Toxicity of copper excess on the lichen Dermatocarpon luridum: antioxidant enzyme activities

The aim of this study was to investigate the toxicity of copper on the aquatic lichen Dermatocarpon luridum focusing on the activities of some antioxidant enzymes. Investigations were conducted using increasing copper concentrations (0.00, 0.25, 0.50, 0.75 and 1.00 mM CuSO(4) x 5H(2)O) in synthetic freshwater that emulated the major ion compositions of its natural water biota; time course measurement was 0, 3, 6, 12, 24 and 48 h. The copper concentration in thalli increased with its increase in the medium and the duration of treatment. Copper induced lipid peroxidation, measured using the hydroperoxi-conjugated dienes (HPCD) concentration. The decrease in the protein concentrations was similar in thalli exposed to copper concentrations above 0.50 mM and the decrease was twice lower in thalli exposed to 0.25 mM copper. The activities of antioxidant enzymes measured were differently affected by copper excess. For 0.25 mM copper, the activities of SOD (superoxide dismutase) and APX (ascorbate peroxidase) were unchanged when compared with unstressed thalli whereas the CAT (catalase) activity increased and the GR (glutathione reductase) activity decreased. The activities of SOD and APX increased in thalli exposed to concentrations above 0.50mM copper. The CAT activity increased after the first 3h of experiments at these concentrations and then decreased with the duration of treatment at an activity lower than in the unstressed plant. Whereas the APX activity increased, the GR activity similarly decreased for the copper concentration tested whatever the duration of the experiment.     

Simultaneous oxidation of EDTA and reduction of metal ions in mixed Cu(II)/Fe(III)-EDTA system by TiO2 photocatalysis

Both the photooxidation of EDTA and the photoreduction of metal ions in metal-EDTA systems were investigated. EDTA oxidation by TiO(2) photocatalysis occurred sequentially as Cu(II)-EDTA>Cu(II)/Fe(III)-EDTA>Fe(III)-EDTA. For Cu(II)-EDTA, EDTA was completely decomposed after only 60min of irradiation. The rate of EDTA decomposition was directly correlated with the initial Cu(II) concentration in the case of a mixed Cu(II)/Fe(III)-EDTA system. The metal ions in a single metal-EDTA complex were removed following significant decomposition of EDTA. For a mixed Cu(II)/Fe(III)-EDTA system, however, no copper was removed whereas almost all of the iron was removed. The iron and copper species deposited on the TiO(2) surface were identified via EPR and XPS as mixed FeO/Fe(3)O(4) and Cu(0)/Cu(2)O, respectively.     

Elucidation of lead-induced oxidative stress in Talinum triangulare roots by analysis of antioxidant responses and DNA damage at cellular level

Hydroponic experiments were performed with Talinum triangulare (Jacq.) Willd. focusing the root cellular biochemistry with special emphasis on DNA damage, structural, and elemental analyses in Pb(NO₃)₂ exposed with 0, 0.25, 0.5, 0.75, 1.0, and 1.25 mM for 7 days. Lead (Pb) increased reactive oxygen species production, lipid peroxidation, protein oxidation, cell death, and DNA damage and decreased the protein content in a dose-dependent manner. Likewise, a dose-dependent induction of antioxidative enzymes superoxide dismutase and catalase by Pb was evident. Ascorbate peroxidase on the other hand responded biphasically to Pb treatments by showing induction at low (0.25 and 0.50) and repression at high (0.75–1.25 mM) concentrations. The estimation of proline content also indicated a similar biphasic trend. Scanning electron microscope and energy-dispersive X-ray spectroscopy analysis showed that 1.25 mM Pb treatment resulted in ultrastructural modifications in roots and stem tissue that was marked by the change in the elemental profile. The findings pointed to the role of oxidative stress in the underlying Pb phytotoxicity and genotoxicity in T. triangulare.     

土壤中无机钠盐对不同形态Cu含量的影响

采用TESSIER连续提取法研究了不同种类、不同加入量的无机钠盐对土壤中不同形态Cu含量的影响。结果表明,对于可交换态Cu,3种无机钠盐的加入均使其含量减少,其中NaCl的影响最大,4、8g/kg的NaCl分别使其减少了28.13%(质量分数,下同)和50.59%;对于碳酸盐结合态Cu,3种无机钠盐的加入均使其含量增加,其中Na2CO3(8g/kg)对其影响最大;对于铁锰氧化态Cu,Na2SO4和Na2CO3的加入使其含量先升高后降低,NaCl则使其含量降低;有机结合态Cu受Na2SO4和Na2CO3的影响较大,在它们的影响下含量均增加;残渣态Cu在3种无机钠盐的影响下变化幅度均很大,其中4、8g/kg的Na2SO4分别使其含量减少了47.47%和62.21%。     

