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Heavy metals--geochemical bogey men?

Heavy metals is a loose term usually used to indicate environmentally "bad" metals. It is poorly defined with a multitude of often contradictory definitions based on density, atomic weight, atomic number or other properties of the elements or their compounds. Alternative, scientifically rigorous definitions exist for subgroups of metals and should be used instead.

Chemical Phenomena↗

Adsorption of copper ions onto microwave stabilized heavy metal sludge.

Microwave stabilized heavy metal sludge was used as an adsorbent to remove the copper ions from aqueous solution. The adsorption characteristics of copper on the stabilized-sludge were studied by various models, such as Freundlich and Langmuir isotherm equation. Results show that the pH(zpc) of stabilized-sludge was at 9.2-9.5. Moreover, the adsorption of copper ions onto the stabilized-sludge surface was mainly on account of the heterogeneous surface of the stabilized-sludge. In the dynamic study, the experimental data was fitted to the intraparticle diffusion model, pseudo-first order model and pseudo-second order model. However, the experimental data was only well correlated with pseudo-second order model with the correlation coefficient>0.995. Furthermore, both Freundlich and Langmuir isotherm equations were found to represent the measured adsorption data well. From the Langmuir equation, the adsorption capacity increased from 18 to 28 mg/g as the temperature rose from 15 to 55 degrees C, since this adsorption process was an endothermic reaction. After this adsorption process, copper ions can be concentrated on and in a small bead and recovery efficiently.

Adsorption↗

The study of devitrification processes in heavy-metal fluoride glasses.

Heavy-metal fluoride glasses are very promising optical fiber materials because of their predicted ultralow loss and long transparency range. Although conventional silica fibers have attained their theoretical minimum loss of 0.15 dB/km, fluoride glasses have the potential to yield losses of only 0.001 dB/km. Fluoride glasses also exhibit transparency into mid-IR frequencies, a region inaccessible to silica fibers. However, this group of glasses is very unstable to devitrification during both bulk glass synthesis and fiber-drawing. This instability has limited their commercial exploitation to a small niche market in the laser industry. The ZBLAN glass (53ZrF(4)-20BaF(2)-4LaF(3)-3AlF(3)-20NaF) is the most promising of these materials since its fiber-drawing region lies on the edge, or possibly just outside its crystallization region. It is believed that additional research into understanding the nucleation mechanics involved in the devitrification of fluoride glasses will lead to the development of technology to suppress such nucleation, or at least minimize the associated crystallization temperature region, allowing high optical quality fibers to be produced. It has recently been demonstrated that a microgravity environment can suppress devitrification in ZBLAN glass preform preparation, and that devitrification may be reduced when preparing ZBLAN terrestrially in a containerless facility. It is believed that the role of viscosity is critical in the devitrification mechanism of ZBLAN glass and in determining the optimum fiber-drawing temperature. Unfortunately, viscosity data for fluoride glasses are only available above the melting point and around the glass transition. A piezoelectric viscometer has been developed and is being used to determine the missing viscosity data in the fiber-drawing and crystallization temperature regions. Shear thinning of the glasses and/or the application of hydrostatic pressure on the glasses have been recently proposed to be responsible for devitrification during fiber-drawing at 1 g and in reduced gravity. The study we report here is to explore the extent to which such a proposal is realistic.

Chemical Phenomena↗

Heavy metal nephropathy of rodents.

Heavy metal nephropathy is a pathologic entity of the renal tubular epithelium of rats, evoked by lead, gold, and other heavy metals. It is characterized acutely by coagulative necrosis, subacutely by cortical fibrosis, and chronically by cytomegaly and karyomegaly. Finally, adenomas develop, some of which become malignant.

Adenoma↗

Heavy metal binding capacity (HMBC) of municipal solid waste landfill leachates.

This research describes the use of a toxicity assay for the identification of metal toxicity, bioavailability and heavy metal binding capacity (HMBC) of municipal solid waste (MSW) landfill leachates. MetPLATE, an assay specific for heavy metal toxicity, was used to determine the HMBC of MSW leachates collected from 14 sites in Florida, with a wide range of chemical and physical characteristics. The leachates displayed a low toxicity which was attributed to the site-specific parameters, including, high concentrations of both organic and inorganic ligands. The HMBC test was undertaken to measure the effect of these site-specific parameters on metal toxicity. The potential for MSW leachate to bind and, thus, detoxify heavy metals was investigated with copper, zinc, and mercury. The HMBC values obtained ranged from 3 to 115, 5 to 93 and 4 to 101 for HMBC-Cu+2, HMBC-Zn+2, and HMBC-Hg+2, respectively. Additionally, the high strength leachates displayed the highest binding capacities, although the landfills sampled represented a wide range of characteristics. For comparison, the HMBC values reported with local lake water, Lake Alice and Lake Beverly, and a wastewater treatment plant effluent were all below 3. A partial fractionation of MSW leachate samples from sites 1, 5 and 8, was conducted to further investigate the influence of selected site-specific physico-chemical parameters on metal binding. The fractionation revealed that the HMBC of the leachate samples was heavily influenced by the concentration of solids, organics and hardness.

