Effects of emission reductions from the Sudbury smelters on the recovery of acid- and metal-damaged lakes

Aquatic ecosystems in a 17,000 km² area around Sudbury, Ontario, Canada, have been affected by the atmospheric deposition of pollutants from nearly a century of operations at the Sudbury area metal smelters. Effects were most severe in the lakes closest to the smelters which historically received very high deposition of both acid and metal particulates. After smelter emissions were greatly reduced in the 1970‘s, evidence began to emerge of improvements in lake water quality, and some recovery of biological communities, and the emphasis of Sudbury area monitoring programs changed from the assessment of damage to the tracking of recovery patterns. Further reductions in smelter emissions during the1990‘s have been accompanied by continuing improvements in aquatic habitat quality, but the evaluation of lake responses to emission controls is complicated by the interaction of lake acidity and metal concentrations with other factors. Weather-related variations in storage and release of sulphur from lake catchments appear to greatly influence chemical recovery. Despite the general water quality improvements observed to date, some lakes are still highly acidic and elevated levels of copper and nickel persist in the water and sediments of many lakes. Severely damaged biological communities have been slow to recover, probably reflecting a combination of continuing habitat quality limitations and restricted opportunities for dispersal. This revised version was published online in July 2006 with corrections to the Cover Date.     

Density effect on great tit (Parus major) clutch size intensifies in a polluted environment

Long-term data on a great tit (Parus major) population breeding in a metal-polluted zone around a copper–nickel smelter indicate that, against expectations, the clutch size of this species is decreasing even though metal emissions in the area have decreased considerably over the past two decades. Here, we document long-term population-level changes in the clutch size of P. major and explore if changes in population density, population numbers of competing species, timing of breeding, breeding habitat, or female age distribution can explain decreasing clutch sizes. Clutch size of P. major decreased by one egg in the polluted zone during the past 21 years, while there was no significant change in clutch size in the unpolluted reference zone over this time period. Density of P. major nests was similar in both environments but increased threefold during the study period in both areas (from 0.8 to 2.4 nest/ha). In the polluted zone, clutch size has decreased as a response to a considerable increase in population density, while a corresponding density change in the unpolluted zone did not have such an effect. The other factors studied did not explain the clutch size trend. Fledgling numbers in the polluted environment have been relatively low since the beginning of the study period, and they do not show a corresponding decrease to that noted for the clutch size over the same time period. Our study shows that responses of commonly measured life-history parameters to anthropogenic pollution depend on the structure of the breeding population. Interactions between pollution and intrinsic population characters should therefore be taken into account in environmental studies.     

Histopathological characteristics of Coregonus fishes under the impact of metal industry

This article provides results from monitoring studies of the state of common whitefish (Coregonus lavaretus L.) inhabiting the border Pasvik River and a number of lakes of Northern Fennoskandia. The water catchment area is subject to a significant contamination by coper, nickel, and sulfur dioxide due to the airborne transport of emissions from the Pechenganikel smelter. The ecological situation near the smelter is evaluated as very unfavorable and requires constant control, including the monitoring of aquatic systems. We used histopathologies of gills, liver, and kidneys as biomarkers to diagnose the state of sparsely rakered whitefish. Changes in their cellular structure were diagnosed and classified. The presence of the revealed abnormalities is associated with long-term aerotechnogenic stress on the investigated water bodies. The possibility of using the obtained data for assessing water quality has been considered.     

Seminal plasma trace metal levels in industrial workers

This study compares the seminal plasma trace metal levels of hospital workers with groups of industrial workers in a petroleum refinery, smelter, and chemical plant. The metals measured were the essential metals (copper, zinc, nickel, cobalt, and manganese) and the toxic metals (lead, cadmium, and aluminum). The group mean±SE metal level for each group (50 subjects per group) was calculated, and the statistical significance of the group mean differences of the industrial groups with the hospital group (control) was determined by the Student’s t-test. The differences observed in the smelter group were increased copper and zinc (p≤0.001) and decreased nickel, cobalt, and manganese (p≤0.001,≤0.01). The refinery group differences were increased copper, zinc, and nickel (p≤0.001) but decreased cobalt and manganese (p≤0.001). The chemical group differences were increased zinc (p≤0.001) and decreased cobalt (p≤0.001). The seminal plasma levels of the toxic metals lead and aluminum were increased in each of the industrial groups (p≤0.001). Concurrent differences were (1) decreased accumulation of nickel, cobalt, and manganese in the smelter group, (2) decreased cobalt and managanese in the refinery group, and (3) only decreased cobalt in the chemical group.     

