Cu-Ni Smelter Research Articles

Heavy-metal pollution and remediation of forest soil around the Harjavalta Cu-Ni smelter, in SW Finland

Heavy metals and sulphur have been emitted from the Cu-Ni smelter at Harjavalta since 1945. This article reviews the work that has been published in scientific journals after 1975 concerning heavy metal deposition and the effects of pollution on forest ecosystem around Harjavalta. The pollution has had diverse effects on boreal forest ecosystem, e.g. vegetation, nutrient cycle mediated by microbiota and soil animals, herbivorous insects and pathogens, resistance mechanisms of vegetation, and birds. The deposition of heavy metals has increased up to 30 km distance from the smelter. At 8 km distance the ecosystem began to approximate an undisturbed ecosystem where only slight changes in the understorey vegetation were observed. At 4 km distance the species composition of different ecosystem components (vegetation, insects, birds, soil microbiota) had changed and the growth of trees was retarded. At 0.5–1 km distance, where the nutrient cycling was disturbed and only the most resistant organisms were surviving, the ecosystem had ceased to carry out its essential functions. Remediation through liming or mulching with organic matter, of forest soil has had some positive effects on the ecosystem.

Effect of industrial pollution on the distribution of Pu and Am in soil and on soil-to-plant transfer of Pu and Am in a pine forest in SW Finland

The effect of industrial pollution on the behavior of plutonium and americium was evaluated in a pine forest in the vicinity of a Cu-Ni smelter in SW Finland. Soil and vegetation were sampled at distances of 0.5, 2, 4 and 8 km from the smelter. The vertical distribution of plutonium and americium was studied in litter, organic layer and mineral layers. The amount of Pu and Am in the litter layer increased and that in the organic layer decreased towards the smelter. Concentrations of plutonium and americium in different vegetation species decreased in the order mushrooms > lichens (Cladina spp., Cetraria islandica) > Empetrum nigrum > Vaccinium vitis-idaea.

Enrichment of Cu, Ni, Zn, Pb and As in an ombrotrophic peat bog near a Cu-Ni smelter in Southwest Finland

The accumulation of selected trace elements (Cu, Ni, Zn, Pb, As) in the surface peat layer of an ombrotrophic bog 2.4 km from a Cu-Ni smelter at Harjavalta, Finland was studied using a peat core. A reference core was taken from an ombrotrophic bog at a background site, Hietajärvi, in eastern Finland. Element concentrations were analysed from 1-cm slices and enrichment factors (EF) were calculated. The enrichment factors of both Cu and Ni in the Harjavalta peat bog are extremely high compared to the Hietajärvi site. However, only the 6-cm surface peat Pb values are higher in Harjavalta compared to Hietajärvi. Precipitation was collected during 1992–1996, in the vicinity of the Harjavalta smelter, in order to estimate the current atmospheric deposition load. Comparison between the precipitation and peat data reveals that at Harjavalta the surface peat is relatively much more polluted than the current precipitation. The variation in EF of the Harjavalta peat core with respect to depth shows two patterns: Cu and Pb are similar, as are Ni, Zn and As. The vertical gradient in Harjavalta Cu EF suggests that Cu supplied to the peat by atmospheric deposition is very well preserved by the bog.

Trace Metals in Soil and Plants Subjected to Strong Chemical Pollution

The total concentrations of ten elements (Ag, As, Co, Cs, Fe, Ir, Ni, Rb, Sb, and Sc) were determined in soil and vegetation samples from the surroundings of a Cu-Ni smelter in Monchegorsk, Northwest Russia, and a background area in Naruska, North Finland. The samples were analysed by epithermal neutron activation analysis (ENAA). Elements emitted from the smelter (Ag, As, Co, Ir, Ni, and Sb) were mostly accumulated in the topsoil. Some elements also appeared to contaminate deeper soil layers. In both soil and vegetation the metal concentrations decreased with increasing distance from the smelter. The most significant contributor to the high concentrations of Fe and Sc near the smelter was probably damaged ground vegetation and subsequent wind erosion. Possibly high geochemical abundance of Fe and Sc may also have been a contributing factor. Concentrations of Cs and Rb in soil and vegetation generally increased with increasing distance from the pollution source. High negative correlations were evident between these elements and the elements emitted from the smelter, suggesting that cation exchange of Cs and Rb by the elements supplied from the smelter was likely occurring in the surface soil.

Severe photobiont injuries of lichens are strongly associated with air pollution.