Binding Sites↗

Kinetics of inhibition in the biodegradation of monoaromatic hydrocarbons in presence of heavy metals.

The toxicity and inhibitory effects of heavy metals such as cadmium, nickel and zinc on alkylbenzene removal were evaluated with a Bacillus strain. The kinetics of alkylbenzene biodegradation with the different heavy metals at various concentrations were modeled using the Andrews equation which yielded a good fit between model and experimental data. Additional experiments undertaken with a Pseudomonas sp. in presence of nickel confirmed a good fit between experimental data and the Andrews model for this strain as well. The heavy metals inhibition constants (Ki) were calculated for different combinations of volatile organic compounds (VOC) and heavy metals. The present approach provides a method for evaluating and quantifying the inhibition effect of heavy metals on the biodegradtion of pollutants by specific microbial strains.

Bacillus↗

Nutritional factors in relation to heavy metal toxicants.

An increased environmental exposure to various toxic heavy metals such as lead, cadmium, or mercury seems to be a fact of 20th-century life. But relatively little attention has been paid to the possible implications of sucy exposure for the nutritional status of humans and animals. This review summarizes the information available concerning the effect of various nutritional factors in resistance to metal toxicants and the effect of heavy metal toxicity on nutritional status. In particular, the following questions are considered: 1) Are there any examples of heavy metal toxicity that are potentiated by a nutritional deficiency? 2) Is there any evidence that nutritional deficiency can be caused by heavy metal toxicity? 3) Is there any proof that heavy metal toxicity can be decreased by an excess intake of nutrients: 4) Is there any proof that heavy metal toxicity can be increased by an excess intake of nutrients? The discussion is focused primarily on studies with animal models but, wherever possible, implications for human health are pointed out.

Animals↗

Cross talk of heat shock and heavy metal regulatory pathways.

Heavy metals induce transcription of human genes including those coding for metallothionein and heat shock protein 70 (HSP70). It has been suggested that these processes are mediated by metal-activated transcription factors, MTF-1 and HSF1, respectively, and are independent of each other. We raised an antibody against human MTF-1 which efficiently supershifts the protein-DNA complex formed by MTF-1 and its cognate binding sequence, MRE. We discovered that this antibody could also supershift complexes formed by HSF1 and its recognition sequence HSE, which suggested the involvement of MTF-1 in these complexes. This supershift was observed for HSF1/HSE complexes induced by Zn, Cd, Ag, and heat shock. Furthermore, overexpression of MTF-1 in HeLa cells markedly reduced metal-induced transcription from the hsp70-1 gene promoter which depends on HSF1. These data indicate that MTF-1 represses HSF1-mediated transcription probably through a direct protein-protein interaction, suggesting a cross talk of two lines of stress-responsive regulatory pathways.

Antibodies↗

Correlation analyses on binding behavior of heavy metals with sediment matrices.

This article presents the amounts of heavy metals bound to the sediment matrices (carbonates, Fe-oxides, Mn-oxides, and organic matter), the correlations between any two heavy-metal binding fractions, and the correlations between sediment matrices and their heavy-metal binding fractions. Data consisted of 313 sets obtained from five main rivers (located in southern Taiwan) were analyzed by statistical methods. Among six heavy metals analyzed (Zn, Cu. Pb, Ni, Cr, and Co), the statistical results show that Zn is primarily bound to organic matter, and Cr is primarily bound to Fe-oxides. Principal component analysis (PCA) and correlation analysis (CA) result in significant correlations between carbonates bound Ni and carbonates bound Cr, Fe-oxides bound Ni and Fe-oxides bound Cr, and Mn-oxides bound Cu and Mn-oxides bound Cr. From linear regression results, the levels of the six heavy metals bound to either organic matter or Fe-oxides is moderately dependent on the contents of organic matter or Fe-oxides, especially true for Cr and Pb. According to slope values of linear regression, Cu and Cr have the highest specific binding amounts (SBA) to organic matter and Fe-oxides, respectively. A significant correlation between organic matter and organically bound heavy metals implied that organic matter contained in the sediments of the Potzu river and the Yenshui river can be adequately used as a normalizing agent. However, the six heavy metals bound to either carbonates or Mn-oxides do not correlate with carbonates or Mn-oxides. The obtained results also imply that competitions of various sediment phases in association with heavy metals occur, and organic matter and Fe-oxides are more accessible to heavy metals than other sediment phases.