Coordination of Ni2+ and Cu2+ to metal ion binding domains of E. coli SlyD protein

The C-terminal region of Escherichia coli SlyD is unstructured and extremely rich in potential metal-binding amino acids, especially in histidine residues. SlyD is able to bind two to seven nickel ions per molecule, in a variety of coordination geometries and coordination numbers. This protein contributes to the insertion of nickel into the hydrogenase precursor protein and it has a peptidyl-prolyl cis/trans-isomerase activity which can be regulated through nickel ions. This inspired us to undertake systematic studies on the coordination ability of two histidine-rich peptides from the C-terminus of the SlyD protein with nickel. Also, it is known that histidine-rich regions are part of a Cu^2 + binding domain involved in copper uptake under conditions of metal starvation in vivo in other bacteria. For this reason we decided to examine the complex formation of Ac-AHGHVHGAHDHHHD-NH₂ and Ac-GHGHDHGHEHG-NH₂ fragments with copper ions, which are also reference metal ions in this study. Experiments were performed in a DMSO/water 30:70 solvent. The Ac-AHGHVHGAHDHHHD-NH₂ and Ac-GHGHDHGHEHG-NH₂ fragments were synthesized and their interactions with Ni^2 + and Cu^2 + ions were studied by potentiometric, mass spectrometric, UV-vis, CD, EPR, and NMR spectroscopic techniques in solution. The results show that the Ac-GHGHDHGHEHG-NH₂ fragment forms equimolar complexes with both nickel and copper ions. At physiological pH, the metal ion is bound only through nitrogens from imidazole sidechain of histidine residues. On the contrary, Ac-AHGHVHGAHDHHHD-NH₂ binds 2 metal ions per molecule, at pH range 5 to 7, even if the 1:2 metal:peptide ratios were used. NMR studies indicate the involvement of all His residues in this pH-range in metal binding of the latter peptide. At higher pH, the stoichiometry changes to 1:1 and the His residues are displaced by amide nitrogens.     

Pollution-related changes in diets of two insectivorous passerines

Insectivorous birds living in polluted areas are not only exposed to pollutants but they may also be affected by changes in their invertebrate food. The populations of many invertebrate species are affected by environmental pollution and such changes may lead to differences in the diet of insectivorous birds. We examined nestling food quality (invertebrate composition and heavy metal levels) and breeding performance of two cavity-nesting passerines, the Great tit, Parus major, and the pied flycatcher, Ficedula hypoleuca, in an area with long-term heavy metal pollution by a copper smelter. There were no differences in feeding frequencies or the amount of food that parents provided to their nestlings between polluted and unpolluted sites, but food quality in a polluted area differed from that of the control area in both bird species. P. major took more beetles and variable “flying insects” and less caterpillars (of smaller size) and moths in the polluted area as compared to the unpolluted one. F. hypoleuca ate more beetles and larvae and less moths and spiders in the polluted area. Breeding success of P. major was better when the nestling diet contained a large proportion of caterpillars and the relationship was especially strong in the polluted area. On the contrary, F. hypoleuca broods succeeded equally well with variable diets. Our data suggest that a more opportunistic forager, F. hypoleuca, is less vulnerable to a changing invertebrate composition caused by human environmental impacts than a caterpillar specialist, P. major. In a heavy metal polluted area, F. hypoleuca seems to be more sensitive to a decreased amount of Ca rich food items (e.g. snails) while P. major suffers especially from the lack of carotenoid rich caterpillars. Our results emphasize the importance of secondary environmental changes, like food quality, in addition to direct impacts of pollutants.     