Destruction of organic pollutants in reusable wastewater using advanced oxidation technology

This work studied the destruction of various M-EDTA complexes and trace organic pollutants in treated reusable wastewater under advanced oxidation using UV irradiation and ozonation. Effect of dosage of hydrogen peroxide and acidity of reaction matrices on oxidation efficiencies were investigated. The rate constant of mineralization presents a decreasing trend as Fe(III)-EDTA > Fe(II)-EDTA > Al(III)-EDTA > Pb(II)-EDTA > Na(I)-EDTA > Zn(II)-EDTA > Cu(II)-EDTA. The mineralization efficiencies using ozone alone are 15%, 40% and 15% for the water samples after reverse osmosis (RO), microfiltration (MF) and superfiltration (SF) processes, respectively. The presence of hydrogen peroxide in photochemical reaction matrixes can effectively enhance the mineralization of organic carbon species. When 150 mg l(-1) of H2O2 was added in the effluents, the mineralization markedly increased to 80%, 92% and 89%, respectively.     

Imidacloprid induced alterations in oxidative stress,biochemical, genotoxic,and immunotoxic biomarkers in non-mammalian model organism Galleria mellonella L. (Lepidoptera: Pyralidae)

Imidacloprid (IMI), a neonicotinoid insecticide, is widely used to control pests in agriculture. We investigated the changes in antioxidant enzyme activities, lipid peroxidation levels, biochemical effects, genotoxic effect, and immunotoxic effect of sublethal doses (0.25, 0.50, 0.75, and 1.00?µg) of IMI at different time periods (24, 48, 72, and 96?h) on a model organism, Galleria mellonella L. The results indicated that there were dose-dependent increases in both antioxidant enzyme activities (SOD and CAT) and MDA levels. Protein content was not affected by IMI at 24th and 48th, whereas it was decreased by the highest dose of IMI (1.00?µg) at 72nd and 96th h. Lipid and carbohydrate contents were reduced with increasing doses of IMI. Micronucleus frequency significantly increased in all IMI doses. All IMI doses caused a significant decrease in THC at 24th, 48th, and 72nd h. Our results can help to illustrate the effects of IMI in target organisms and indirectly may aid to discover potential risk of it on nontarget organisms. Future studies, at molecular levels, will be helpful in understanding the mechanism of action of IMI on these biomarkers.     

Physiological adaptations in the lichens Peltigera rufescens and Cladina arbuscula var. mitis, and the moss Racomitrium lanuginosum to copper-rich substrate

Two lichen species (Peltigera rufescens and Cladina arbuscula subsp. mitis) and one moss species (Racomitrium lanuginosum) growing on a copper mine heaps (probably 200–300 yr old) in the village of Špania dolina (Slovak Republic) were assessed for selected physiological parameters, including composition of assimilation pigments, chlorophyll a fluorescence, soluble proteins and free amino acid content. The lichen C. arbuscula subsp. mitis was collected also at a control locality where total copper concentration in the soil was approximately 3% that of the waste heaps. Concentrations of Al, Co, Cu, Ni, Sb and Zn were highest in thalli of Peltigera, while the moss Racomitrium contained the highest content of Fe and Pb. Thalli of Cladina contained less metals than the cyanolichen Peltigera, and except for Zn metal concentrations in Cladina from the control locality were lower than in thalli of the same species from copper mine heaps. Regardless of the species or locality, the composition of assimilation pigments and chlorophyll a fluorescence showed that the tested lichens and moss were in good physiological condition and adapted to increased copper levels in the soil. There were significantly different amounts of total free amino acids in Peltigera, Cladina and Racomitrium from the Cu-polluted field. However, differences in amount of free amino acids in control, as well as Cu-polluted thalli of Cladina were less pronounced.     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R2 > or = 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10(-4) for Co/PMS and a k value of 10(-3) for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

Assessment of the relationship between total suspended particles and the response of two biological indicators transplanted to an urban area in central Argentina

Samples of the vascular plant Tradescantia pallida and the lichen Usnea amblyoclada were exposed from October 2004 to April 2005 in three sites with different local sources of air pollution in Córdoba city, Argentina. Simultaneous determinations of the ambient levels of total suspended particles were made for each site. Young inflorescenses of T. pallida were collected in November, February and April and the frequency of micronuclei was determined on early tetrads of pollen mother cells. Physiological parameters and the elemental composition of lichen thalli were measured from samples exposed and replaced every month. Significant differences among sampling sites were observed in the frequency of micronuclei measured in T. pallida as well as in many physiological parameters and elements accumulated in lichen thalli. The mass of particulate material as well as the concentration of Ca, Mn, Cu, Zn and Sr was significantly different in different sampling sites, too. These results suggest that in situ biomonitoring using both higher plants and lichens may be of use to characterize air pollution in areas devoid of instrumental monitoring techniques or where it is necessary to explore the distribution of air contaminants at a microscale.     