Binding Sites↗

A novel histidine-rich CPx-ATPase from the filamentous cyanobacterium Oscillatoria brevis related to multiple-heavy-metal cotolerance.

A novel gene related to heavy-metal transport was cloned and identified from the filamentous cyanobacterium Oscillatoria brevis. Sequence analysis of the gene (the Bxa1 gene) showed that its product possessed high homology with heavy-metal transport CPx-ATPases. The CPC motif, which is proposed to form putative cation transduction channel, was found in the sixth transmembrane helix. However, instead of the CXXC motif that is present in the N termini of most metal transport CPx-ATPases, Bxa1 contains a unique Cys-Cys (CC) sequence element and histidine-rich motifs as a putative metal binding site. Northern blotting and real-time quantitative reverse transcription-PCR showed that expression of Bxa1 mRNA was induced in vivo by both monovalent (Cu(+) and Ag(+)) and divalent (Zn(2+) and Cd(2+)) heavy-metal ions at similar levels. Experiments on heavy-metal tolerance in Escherichia coli with recombinant Bxa1 demonstrated that Bxa1 conferred resistance to both monovalent and divalent heavy metals. This is the first report of a CPx-ATPase responsive to both monovalent and divalent heavy metals.

Adenosine Triphosphatases↗

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.

Acid Rain↗

The Drosophila homolog of mammalian zinc finger factor MTF-1 activates transcription in response to heavy metals.

Metallothioneins (MTs) are short, cysteine-rich proteins for heavy metal homeostasis and detoxification; they bind a variety of heavy metals and also act as radical scavengers. Transcription of mammalian MT genes is activated by heavy metal load via the metal-responsive transcription factor 1 (MTF-1), an essential zinc finger protein whose elimination in mice leads to embryonic lethality due to liver decay. Here we characterize the Drosophila homolog of vertebrate MTF-1 (dMTF-1), a 791-amino-acid protein which is most similar to its mammalian counterpart in the DNA-binding zinc finger region. Like mammalian MTF-1, dMTF-1 binds to conserved metal-responsive promoter elements (MREs) and requires zinc for DNA binding, yet some aspects of heavy metal regulation have also been subject to divergent evolution between Drosophila and mammals. dMTF-1, unlike mammalian MTF-1, is resistant to low pH (6 to 6.5). Furthermore, mammalian MT genes are activated best by zinc and cadmium, whereas in Drosophila cells, cadmium and copper are more potent inducers than zinc. The latter species difference is most likely due to aspects of heavy metal metabolism other than MTF-1, since in transfected mammalian cells, dMTF-1 responds to zinc like mammalian MTF-1. Heavy metal induction of both Drosophila MTs is abolished by double-stranded RNA interference: small amounts of cotransfected double-stranded RNA of dMTF-1 but not of unrelated control RNA inhibit the response to both the endogenous dMTF-1 and transfected dMTF-1. These data underline an important role for dMTF-1 in MT gene regulation and thus heavy metal homeostasis.

Amino Acid Sequence↗

Arbuscular mycorrhiza and heavy metal tolerance.

Arbuscular mycorrhizal fungi (AMF) have repeatedly been demonstrated to alleviate heavy metal stress of plants. The current manuscript summarizes results obtained to date on the colonization of plants by AMF in heavy metal soils, the depositions of heavy metals in plant and fungal structures and the potential to use AMF-plant combinations in phytoremediation, with emphasis on pennycresses (Thlaspi ssp.). The focus of this manuscript is to describe and discuss studies on the expression of genes in plants and fungi under heavy metal stress. The summary is followed by data on differential gene expression in extraradical mycelia (ERM) of in vitro cultured Glomus intraradices Sy167 supplemented with different heavy metals (Cd, Cu or Zn). The expression of several genes encoding proteins potentially involved in heavy metal tolerance varied in their response to different heavy metals. Such proteins included a Zn transporter, a metallothionein, a 90 kD heat shock protein and a glutathione S-transferase (all assignments of protein function are putative). Studies on the expression of the selected genes were also performed with roots of Medicago truncatula grown in either a natural, Zn-rich heavy metal "Breinigerberg" soil or in a non-polluted soil supplemented with 100 microM ZnSO(4). The transcript levels of the genes analyzed were enhanced up to eight fold in roots grown in the heavy metal-containing soils. The data obtained demonstrate the heavy metal-dependent expression of different AMF genes in the intra- and extraradical mycelium. The distinct induction of genes coding for proteins possibly involved in the alleviation of damage caused by reactive oxygen species (a 90 kD heat shock protein and a glutathione S-transferase) might indicate that heavy metal-derived oxidative stress is the primary concern of the fungal partner in the symbiosis.