The photobiont ultrastructure of the epiphytic lichens Bryoria fuscescens and Bryoria fremontii was studied along the pollution gradient from two Cu-Ni smelters in Nikel and Monchegorsk in northern Finland and north-western Russia. The relationship between ultrastructural characteristics of B. fuscescens and environmental factors (i.e. climate, atmospheric SO2 and bark element concentrations) was studied by using a principal component analysis (PCA) aiming to assess the air quality in a northern environment. Based on PCA, increased plasmolysis and mitochondrial changes in the Trebouxia photobiont were significantly correlated with elevated pollutant concentrations. Degenerated cells, showing altered chloroplasts and electron-translucent pyrenoglobuli, occurred in lichens growing 35-50 km from the Monchegorsk smelter. Cell wall and cytoplasmic lipid volumes, and size of pyrenoglobuli, positively correlated with the distance from the Monchegorsk smelter. Vacuoles and electron-opaque vacuolar deposits were significantly increased at the Finnish site in the vicinity of a pulp mill. Swelling of mitochondrial cristae and thylakoids showed little correlation with environmental factors, but indicated of initial stage of injuries and were observed at several slightly polluted sites in northern Finland and north-western Russia. The results suggest that the severe photobiont injuries of lichens are strongly associated with poor air quality.

Decreased photosynthetic efficiency in plant species exposed to multiple airborne pollutants along the Russian-Norwegian border

Photosynthetic efficiency was estimated by chlorophyll fluorescence measurements (Fv/Fm) in 11 plant species growing along a steep gradient of airborne pollution along the Russian-Norwegian border (70°N, 30°E). Photosynthetic efficiency was positively correlated with environmental variables including annual temperature and a maritime gradient and was negatively correlated with the airborne concentrations of Cu, Ni, and SO2 from the Cu-Ni smelters. Photosynthetic efficiency in six plant species from the mixed forest, but not pine (Pinus sylvestris L.), and three species from the birch forest was inversely correlated with SO2 and the concentrations of Ni and Cu in lichens. Measurement of fluorescence in these species was a sensitive indicator of pollutant impact. Plant cover at the 16 study sites and the photosynthetic efficiency of five target species correlated with normalized difference vegetation index (NDVI) values. This study demonstrated that it is possible to detect relations among field-measured ecophysiological responses in plants, levels of airborne pollutants, and satellite remote-sensed data.Key words: chlorophyll fluorescence, smelters, sulfur dioxide, nickel, copper, normalized difference vegetation index (NDVI).

Decreased photosynthetic efficiency in plant species exposed to multiple airborne pollutants along the Russian-Norwegian border

Photosynthetic efficiency was estimated by chlorophyll fluorescence measurements (Fv/Fm) in 11 plant species growing along a steep gradient of airborne pollution along the Russian-Norwegian border (70°N, 30°E). Photosynthetic efficiency was positively correlated with environmental variables including annual temperature and a maritime gradient and was negatively correlated with the airborne concentrations of Cu, Ni, and SO2 from the Cu-Ni smelters. Photosynthetic efficiency in six plant species from the mixed forest, but not pine (Pinus sylvestris L.), and three species from the birch forest was inversely correlated with SO2 and the concentrations of Ni and Cu in lichens. Measurement of fluorescence in these species was a sensitive indicator of pollutant impact. Plant cover at the 16 study sites and the photosynthetic efficiency of five target species correlated with normalized difference vegetation index (NDVI) values. This study demonstrated that it is possible to detect relations among field-measured ec...

Small-scale dynamics of plant communities in an experimentally polluted and fungicide-treated subarctic birch-pine forest

Pollution from the Cu-Ni smelter at Monchegorsk, Kola peninsula, has resulted in major changes in the plant communities surrounding the smelter. However, very little pollution reaches northern Finland, which makes it possible to use this area for field experiments to study the mechanism of community change under pollution load. A field experiment was established to study the possible effect of pollution on the subarctic forest community, with Cu-Ni pollution and acid rain (AR) used as treatments. A fungicide (F)-treatment was also added to estimate the significance of plant-fungus interactions in community response. Floristic similarity decreased during the experiment, both within and between treatments. Cu-Ni- and AR-treatments did not have any effect on species richness. The Cu-Ni treatment reduced significantly the number of new species arrivals in plots, whereas the number of local extinctions remained constant. The heavy metal treatment resulted in a decrease in the bryophyte cover. The cover of Linnea borealis increased slightly due to the Cu-Ni-treatment, but decreased due to the AR-treatment. The F-treatment also resulted in a lower richness than in the untreated variant. Again, this effect was due to the reduced number of arrivals, whereas the number of local extinctions remained unchanged. The F-treatment also resulted in a higher cover of bryophytes and dwarf shrubs. Changes in species richness of subarctic understorey plant communities were mainly caused by the differential arrival of species under different environmental conditions. As the number of arrivals was negatively correlated to the F-treatment, the presence of (presumably positive) interactions between vascular plants and fungi may have an influence on the response of a community to pollution.