Lichen response to changes in atmospheric sulphur: isotopic evidence.

In June of 1997, several thalli of the lichen species Alectoria sarmentosa were transplanted from a remote area (Bonavista) to an urban area (St John's) on the island of Newfoundland, Canada. The purpose was to assess the response of these epiphytic lichens to a change in the level of atmospheric sulphur pollution as measured by sulphur concentration and isotopic composition. The dominant source of atmospheric sulphur in the Bonavista area is sea spray, therefore, lichens growing there have relatively high sulphur isotopic compositions and low concentrations (approximately + 15 per/thousand, 250 ppm). Atmospheric sulphur in the St John's area is dominated by anthropogenic sources, primarily oil burning. Lichens in this area have lower isotopic compositions and higher concentrations (approximately + 6 per thousand, 500 ppm). The transplanted lichens were monitored monthly for a period of 1 year. In all experiments the sulphur isotopic composition decreased and the sulphur concentration increased linearly. It is estimated that, within 18 months, transplanted A. sarmentosa would be indistinguishable from the same species naturally growing in the transplant site, both in terms of sulphur concentration and isotopic composition.     

A biological method to monitor early effects of the air pollution caused by the industrial exploitation of geothermal energy

The suitability of a set of ecophysiological parameters, to be used as early warning indicator to detect signs of a worsening environment around geothermal power plants, was tested by comparison with the diversity of epiphytic lichens, a well-established indicator of geothermal air pollution. Samples of the lichen Evernia prunastri were transplanted around a geothermal power plant at Larderello (Tuscany, Italy) and at a control site, and integrity of cell membranes, concentration of chlorophyll a, b and carotenoids, chlorophyll integrity and variations in pH of thalli were measured. The results showed that cell membrane damage, expressed by changes in electrical conductivity, could be used to detect early (exposure periods as short as 1 month) deleterious effects of geothermal air pollution.     

Lead toxicity, defense strategies and associated indicative biomarkers in Talinum triangulare grown hydroponically

Talinum species have been used to investigate a variety of environmental problems for e.g. determination of metal pollution index and total petroleum hydrocarbons in roadside soils, stabilization and reclamation of heavy metals (HMs) in dump sites, removal of HMs from storm water-runoff and green roof leachates. Species of Talinum are popular leaf vegetables having nutrient antinutrient properties. In this study, Talinum triangulare (Jacq.) Willd (Ceylon spinach) grown hydroponically were exposed to different concentrations of lead (Pb) (0, 0.25, 0.5, 0.75, 1.0 and 1.25 mM) to investigate the biomarkers of toxicity and tolerance mechanisms. Relative water content, cell death, photosynthetic pigments, sulphoquinovosyldiacylglycerol (SQDG), anthocyanins, α-tocopherol, malondialdehyde (MDA), reactive oxygen species (ROS) glutathione (GSH and GSSG) and elemental analysis have been investigated. The results showed that Pb in roots and shoots gradually increased as the function of Pb exposure; however Pb concentration in leaves was below detectable level. Chlorophylls and SQDG contents increased at 0.25 mM of Pb treatment in comparison to control at all treated durations, thereafter decreased. Levels of carotenoid, anthocyanins, α-tocopherol, and lipid peroxidation increased in Pb treated plants compared to control. Water content, cells death and elemental analysis suggested the damage of transport system interfering with nutrient transport causing cell death. The present study also explained that Pb imposed indirect oxidative stress in leaves is characterized by decreases in GSH/GSSG ratio with increased doses of Pb treatment. Lead-induced oxidative stress was alleviated by carotenoids, anthocyanins, α-tocopherol and glutathione suggesting that these defense responses as potential biomarkers for detecting Pb toxicity.     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R² ≥ 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10^?4 for Co/PMS and a k value of 10^?3 for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

Elemental composition of Hoh Rainforest Olympic National Park Washington, USA

The concentration, enrichment factor and storage of 27 elements was examined for growing in Olympic National Park, Washington. Most element concentrations changed significantly as the moss aged. Concentrations of copper, zinc, and lead were among the lowest found to date. Crustal enrichment factors indicated many elements were initially derived from atmospheric sources. These data indicate concentrations of heavy metals in remote, unpolluted sites may be considerably lower than initially thought.Mosses have been used to monitor air pollution because they accumulate trace elements and their growth is sensitive to pollutants. and were used to monitor trace element contamination in Europe (Yale and Lloyd 1984, Goodman and Roberts 1971, Lotschert and Wardtner 1982). The older portions of tended to have higher concentrations of copper and zinc than the newer portions. Sweiboda and Kalemba (1981) used and other mosses to monitor the presence of sulfur and flourine. An ecological index of contamination was developed by Le Blanc, et al. (1974) based heavily on the presence and absence of lichen and moss species around a copper mill area in Quebec, Canada. These studies demonstrate that the chemical composition of moss tissues and changes in species abundance are sensitive to atmospheric chemical composition.     