Effects of Copper,Nickel, and Sulfate from the Smelters at Sudbury,Ontario (Canada) on Microbial Communities in Lakes

Analysis of water and sediments from deep and shallow environments in lakes located 6–154 km east or southeast of the smelters at Sudbury, Ontario (Canada) revealed variable, interactive effects of copper, nickel, and sulfate from smelter fallout on lacustrine microfloras. Metal species in sediments were differentiated by sequential extractions, and the nature, abundances, and activities of microbial populations were represented by chlorophyll-a in water and by CO₂ production, fatty acids, phospholipids, dehydrogenase, alkaline phosphatase, and spectral properties of humic matter in sediments. Smelter fallout declined logarithmically with distance from the smelters, and its effects on microfloras depended on the type of microorganism or microbial process and on environmental factors and the abundances of metal species and detoxifying agents. Extractable copper and nickel had toxic effects, which were not attributable solely to the exchangeable fractions, but in certain cases nickel counteracted copper toxicity. Sedimentary sulfide as a whole or sulfide produced by bacterial sulfate reduction, or low oxidation–reduction potential regardless of sulfide concentration, ameliorated metal toxicity by making the metals less bioavailable; and toxicity showed a “quantum jump” when detoxifying agents fell below certain critical concentrations, implying the existence of threshold levels of bioavailable metals above which toxicity increased abruptly. In some cases metal toxicity was lowest in the lakes closest to the smelters (because sulfate concentrations were highest) as well as in the lakes furthest away, and was highest at intermediate distances. The results also suggest that nickel pollution led to ecological succession whereby nickel-tolerant microbial populations replaced nickel-sensitive ones.     

Environmental pollution affects genetic diversity in wild bird populations

Many common environmental pollutants, together with nuclear radiation, are recognized as genotoxic. There is, however, very little information on pollution-related genetic effects on free-living animal populations, especially in terrestrial ecosystems. We investigated whether genetic diversity in two small insectivorous passerines, the great tit (Parus major) and the pied flycatcher (Ficedula hypoleuca), was changed near point sources of heavy metals (two copper smelters) or radioactive isotopes (nuclear material reprocessing plant). We measured concentration of heavy metals and nucleotide diversity in mitochondrial DNA in feather samples taken from nestlings in multiple polluted areas and at control sites. In both species, heavy metal concentrations - especially of arsenic - were increased in feathers collected at smelter sites. The P. major population living near a smelter showed significantly higher nucleotide diversity than a control population in an unpolluted site, suggesting increased mutation rates in a polluted environment. On the contrary, F. hypoleuca showed reduced nucleotide diversity at both smelter sites but increased nucleotide diversity near the source of radioactivity. Our results show that heavy metal pollution and low level nuclear radiation affect the nucleotide diversity in two free-living insectivorous passerines. We suggest that the different response in these two species may be due to their different ability to handle toxic compounds in the body.     

Molecular identification,differential expression and protective roles of iron/manganese superoxide dismutases in the green algae Closterium ehrenbergii against metal stress

The green microalgae Closterium ehrenbergii is an ideal organism for ecotoxicology assessments; however, its toxicogenomics has been insufficiently examined. Here, we identified three iron/manganese superoxide dismutase (SOD) genes (designated as CeFeSOD1, CeFeSOD2, and CeMnSOD) from C. ehrenbergii and examined their expressional patterns for four metals (iron, manganese, copper, and nickel). These genes encoded 362, 224, and 245 amino acids, respectively; signal-peptide analysis showed that they were differentially located in chloroplasts, cytosol, or mitochondria. Real-time PCRs revealed differential expression patterns according to metal and doses. Interestingly, CeSODs displayed no noticeable changes to treatment with their corresponding cofactor metals, iron or manganese, even at high doses. However, they were obviously up-regulated under toxic metal (copper and nickel) exposure, exhibiting approximately 10.8- and 4.4-fold increases, respectively. Copper (0.2 mg/L) dramatically stimulated intracellular reactive oxygen species (ROS) formation, increased SOD activity, and reduced photosynthetic efficiency in C. ehrenbergii. These results suggest that CeFeSODs and CeMnSOD might be involved in protecting cells against damage and oxidative stress caused by non-cofactor metals, such as copper and nickel. These genes were sensitively responsive at levels well below the EC₅₀, showing that they can be used as molecular biomarkers to assess the toxicity of specific metal contaminants.     

