EVALUATION of HEAVY METAL AVAILABILITY IN CONTAMINATED SEDIMENTS FROM THE ILHA SOLTEIRA HYDROELECTRIC DAM on THE PARANA RIVER AT ILHA SOLTEIRA, SP, BRAZIL

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Shaping mechanisms of metal specificity in a family of metazoan Metallothioneins: evolutionary differentiation of Mollusc MTs.

Background: The degree of metal binding specificity in metalloproteins such as metallothioneins (MTs) can be crucial for their functional accuracy. Unlike most other animal species, pulmonate molluscs possess homometallic MT isoforms loaded with Cu+ or Cd2+. They have, so far, been obtained as native metal-MT complexes from snail tissues, where they are involved in the metabolism of the metal ion species bound to the respective isoform. However, it has not as yet been discerned if their specific metal occupation is the result of a rigid control of metal availability, or isoform expression programming in the hosting tissues or of structural differences of the respective peptides determining the coordinative options for the different metal ions. In this study, the Roman snail (Helix pomatia) Cu-loaded and Cd-loaded isoforms (HpCuMT and HpCdMT) were used as model molecules in order t o elucidate the biochemical and evolutionary mechanisms permitting pulmonate MTs to achieve specificity for their cognate metal ion. Results: HpCuMT and HpCdMT were recombinantly synthesized in the presence of Cd2+, Zn2+ or Cu2+ and corresponding metal complexes analysed by electrospray mass spectrometry and circular dichroism (CD) and ultra violet-visible (UV-Vis) spectrophotometry. Both MT isoforms were only able to form unique, homometallic and stable complexes (Cd6-HpCdMT and Cu12-HpCuMT) with their cognate metal ions. Yeast complementation assays demonstrated that the two isoforms assumed metal-specific functions, in agreement with their binding preferences, in heterologous eukaryotic environments. In the snail organism, the functional metal specificity of HpCdMT and HpCuMT was contributed by metal-specific transcription programming and cell-specific expression. Sequence elucidation and phylogenetic analysis of MT isoforms from a number of snail species revealed that they possess an unspecific and two metal-specific MT isoforms, whose metal specificity was achieved exclusively by evolutionary modulation of non-cysteine amino acid positions. Conclusion: The Roman snail HpCdMT and HpCuMT isoforms can thus be regarded as prototypes of isoform families that evolved genuine metal-specificity within pulmonate molluscs. Diversification into these isoforms may have been initiated by gene duplication, followed by speciation and selection towards opposite needs for protecting copper-dominated metabolic pathways from nonessential cadmium. The mechanisms enabling these proteins to be metal-specific could also be relevant for other metalloproteins.

Influence of time on the plant availability of Cd, Ni and Zn after sewage sludge has been applied to soils

A pot experiment was conducted to test the hypothesis that decomposition of organic matter in sewage sludge and the consequent formation of dissolved organic compounds (DOC) would lead to an increase in the bioavailability of the heavy metals. Two Brown Earth soils, one with clayey loam texture (CL) and the other a loamy sand (LS) were mixed with sewage sludge at rates equivalent to 0, 10 and 50 1 dry sludge ha(-1) and the pots were sown with ryegrass (Lolium perenne L.). The organic matter content and heavy metal availability assessed with soil extractions with 0.05 M CaCl2 were monitored over a residual time of two years, while plant uptake over one year, after addition of the sludge. It was found that the concentrations of Cd and Ni in both the ryegrass and the soil extracts increased slightly but significantly during the first year. In most cases, this increase was most evident especially at the higher sludge application rate (50 t ha(-1)). However, in the second year metal availability reached a plateau. Zinc concentrations in the ryegrass did not show an increase but the CaCl2 extracts increased during the first year. In contrast, organic matter content decreased rapidly in the first months of the first year and much more slowly in the second (total decrease of 16%). The concentrations of DOC increased significantly in the more organic rich CL soil in the course of two years. The pattern followed by the decomposition of organic matter with time and the production of DOC may provide at least a partial explanation for trend towards increased metal availability.

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50 t ha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50 t ha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50 t ha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability. (c) 2007 Elsevier Ltd. All rights reserved.