Compensatory fertilization of Scots pine stands polluted by heavy metals

The results from four compensatory fertilization experiments located at different distances (0.5, 2, 4 and 8 km) along a heavy metal deposition gradient extending from the Harjavalta Cu-Ni smelter in SW Finland are presented. The experiments were established in middle-age Scots pine stands growing on dryish sites of sorted glaciofluvial sediments. The soil type in all the experiments is ferric podsol. The treatments in the experiments consisted of liming, a powdered slow-release mineral mixture and stand-specific fertilization which comprised at least methylene urea and ammonium nitrate.

Fine-root growth, mortality and heavy metal concentrations in limed and fertilized Pinus silvestris (L.) stands in the vicinity of a Cu-Ni smelter in SW Finland

This study was conducted to assess 1) the growth of fine roots into ingrowth cores and fine root mortality, 2) the effects of liming and correction fertilization on fine-root growth and mortality, and 3) the concentrations of heavy metals in fine roots in control, limed or fertilized Scots pine stands at different distances from a copper-nickel smelter. Fine-root biomass in the ingrowth cores in the control plots varied between 1 (at 0.5 km from the smelter) and 252 and 271 g/m2 (at 4 and 8 km, respectively). In the most polluted stand at 0.5 km, 98% of the fine roots that had grown into the ingrowth cores had died before sampling. Corresponding values for the other stands (4 and 8 km) were only 13-18%. At 0.5 km, liming increased the growth and survival of fine roots. The concentrations of Cu and Ni were also smaller in fine roots from the limed plot than those from the control plot. In the correction fertilization treatment at 0.5 km the total ingrowth of fine roots was at the same level as in the control, but less fine roots had died. Thus, the correction fertilizer treatment increased the survival but not the growth of fine roots. At 4 or 8 km, there were no significant differences in the fine-root biomass or necromass or element concentrations between the treatments.

Multi-Element Analysis of Dry-Ashed Honey Samples by Thick-Target PIXE

Honey samples were dry ashed at 550°C and the ashes were directly analysed with the Thick-Target Particle Induced X-ray Emission (TTPIXE) technique. The elements P, K, Ca, Mn, Fe, Ni, Cu, Zn, Pb, Rb and Sr, were analysed quantitatively. The method allowed the determination of concentrations well below 100 ng/g for most of the elements studied. The ash content can be used for characterization of a honey sample. The samples were collected from two areas in Finland and from the Prague region in the Czech Republic. A Cu-Ni smelter, documented as a source of heavy-metal emission, is situated in one of the areas in Finland. A comparison of metal concentrations in ashes of honey samples proved to be useful for environmental monitoring

Forms of Cu, Ni, and Zn in soils of sudbury, ontario and the metal concentrations in plants

Forms of Cu, Ni, and Zn in the contaminated soils of the Sudbury mining/smelting district were studied to assess metal mobility and plant availability. Soil, tufted grass (Deschampsia caespitosa (L.) Beauv.), tickle grass (Agrostis scabra Willd.), dwarf birch (Betula pumila L. var. glandulifera Regel) and white birch (Betula paprifera Marsh.) leaf and twig samples were taken from 20 locations around three Cu-Ni smelters. The sampling sites were collected to cover a wide range of soil pH and soil Cu and Ni concentrations. The water-soluble, exchangeable, sodium acetate-soluble, and total concentrations of the metals in the soils were analyzed. The soils were contaminated with Cu and Ni up to 2000 µg g−1. Zinc concentrations were also elevated in some samples above the normal soil level of 100 µg g−1. The mobility of Cu and Zn, expressed as the proportion of metals in Fl and F2 forms, increased with soil pH decrease. A strong positive correlation was found between the soil exchangeable (F2) Ni and the soil pH. Concentrations of Cu and Ni in birch twigs showed a good linear relationship with exchangeable forms of the metals in soils. A highly significant correlation was also found between total Ni in soils and the metal content of the twigs. No significant correlation was found between Zn concentrations in the soils and plants. Birch twigs are a good indicator (better than leaves) of Cu and Ni contamination of the Sudbury soils. The mobile forms of Cu and Ni and low pH seem to be the main factors that will control the success of revegetation. Strong variability of the soil metal mobility requires any reclamation effort be site-specific.