Pollution related effects on immune function and stress in a free-living population of pied flycatcher Ficedula hypoleuca

We investigated whether exposure to heavy metal pollution affected the immune function of individuals in a free living population of a small insectivorous passerine bird, the pied flycatcher Ficedula hypoleuca . We measured humoral immune responses in two study areas: a polluted area in the vicinity of a copper smelter and a control area far from the smelter. Plasma corticosterone level and blood heterophil/lymphocyte ratio (H/L) were used as more general physiological measures of stress. The immune response of F. hypoleuca was not suppressed by pollution stress. In contrast, we found that F. hypoleuca males showed stronger humoral immune responses to a novel antigen (tetanus toxoid) in the polluted environment than in the unpolluted one. After the immunization of males, numbers of lymphocytes rose significantly more in the polluted area, leading to a smaller H/L ratio than in males from the control area. Females showed no pollution related effects on their immune responses. Corticosterone levels of males and nestlings were not related to pollution levels. Nestlings showed somewhat higher H/L ratios and lower fledging success in the polluted area, both factors indicating increased stress levels in a polluted area. Our results suggest that humoral immune response of male F. hypoleuca may be enhanced under moderate levels of heavy metal pollution. Enhanced immune function may, however, also be costly for birds and the higher humoral immune responses in polluted areas may thus have negative effects on the birds' breeding performance and survival.     

分离自活性污泥的硫酸盐还原菌用于铅锌冶炼渣重金属污染修复

【背景】从活性污泥中分离出一类具有硫酸盐还原能力的菌株,探讨了其用于铅锌冶炼渣重金属污染修复的可行性。【目的】研究硫酸盐还原菌(Sulfate reducing bacteria)对铅锌冶炼渣中重金属的固化作用。【方法】将从活性污泥中分离出的硫酸盐还原菌接种到铅锌冶炼渣中进行修复,采用X射线衍射、Tessier、电感耦合等离子体发射光谱仪检测、高通量测序等方法进行实验。检测铅锌冶炼渣中矿物组成,以及修复过程中重金属化学形态、各金属离子浓度和微生物群落结构的变化。【结果】修复实验表明,体系中电位降低、pH值提高、各重金属稳定态增加、离子浓度降低且微生物群落结构变化显著,硫酸盐还原菌成为优势菌群。【结论】接种硫酸盐还原菌后铅锌冶炼渣中的重金属原位固化效果显著,从而降低生物可利用性,将恶性循环变为良性循环,所以硫酸盐还原菌可用作重金属污染修复的固化药剂。     

Use of poly(lactic acid) amendments to promote the bacterial fixation of metals in zinc smelter tailings

The ability of poly(lactic acid) (PLA) to serve as a long-term source of lactic acid for bacterial sulfate reduction activity in zinc smelter tailings was investigated. Solid PLA polymers mixed in water hydrolyzed abiotically to release lactic acid into solution over an extended period of time. The addition of both PLA and gypsum was required for indigenous bacteria to lower redox potential, raise pH, and stimulate sulfate reduction activity in highly oxidized smelter tailings after one year of treatment. Bioavailable cadmium, copper, lead and zinc were all lowered significantly in PLA/gypsum treated soil, but PLA amendments alone increased the bioavailability of lead, nickel and zinc. Similar PLA amendments may be useful in constructed wetlands and reactive barrier walls for the passive treatment of mine drainage, where enhanced rates of bacterial sulfate reduction are desirable.     

Sorption of Heavy Metals to the Filamentous Bacterium Thiothrix Strain A1

A study was undertaken to determine the ability of the filamentous bacterium Thiothrix strain A1 to sorb heavy metals from solution. Cells of Thiothrix strain A1 were harvested, washed, and suspended in solutions of metals. After an equilibration period, biomass was separated from solution and the metal content in acid-digested cells and/or filtrates was determined by atomic absorption spectrophotometry. Sorption of nickel and zinc was very rapid; most of the sorbed metal was bound in less than 10 min. The sorption data for copper fit the Freundlich isotherm, and nickel and zinc data fit biphasic Freundlich isotherms. Sorption of both nickel and zinc was dependent on cell age. Cells harvested 24 h after inoculation sorbed approximately one-half of the amount of metal per gram cell protein than did cells harvested after 48, 72, or 96 h. Calcium and magnesium effectively competed with zinc for binding sites, whereas potassium had only a slight effect on the capacity of cells to sorb zinc. The primary mechanism of metal sorption apparently was ion exchange, because 66 to 75% of nickel or zinc could be desorbed by placing metal-laden cells in a solution of 5 mM CaCl₂. A competition experiment with nickel and zinc indicated that both metals occupied the same sorption sites. The strong chelating agents EDTA and NTA effectively prevented metal uptake, but lactate enhanced the uptake of nickel. Thiothrix strain A1 grown in nickel-containing medium had a relatively low uptake of nickel compared with uptake by resting cells suspended in a simple buffer solution.     