Extraction and exchange behavior of metal species in therapeutically applied peat

The binding and availability of metals (Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Zn) in therapeutically applied peat (GroBes Gifhorner Moor, Sassenburg/North Germany) was characterized by means of a versatile extraction approach. Aqueous extracts of peat were obtained by a standardized batch equilibrium procedure using high-purity water (pH 4.5 and 5.0), 0.01 mol l(-1) calcium chloride solution, 0.0 1 mol l(-1) ethylenediaminetetraacetic acid (EDTA) and 0.01 mol l(-1) diethylenetriarnine pentaacetic acid (DTPA) solution as metal extractants. In addition, the availability of peat-bound metal species was kinetically studied by collecting aliquots of extracts after different periods of extraction time (5, 10, 15, 30, 60 and 120 min). Metal determinations were performed by atomic spectrometry methods (AAS, ICP-OES) and dissolved organic matter (DOM) was characterized by UV/Vis measurements at 254 and 436 nm, respectively. of the extractants studied Ca, Mg and Mn were the most available metals, in contrast to peat-bound Fe and Al. The relative standard deviation s(r) of the developed extraction procedures was mostly in the range of 4 to 20%, depending on the metal and its concentration in peat. A pH increase favored the extraction of metals and DOM from peat revealing complex extraction kinetics. Moreover, a competitive exchange between peat-bound metal species and added Cu(II) ions showed that > 100 mg of Cu(II) per 50 g wet peat was necessary to exchange the maximum of bound metals (e.g. 21.8% of Al, 3.9% of Fe, 79.0% of Mn, 81.9% of Sr, related to their total content). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Environmental assessment and biomonitoring of the Twelve Mile Creek watershed, Niagara Peninsula, Ontario

In light of the heavy reliance of the people of the Niagara Peninsula on the T\\'elve Mile Creek (TMC) watershed for recreational activities and for municipal and industrial uses ( e.g., drinking water, shipping and discharge of effluents), it was deemed prudent to assess the envirol1tnental health of the system by analysing the sediments total and exchangeable metal, and TPH contents. The MOEE has set guidelines with limits for the protection and management of aquatic sediments, and the sediments from the headwaters of the TMC have total metal and TPH (subset of O&G) contents well below the lower provincial limits. Areas of environmental concern where total metal contents in sediments, either individually or collectively, exceed the guideline, are the south side of Lake Gibson, the Old WeIland Canal, a segment of TMC just south of the QEW and Martindale Pond. The total metal content of sediments does not in all instances identify areas of biological concern. Instead, it has been found that the exchangeable metal fraction of sediments is a better indicator of metal availability and thus potential accumulation in organisms. In some instances, the exchangeable metal fraction agrees with the total metal fraction defining areas of environmental concern, but it does vary from site to site reflecting the natural variability of the ambient environment. Overall, the exchangeable metal fraction of sediments appears to be a better indicator of anthropogenic pollution and ecosystem impact. A histochemical study of Anodon.ta sp., Elliptio sp. and zebra mussels (Dreissena polyn'101pha) was done in conjunction with passive biomonitoring of zebra and quagga mussels (Dreissena bugensis) from the Twelve Mile Creek watershed and Lake 51. Clair (Jeanette's Creek, Chatham, Ontario). The highest concentrations of divalent metals such as Cu, Ni, Cd, and Zn, and trivalent Al appear to accumulate in gill and kidney tissues. Metal contents of organ tissues in Anodonta sp. vary with size class. Organ metal content varies among size classes, thus requiring consideration of size in biomonitoring studies. Shucked zebra and quagga mussel tissues, exhibited similar size class to Al content trends. In addition they reflected the Al content trends of top (approximately 10 cm) most sediments in the Twelve Mile Creek watershed. Quagga mussels appear to have higher Al concentrations than zebra mussels, thus suggesting that quagga mussels may be better passive biomonitors of AI. Cd content in zebra mussel tissues, seemed to increase with size class trends. This was not demonstrated in the quagga mussel tissues. This suggests that Cd may be regulated by quagga mussels and not by zebra mussels, and that zebra mussels may be better passivebiomonitors of Cd than are quagga mussels. Zebra mussel, quagga mussel, Anodonta sp., and Elliptio sp. were used in a two part, active (translocated) biomonitoring study of the Twelve Mile Creek watershed. There was no statistical difference in death rates between zebra and quagga mussels after 65 days of biomonitoring. However there does appear to be a difference of death rates between sites. Unfortunately the data base did not permit us to differentiate between sites. Relative to Port Colborne Harbour (Port Colborne, Ontario), the Twelve Mile Creek watershed appears to be elevated in bioavailable AI. An area near the terminus of the Twelve Mile Creek appears to be an area of environmental concern since mussels seemed to have accumulated relatively large concentrations of Cd, Zn, and Pb. In addition to possible metal loading from a nearby outfalls, or possible upstream outfalls, road salt runoff from storm sewers may have contributed to metal accumulation through cation exchanges processes. Similar trends in cumulative quagga mussel metal concentrations during the two time periods (65 and 159 days), suggest that quagga mussels may reach equilibrium within 65 days of translocation. Differences in bioaccumulated metal concentrations of the two dreissenid species demonstrate that active biomonitoring studies must use a variety of organisms to adequately assess the environmental situation of specific waterways and/or bodies.