Vitality fertilization of Scots pine stands growing along a gradient of heavy metal pollution: short-term effects on microbial biomass and respiration rate of the humus layer.

In 1992 forest vitality fertilization experiments were established on a heavy metal deposition gradient with four treatments in three replications at distances of 0.5, 4 and 8 km from a Cu-Ni smelter in order to estimate their impact on the disturbed forest ecosystem. The increase in Cu concentration in the humus (F/H) layer of the Calluna site type Scots pine (Pinus sylvestris) stands from ca. 300 to 8000 mg kg(-1) d.m. (dry matter) along the 8 km long transect towards the smelter resulted in declining soil microbial biomass and soil respiration activity. Three independent measurements of microbial biomass: C(mic)-FE (fumigation extraction), C(mic)-SIR (substrate induced respiration), and ATP have been used together with an indicator of fungal biomass (ergosterol) and microbial activity (soil respiration). Within this Cu pollution range, all the measured microbial biomass levels declined to 10%-28% of the control plot values and activity assessed by respiration was lowered to 16%. Liming has increased the C(mic)-SIR and respiration rate. Treatments with test fertilizer, made from grounded apatite, did not result in different microbial biomass and respiration rate values compared to the respective controls along the whole gradient. Nitrogen + lime treatments resulted in similar changes to lime alone. No changes, as compared to the respective control, could be detected with nitrogen fertilization at the less polluted end of the gradient.

Decomposer animal communities in forest soil along heavy metal pollution gradient.

Responses of soil decomposer animals to heavy metal contamination and to concomitant changes in organic matter quality and quantity and in soil microbial biomasses have been studied along a pollution gradient from a Cu-Ni smelter. Samples have been taken separately for nematodes, enchytraeids and microarthropods 0.5, 2 and 8 km from the smelter. Special attention has been paid to the changes in the collembolan fauna. The sampling sites have been located in homogeneous Scots pine ( Pinus sylvestris) forests with podsolic soil profiles. In addition, an experiment has been carried out in which intact soil cores have been transferred in mesh baskets between the sites 2 and 8 km from the smelter (control samples have been transferred within the sites). Although most soil animals seemed to be quite resistant to direct and indirect effects of heavy metals, results indicate that certain soil animals like enchytraeids can be useful and easy to monitor when the effects of heavy metals on soil decomposition systems are assessed.

Soil geochemistry in relation to water chemistry and sensitivity to acid deposition in Finnish Lapland

Ecosystems in Finnish Lapland are threatened by heavy metal pollution and acid deposition derived from emissions of Cu-Ni smelters in Kola Peninsula and to varying extent to pollution from southern Fennoscandian and Central European sources. Extensive chemical analyses of small lake waters collected in Finnish Lapland have demonstrated that a significant number of lakes are acidified (ANC < 0μcq/l) or their buffering capacity is critical (ANC = 0–50μe/l). The relative abundance of mafic, ultramafic and carbonate rock components in the catchment were the chief factors controlling ANC and the main base cation (Ca2+, Mg2+) concentrations of lake waters. Both humic and clearwater lakes with low buffering capacity (ANC < 50μeq/l) were mainly located in the catchment areas identified as sensitive to acidification on the basis of low content of base cations (Ca2+ +Mg2+ +K+ < 500 meq/kg) in till. The ratio of the catchment area to the lake area was distinctly smaller for acidic lakes than for the well-buffered lakes, indicating the importance of catchment processes in determining the ANC and main base cations. The high sulphur concentrations (median 60μeq/1) of acidic lakes in northeastern Lapland, near the Finnish-Norwegian border, were strongly correlated with the highest deposition of sulphur derived from smelters of Kola Peninsula. The anomalously high concentrations of sulphur of well-buffered lakes in the western part of Lapland were due to sulphide minerals of soil and bedrock. The acidity of humic lakes in southern Lapland was in large part due to the organic acidity derived from peatlands.

Snowpack quality as an indicator of air pollution in Finnish Lapland and the Kola Peninsula, NW Russia

Bulk snow samples were collected from the snowpack in open areas along two sampling lines running to the west from the Cu-Ni smelters at Nikel and Monchegorsk, NW Russia, during 1991–1993. The aim of the study was to estimate the area affected by sulphur and heavy metal deposition from the smelters. Snowpack quality was used as an indicator of deposition during winter time. The total sulphur, copper and nickel concentrations in the snowpack decreased significantly (p<0.001) with increasing distance from the smelters along the sampling line running directly to the west from Monchegorsk. The deposition pattern was similar each winter during 1991–1993. The pH values did not correlate with the corresponding sulphur concentrations, and there was no decreasing pH gradient in the snowpack on moving towards Monchegorsk. The effects of sulphur emissions from Monchegorsk on snowpack chemistry were not detectable on the Finnish side of the border. The 3-year mean of the total sulphur concentration was 0.27 mg/kg, and of the pH values 4.92, along the sampling line running to the west of Monchegorsk. The total sulphur concentrations near the smelters (< 20 km) varied between 0.37 and 0.95 mg/kg. The effect of the Cu-Ni smelters at Nikel on snowpack quality was not detectable in northern Finnish Lapland. The 3-year mean for total sulphur was 0.20 mg/kg and for pH 4.96 along the sampling line running to the west of Nikel.