Pollution-related changes in oxidative stress and antioxidant defense profile in the blood of white stork Ciconia ciconia chicks from different regions of Poland

Changes in the lipid peroxidation and oxidatively modified protein levels as well as the antioxidant defense system in the blood of white stork (Ciconia ciconia) chicks were analyzed during their development in nests in polluted and control environments. The control, relatively pure, environment was the village of K?opot, with no industrial plants within a radius of 150 km. Blood samples were also collected in two polluted areas, including (1) the suburban village of Czarnowo, located 20 km from the city of Zielona Góra (southwestern Poland) and (2) an area near the town of G?ogów, where a large copper smelter is situated. The effects of various ecological threats from different environments tended to initiate oxidative stress and decrease total antioxidant capacity. The initiation of lipid peroxidation and increases in the levels of carbonyl derivatives of oxidative amino acids were observed in the plasma of chicks from polluted areas. Plasma catalase and the selenium-dependent glutathione peroxidase activities of erythrocytes were significantly higher in chicks from polluted areas than in those from control areas. Oxidative stress and components of the antioxidant defense system, especially glutathione peroxidase activity, can be used as indicators of oxidative stress, which was found to be greater in the polluted areas (near the G?ogów copper smelter). Research into oxidative stress biomarkers can aid assessments of the conditions of birds, and points to a positive association with miscellaneous environmental loads.     

Nickel: a review of its occupational and environmental toxicology

Nickel and nickel compounds belong to the classic noxious agents encountered in industry, but is also known to affect non-occupationally exposed individuals, especially those handling stainless-steel and nickel plated articles of everyday use. For plants and some vertebrates, specifically for mammals, nickel is indispensable as one of the essential trace elements. The most important health problems due to exposure to nickel and nickel compounds are allergic dermatitis (nickel itch) and increased incidence of cancers of the lungs and nasal mucosa encountered among the workers after a long-term over-exposure to nickel. In this respect the most hazardous nickel compounds appear to be nickel sulfide and nickel oxide. The monitoring of nickel exposure levels can be based on blood serum and urine analyses, but also on nickel determinations in hair which have proved promising even in groups of non-occupationally exposed individuals. Nickel carbonyl is the most toxic of all of the nickel compounds encountered, but because of its relatively short half-life it does not seem to represent any actual biohazard from the standpoint of environmental pollution. To prevent incidence of malignancies it is recommended to include in the routine plan of the preventive medical examinations also the cytologic analysis supplemented, in the case of cytologic positivity, with the bioptic examination for epithelial dysplasia. A systematic medical surveillance of workers with known long-term exposure to nickel is, of course, essential. At present, a major attention is centered on biochemical interactions of nickel with copper, cadmium, iron, iodine and particularly with manganese known to significantly reduce the experimental carcinogenicity of nickel and nickel compounds.     

Abundance,Composition and Activity of Ammonia Oxidizer and Denitrifier Communities in Metal Polluted Rice Paddies from South China

While microbial nitrogen transformations in soils had been known to be affected by heavy metal pollution, changes in abundance and community structure of the mediating microbial populations had been not yet well characterized in polluted rice soils. Here, by using the prevailing molecular fingerprinting and enzyme activity assays and comparisons to adjacent non-polluted soils, we examined changes in the abundance and activity of ammonia oxidizing and denitrifying communities of rice paddies in two sites with different metal accumulation situation under long-term pollution from metal mining and smelter activities. Potential nitrifying activity was significantly reduced in polluted paddies in both sites while potential denitrifying activity reduced only in the soils with high Cu accumulation up to 1300 mg kg⁻¹. Copy numbers of amoA (AOA and AOB genes) were lower in both polluted paddies, following the trend with the enzyme assays, whereas that of nirK was not significantly affected. Analysis of the DGGE profiles revealed a shift in the community structure of AOA, and to a lesser extent, differences in the community structure of AOB and denitrifier between soils from the two sites with different pollution intensity and metal composition. All of the retrieved AOB sequences belonged to the genus Nitrosospira, among which species Cluster 4 appeared more sensitive to metal pollution. In contrast, nirK genes were widely distributed among different bacterial genera that were represented differentially between the polluted and unpolluted paddies. This could suggest either a possible non-specific target of the primers conventionally used in soil study or complex interactions between soil properties and metal contents on the observed community and activity changes, and thus on the N transformation in the polluted rice soils.     