Effect of phosphate addition on the sorption-desorption reaction of selenium in Japanese agricultural soils

Desorption levels of soil-sorbed selenium (Se) were studied by adding phosphate to 22 typical Japanese agricultural soils. Soil-soil solution distribution coefficients of Se (Kd-Se) were measured using a batch process as an index of Se sorption level, adding 75Se as a tracer. After the Kd measurement, extraction of soil-sorbed 75Se with a 0.1 M or 1 M Na2HPO4 solution followed to determine the amount of 75Se desorbed by the phosphate. When the 0.1 M Na2HPO4 solution was used, 18-70% of soil-sorbed Se was extracted (average: 47%). However, when the 1 M Na2HPO4 solution was used, 27-83% of soil-sorbed Se was extracted (average: 57%). The observed 75Se desorption percentage indicated the maximum Se removability by phosphate addition. The desorption percentage of Se with 1 M Na2HPO4 correlated with Kd-Se values, suggesting that the soil sample with higher Kd-Se contained more reactive components for phosphate-sorption than the soil sample with lower Kd-Se. To evaluate the effect of phosphate concentration on the Se sorption, the Kd-Se was measured for two typical soils under different levels of phosphate (0.1-10 mM PO4). The Kd values were decreased by phosphate addition for both soils. The Kd decrease was observed even for just 1 mM PO4. The phosphate addition with 1 mM PO4 is the same level as in P fertilizer applied to paddy fields in Japan. Therefore, it was suggested that Se desorption should occur in Japanese soils due to the phosphate input.     

Susceptibility to acidic precipitation contributes to the decline of the terricolous lichens Cetraria aculeata and Cetraria islandica in central Europe

The effective quantum yield of photochemical energy conversion in photosystem II (Phi2) was shown to be reduced in the terricolous lichens Cetraria aculeata and Cetraria islandica by short-term exposure to aqueous SO2 at pH values occurring in the precipitation of areas with high SO2 pollution. Significant reduction of Phi2 was found at pH相似文献   

Influence of growth form on the accumulation of airborne copper by lichens

Lichens are known to accumulate airborne elements. This characteristic makes them useful as biomonitors of air quality. However, direct correlations of element concentrations in the air with element concentrations in lichen thalli are generally unavailable. The purpose of this study was to quantitatively examine the relationship between concentrations of copper in ambient air samples and thalli of foliose and fruticose lichens. Lichen samples from four sites along an air copper gradient were collected and analyzed. Foliose specimens consistently accumulated more than twice as much copper as fruticose specimens at all four sites. The relationship between copper concentrations in foliose and fruticose lichens and ambient air samples along an airborne copper gradient was examined using a stepwise regression model. An R² value of (0.84) and an F-statistic of (182.5, p<0.001) for the model indicate that variability in lichen copper concentrations between sites is explained by airborne copper concentrations. Based on the regression analysis both foliose and fruticose growth forms appear to accurately predict airborne copper concentrations. A significant interaction between the airborne copper and growth form variables and large differences in the calculated slopes suggests that foliose lichens more efficiently accumulate airborne copper than fruticose lichens.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Euglena gracilis as a model for the study of Cu2+ and Zn2+ toxicity and accumulation in eukaryotic cells

We have observed the effect of copper and zinc on the biology of Euglena gracilis. The cells displayed different sensitivities to these metals, as the apparent LC50 for Cu2+ was 0.22 mM, and for Zn2+ it was 0.88 mM. While Zn2+ was able to increase cell proliferation even at 0.1 mM, the minimal CuCl2 concentration tested (0.02 mM) was sufficient to impair cell division. Higher concentrations of these metals not only inhibited cell division in a concentration-dependent manner, but also interfered with the metabolism of E. gracilis. A higher accumulation of proteins and lipids per cell was observed at the DI50 concentration for metal-treated cells. These results suggest that the test concentration of both metals leads to a failure in completing cell division. Ultrastructural analysis indicated a chloroplast disorganization in copper-treated cells, as well as the presence of electron dense granules with different shapes and sizes inside vacuoles. Microanalysis of these granules indicated an accumulation of copper, thus suggesting a detoxification role played by the vacuoles. These results indicate that E. gracilis is an efficient biological model for the study of metal poisoning in eukaryotic cells. They also indicate that copper and zinc (copper being more poisonous) had an overall toxic effect on E. gracilis and that part of the effect can be ascribed to defects in the structure of chloroplast membranes.     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.