Acúmulo e disponibilidade de cromo, cádmio e chumbo em solos tratados com lodo de esgoto por onze anos consecutivos

The sewage sludge used for agricultural purposes provides many benefits to soil, but it contain harmful elements to environment, that infers in a great attention on its use. The aim of this work was to evaluate the effects of successive applications of sewage sludge on heavy metals accumulation (cadmium, chromium and lead) in samples of soils and corn plants, as well as evaluate the chemicals extractants efficiency in estimate the phyto disponibility of those elements. The experiment was conducted in randomized blocks design in the 2007/08 season, with 4 treatments (0, 5, 10 and 20 Mg ha-1 of sewage sludge) and 5 replicates. It was evaluated: the quantities available of Cd, Cr and Pb in soil by Melich-1, Melich-3 and DTPA extractants; the quantities extracted by corn plants; and the correlation between the disposition and quantities of those metals on whole plants, diagnosis leaves and corn grains. The application of sewage sludge for eleven consecutive years has not showed increase in total quantity nor availability of Cr, Cd and Pb in the evaluated soils. The extractor Melich-1 was the only one that showed significant correlation for availability of Cd, Cr and Pb in soil and corn plants. The correlation of metal availability in soil x leaf diagnosis was significant only for Pb with the Melich-3 and DTPA extractants

Metais pesados do solo após aplicação de biossólido: I - Fracionamento

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Heavy metals in Oxisols amended with biosolids and cropped with maize in a long-term experiment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Atividade enzimática em lodo de esgoto contaminado com cádmio e uso em solo cultivado com sorgo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Adsorção de cádmio em Latossolos sob vegetação de mata nativa e cultivados

Heavy metals are found naturally in soils at low concentrations, but their content may be increased by human activity, making them one of the barriers in management of tropical soils. These chemical elements can be found in the composition of organic and inorganic fertilizers, insecticides, fungicides, mine tailings, and urban waste, and may cause serious damage to the environment and human health. Thus, adsorption studies are essential in assessing the behavior of heavy metals in the soil. The objective of this study was to evaluate the influence of soil chemical, particle size, and mineralogical properties on adsorption of cadmium (Cd), evaluated by Langmuir and Freundlich models, in Latossolos (Oxisols) with or without human activity. Soil samples were collected from the surface layer, 0.00-0.20 m, and chemical, particle size, and mineralogical analyzes were performed. In the adsorption study, concentrations of 0, 5, 25, 50, 100, 200, 300, and 400 mu g L-1 of Cd were used in the form of Cd(NO3)(2). The empirical mathematical models of Langmuir and Freundlich were used for construction of adsorption isotherms. Data were analyzed by means of multivariate statistical techniques, Cluster Analysis and Principal Component Analysis. The data from the adsorption experiment showed a good fit to the Langmuir and Freundlich models. Soils with a lower goethite/hematite ratio and greater cation exchange capacity and pH, showed higher maximum adsorption capacity of Cd.

Denitrification in the Hypolimnion of Permanently Ice-Covered Lake Bonney, Antarctica

The distribution of denitrification was investigated in the hypolimnion of the east and west lobes of permanently ice-covered Lake Bonney, Taylor Valley, Antarctica. Anomalously high concentrations of dissolved inorganic nitrogen (DIN; nitrate, nitrite, ammonium and nitrous oxide) in the oxygen-depleted hypolimnion of the east lobe of the Lake implied that denitrification is or was active in the west, but not in the east lobe. While previous investigations reported no detectable denitrification in the east lobe, we measured active denitrification in samples from both the east and west lobes. In the west lobe, measured denitrification rates exhibited a maximum at the depth of the chemocline and denitrification was not detectable in either the oxic surface waters or in the deep water where nitrate was absent. In the east lobe, denitrification was detected below the chemocline, at the depths where ammonium, nitrate, nitrite and nitrous oxide are all present at anomalously high levels, Trace metal availability was manipulated in incubation experiments in order to determine whether trace metal toxicity in the east lobe could explain the difference in nitrogen cycling between the 2 lobes. There were no consistent stimulatory effects of metal chelators or nutrient addition on the rate of denitrification in either lobe, so that the mechanisms underlying the unusual N cycle of the east lobe remain unknown. We conclude that all the ingredients necessary to allow denitrification to occur are present in the east lobe. However, even though denitrification could be detected under certain conditions in incubations, denitrification is inhibited under the in situ conditions of the lake.