Trace Metal Acquisition by Marine Heterotrophic Bacterioplankton with Contrasting Trophic Strategies

Heterotrophic bacteria in the SAR11 and Roseobacter lineages shape the marine carbon, nitrogen, phosphorous, and sulfur cycles, yet they do so having adopted divergent ecological strategies. Currently, it is unknown whether these globally significant groups partition into specific niches with respect to micronutrients (e.g., trace metals) and how that may affect marine trace metal cycling. Here, we used comparative genomics to identify diverse iron, cobalt, nickel, copper, and zinc uptake capabilities in SAR11 and Roseobacter genomes and uncover surprising unevenness within and between lineages. The strongest predictors for the extent of the metal uptake gene content are the total number of transporters per genome, genome size, total metal transporters, and GC content, but numerous exceptions exist in both groups. Taken together, our results suggest that SAR11 have strongly minimized their trace metal uptake versatility, with high-affinity zinc uptake being a unique exception. The larger Roseobacter genomes have greater trace metal uptake versatility on average, but they also appear to have greater plasticity, resulting in phylogenetically similar genomes having largely different capabilities. Ultimately, phylogeny is predictive of the diversity and extent of 20 to 33% of all metal uptake systems, suggesting that specialization in metal utilization mostly occurred independently from overall lineage diversification in both SAR11 and Roseobacter. We interpret these results as reflecting relatively recent trace metal niche partitioning in both lineages, suggesting that concentrations and chemical forms of metals in the marine environment are important factors shaping the gene content of marine heterotrophic Alphaproteobacteria of the SAR11 and Roseobacter lineages.     

Long-term changes in heavy metal loadings of Ascophyllum nodosum from the Firth of Clyde,UK

The aim of this work is to describe changes in heavy metal concentrations in Ascophyllum nodosum from 1964 to 1994. Samples were collected from three sites in the Firth of Clyde and analysed for zinc, manganese, iron, copper, lead and nickel. The results were analysed using the multivariate technique Principal Components Analysis (PCA). At the Wemyss Bay site there was a trend towards increasing lead and nickel over the study period, which could not be accounted for by local industrial activity. At the Hunterston site, two groups were well separated by the PCA ordination, based on manganese and zinc concentrations, which corresponded to land reclamation activities in the area. The separation of samples at the Ardneil Bay site correlated well with copper concentration and this corresponded to the termination of industrial effluent with heavy copper loadings. Other changes in industrial effluent were also reflected in the Hunterston and Ardneil Bay site ordinations. The PCA technique highlighted the interplay between metals. The work demonstrated the potential for using multivariate analysis of seaweed metal concentrations in monitoring a posteriori the environmental impact of industrial change.     

Distribution,Fraction, and Ecological Assessment of Heavy Metals in Sediment-Plant System in Mangrove Forest,South China Sea

Overlying water, sediment, rhizosphere sediment and mangrove seedlings in the Futian mangrove forest were analyzed for heavy metals. The results showed that mangrove plant acidified sediment and increased organic matter contents. Except for chromium (Cr), nickel (Ni) and copper (Cu) in Aegiceras corniculatum sediment, heavy metals in all sediments were higher than in overlying water, rhizosphere sediment and mangrove root. Heavy metals in Avicennia marina sediments were higher than other sediments. The lower heavy metal biological concentration factors (BCFs) and translocation factors (TFs) indicated that mangrove plant adopted exclusion strategy. The geo-accumulation index, potential ecological risk index and risk assessment code (RAC) demonstrated that heavy metals have posed a considerable ecological risk, especially for cadmium (Cd). Heavy metals (Cr, Ni, Cu and Cd) mainly existed in the reducible fractions. These findings provide actual heavy metal accumulations in sediment-plant ecosystems in mangrove forest, being important in designing the long-term management and conservation policies for managers of mangrove forest.