 0.043 +/- 0.013 to 0.130 +/- 0.015 day-1. Isotope enrichment factors (epsilon) computed from sulfur isotope fractionation of extracted, unconsumed SO4(2-) ranged from 20.2 +/- 5.5@1000 to 22.8 +/- 3.4@1000. Together with observed fractionation in extracted S(-II), isotope enrichment factors provided strong evidence for microbially mediated sulfate reduction. Thus, push-pull tests combined with stable sulfur isotope analyses proved useful for the in situ quantification of microbial sulfate reduction in a PHC-contaminated aquifer.     

Changes in the concentrations of phenolics and photosynthates in Scots pine (Pinus sylvestris L.) seedlings exposed to nickel and copper

Studies were done on the effects of elevated soil concentrations of copper (Cu) and (Ni) on foliar carbohydrates and phenolics in Scots pine (Pinus sylvestris L.). Four year-old seedlings were planted in pots filled with metal-treated mineral forest soil in early June. The experimental design included all combinations of four levels of Cu (0, 25, 40 and 50 mg kg(-1) soil dw) and Ni (0, 5, 15 and 25 mg kg(-1) soil dw). Current year needles were sampled for soluble sugar, starch and phenolics at the end of September. Ni increased sucrose concentration in the needles, indicating disturbances in carbohydrate metabolism. Trees exposed to Ni had higher concentrations of condensed tannins compared with controls. In contrast, concentrations of several other phenolic compounds decreased when seedlings were exposed to high levels of Cu or to a combination of Ni and Cu. The results suggest that concentrations of phenolics in Scots pine needles vary in their responses to Ni and Cu in the forest soil.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

Spatial relationships between nitrogen status and pitch canker disease in slash pine planted adjacent to a poultry operation

Pitch canker disease (Fusarium circinatum Nirenberg & O'Donnell) causes serious shoot dieback, reduced growth and mortality in pines found in the southern and western USA, and has been linked to nutrient imbalances. Poultry houses with forced-air ventilation systems produce nitrogen (N) emissions. This study analyzed spatial correlations between pitch canker disease and foliar, forest floor, soil, and throughfall N in a slash pine (Pinus elliottii var. elliottii Engelm.) plantation adjacent to a poultry operation in north Florida, USA. Tissue and throughfall N concentrations were highest near the poultry houses and remained elevated for 400 m. Disease incidence ranged from 57-71% near the poultry houses and was spatially correlated with N levels. Similarly, stem mortality ranged from 41-53% in the most heavily impacted area, and declined to 0-9% at distances greater than 400 m. These results suggest that nutritional processes exacerbate changes in disease susceptibility and expression in slash pine.     

Tree decline in North America

Air-borne, phytotoxic pollutants are known to adversely affect forest tree growth in North America. On a local scale, exposure to high concentrations of toxic gases, such as sulphur dioxide and fluoride, result in foliar injury, branch dieback, reduced radial growth and increased mortality in a variety of tree species. On a regional scale, the photochemical oxidant, ozone, is responsible for growth decline of pollutant-sensitive eastern white pine genotypes in the eastern United States, and of ponderosa and Jeffrey pines in the mountains of southern and central California. The etiology associated with the reported declines of high elevation red spruce in the Appalachian Mountains and of sugar maple in the northeastern United States and southeastern Canada is incompletely known at present. A complex of predisposing and inciting factors, including temperature and moisture stress, edaphic conditions, aluminium toxicity, insect depredation, and air-borne pollutants are probably involved in these declines.     

The effects of simultaneous large acidic and alkaline airborne pollutants on forest soil

The effects of air pollutants on soil were studied in Scots pine (Pinus sylvestris L.) forests near the boundary of Russia and Estonia. The study area is characterized by large amounts of acidic and basic pollutants, mainly sulphur dioxide (SO(2)) and calcium (Ca). Several variables were measured in different horizons of the podzolic soil polluted by emissions from local sources in areas of several thousands of square kilometers. Alkalinization dominates the processes in the soil, since sulphur is absorbed only in small quantities and Ca is much better absorbed. Ca content in humus horizon may rise even to 100 000 mg kg(-1) and the pH of originally very acidic soil may rise to 8.3. Total aluminum (Al) content was high in the heavily polluted plots, since emissions contain much Al. On the other hand, the exchangeable Al was very low in these alkaline sites. A larger quantity of exchangeable Al occurred farther from the pollutant sources, even though total Al in these plots was low. These plots had acidic soils in which Al is in exchangeable form. Due to the neutralizing effect of acidic and basic pollutants, forest damage in the study area was not as serious as might be supposed. Complicated pollutant situations must be taken into consideration when pollution-caused environmental protection measures are planned. It is not reasonable to reduce only SO(2) emissions, but necessary to lower the basic emissions at the same time.     

Iron content and its relations to the sulphur and titanium contents of epiphytic and terricolous lichens and pine bark in Finland

The iron content was studied in the epiphytic lichens Hypogymnia physodes (L.) Nyl. and Pseudevernia furfuracea (L.) Zopf, in the terricolous lichens Cladina sp. and Peltigera aphthosa (L.) Willd., and in pine bark collected from 31 sites in Finland. There appeared to be differences between lichen species, epiphytes having generally higher concentrations. The iron content of H. physodes was highly significantly correlated (p<0.001) with its sulphur content, reflecting the relations of these elements in precipitation. The highly significant correlations between the iron and titanium contents indicated differences of the phorophytes. The iron/sulphur ratio of H. physodes on pine was 1.3 and on birch 1.4 and iron/titanium ratios were 10.4 and 11.3 respectively. The iron content of Cladina sp. showed highly significant parallel correlations (p<0.001) with its sulphur and titanium contents. The iron/titanium ratio decreased from 9.6 to 8.2 when the iron content increased by 95%, the sulphur content being equal. The iron/titanium ratio of Cladina sp. was nearly identical to that of P. furfuracea. The relation between iron and sulphur, and the fraction of soluble and insoluble iron in precipitation versus lichens and pine bark were considered. Special attention was paid in the discussion to differences in substrate: pine and birch bark for H. physodes, and soil for Cladina sp.