The relationship between dissolved organic matter and percolation water chemistry in northern Finland

The aim of this study was to investigate the relationship between dissolved organic matter and chemical constituents of percolation water collected at 5, 20 and 40 cm depths from 13 ion-balance sampling plots located along lines extending through Finnish Lapland from Cu-Ni smelters in the Kola Peninsula, Russia. All the monitoring plots have as uniform as possible stand and site characteristics. The plots were located in Scots pine stands on dry and dryish sites with genetic horizons characteristic of Fe-humus podsols. The soil type on most of the sites was sorted fine sand or sand. Significant positive correlations were found between dissolved organic matter (DOM) and total dissolved Al concentrations at 5 and 20 cm, but not at 40 cm. A significant negative correlation was found between DOM and pH at 5 cm, but not at 20 or 40 cm. The anion deficit was positively correlated with DOM at 5 cm in the percolation water. Organic matter thus plays an important role as an anion in percolation water, and regulates water pH in the surface soil. A high proportion of dissolved Al was in the form of organic complexes. Total dissolved Al levels were well below the toxic limits for pine.

Acidity of podzolic soils subjected to sulphur pollution near a Cu-Ni smelter at the Kola Peninsula

The acidity of the podzolic soils in coniferous forests on the northern tree line (Kola Peninsula) subjected to severe sulphur pollution is considered. The pH values of precipitation were positively correlated with the distance from the pollution point source. There was also a correlation between base saturation of the organic horizon and distance. The long-term SO2-emissions have resulted in the higher leachability of base cations and dissolution of fulvic acids in the humus horizon. In polluted areas the flux of H+ from the organic layer could be stronger owing to higher proportion of hydrolysable humus compounds. Inputs of H+ from the atmosphere and humus horizon have resulted in the higher concentrations of the exchangeable aluminium in the illuvial horizon.

Deposition of sulfate and heavy metals on the Kola Peninsula

Snowpack samples were collected at 20 sites on the Kola Peninsula, Russia, in April 1991. Samples were collected both in remote regions and in areas impacted by nearby emission sources, including the Severonikel CuNi smelter in the city of Monchegorsk. In the background regions, total winter deposition for non-seasalt SO42−, NO3−, Cu, and Ni were 120–300, 70–300, 6–14, and 0.3-1.5 mg/m2, respectively, and the snowpack pH ranged from 4.4 to 4.9. In the region near the Severonikel CuNi smelter, snowpack SO42−, Cu, and Ni concentrations were enhanced considerably. Total winter deposition in this area was in the range of 390–500, 190–280, and 14–32 mg/m2 for non-seasalt SO42−, Cu, and Ni, respectively, with little influence on snowpack pH. In the vicinity of the Severonikel complex, the data indicate relatively inefficient removal of sulfur dioxide by snow and more efficient removal of particles containing metal. The 6-month sulfate deposition within 20 km of the smelter accounts for much less than 1% of the smelter SO2 emissions over the same period. In contrast, approximately 24% of the smelter copper emissions are deposited within 20 km of the source, which suggests an important role for sedimentation of relatively large particles containing metal in the vicinity of the smelter. Pb, As, and Cd deposition to the snowpack is much less, suggesting that emissions of these more toxic elements are largely absent or occur in smaller particles (Kelley et al., this volume).

Soil microbial effects of a Cu-Ni smelter in southwestern Finland

The influence of a Cu-Ni smelter on the soil microbial parameters: physiological groups of bacteria, soil respiration, fungal hyphal length, and green-needle litter decomposition, were investigated. The microbial parameters were reduced and this was significantly explained (P<0.01) by the supplied environmental variables: exchangeable Ca, Mg, K, Mn, Cu, Ni, Cd, Zn, soil moisture, pH, and organic C as loss on ignition (Canoco, RDA-analysis). The importance of measuring exchangeable cations for major and trace elements appeared to be a relevant factor that must be considered when establishing relationships between microbial populations, their activity and the effect of heavy metals.