Biodegradation, Environmental↗

Heavy metals in plants and phytoremediation.

GOAL, SCOPE AND BACKGROUND: In some cases, soil, water and food are heavily polluted by heavy metals in China. To use plants to remediate heavy metal pollution would be an effective technique in pollution control. The accumulation of heavy metals in plants and the role of plants in removing pollutants should be understood in order to implement phytoremediation, which makes use of plants to extract, transfer and stabilize heavy metals from soil and water. METHODS: The information has been compiled from Chinese publications stemming mostly from the last decade, to show the research results on heavy metals in plants and the role of plants in controlling heavy metal pollution, and to provide a general outlook of phytoremediation in China. Related references from scientific journals and university journals are searched and summarized in sections concerning the accumulation of heavy metals in plants, plants for heavy metal purification and phytoremediation techniques. RESULTS AND DISCUSSION: Plants can take up heavy metals by their roots, or even via their stems and leaves, and accumulate them in their organs. Plants take up elements selectively. Accumulation and distribution of heavy metals in the plant depends on the plant species, element species, chemical and bioavailiability, redox, pH, cation exchange capacity, dissolved oxygen, temperature and secretion of roots. Plants are employed in the decontamination of heavy metals from polluted water and have demonstrated high performances in treating mineral tailing water and industrial effluents. The purification capacity of heavy metals by plants are affected by several factors, such as the concentration of the heavy metals, species of elements, plant species, exposure duration, temperature and pH. CONCLUSIONS: Phytoremediation, which makes use of vegetation to remove, detoxify, or stabilize persistent pollutants, is a green and environmentally-friendly tool for cleaning polluted soil and water. The advantage of high biomass productive and easy disposal makes plants most useful to remediate heavy metals on site. RECOMMENDATIONS AND OUTLOOK: Based on knowledge of the heavy metal accumulation in plants, it is possible to select those species of crops and pasturage herbs, which accumulate fewer heavy metals, for food cultivation and fodder for animals; and to select those hyperaccumulation species for extracting heavy metals from soil and water. Studies on the mechanisms and application of hyperaccumulation are necessary in China for developing phytoremediation.

Biodegradation, Environmental↗

Emissions of heavy metals into river basins of Germany.

The input of seven heavy metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) into the large river basins of Germany via various point and diffuse pathways were estimated for the period of 1985 through 2000. To quantify the emissions via point sources a nationwide survey on heavy metal data of municipal wastewater treatment plants and industrial direct discharges was carried out. The input via diffuse pathways was calculated using an adapted version of the model MONERIS. This model accounts for the significant transport processes, and it includes a Geographical Information System (GIS) that provides digital maps as well as extensive statistical information. For a comparison of the calculated heavy metal emission with the measured heavy metal load at monitoring stations the losses of heavy metals due to retention processes within the river systems have to be considered. Therefore heavy metal retention was calculated according to the retention functions given by Vink and Behrendt. For the large river basins a good correspondence could be found between estimated and measured heavy metal loads in rivers. The total emission into the North Sea decreased for each metal during the period of 1986 to 2000. The reduction varies between 87% for Hg and 41% for Ni mainly caused by the decline via point sources. Today's emissions of heavy metals into river basins of Germany are dominated by the input via diffuse pathways. The most important diffuse emission pathways are "paved urban areas" and "erosion".

Geographic Information Systems↗

The level of jasmonic acid in Arabidopsis thaliana and Phaseolus coccineus plants under heavy metal stress.

The effect of heavy metal stress as a potent abiotic elicitor for triggering an accumulation of jasmonic acid (JA) was investigated. Copper and cadmium in in vivo conditions induced accumulation of jasmonates in mature leaves of Arabidopsis thaliana and in young and oldest Phaseolus coccineus plants. The dynamics of jasmonate accumulation showed a biphasic character in both plants. In the first phase, after 7 (A. thaliana) or 14h (P. coccineus) of exposure to Cu or Cd, a rapid increase of JA level occurred, followed by a rapid decrease observed during 7 successive hours. In the next phase, a repeated but slow increase of JA content occurred. The heavy metal stress induced in particular a more stable (3R,7R) form of jasmonates. These results indicate that JA is connected with the mechanism of toxic action of both heavy metals in plants, differentially reacting to exogenous JA and possessing variable dynamics depending on the plants studied as well as their growth stage.

Arabidopsis↗

The significance of amino acids and amino acid-derived molecules in plant responses and adaptation to heavy metal stress.

Plants exposed to heavy metals accumulate an array of metabolites, some to high millimolar concentrations. This review deals with N-containing metabolites frequently preferentially synthesized under heavy metal stress such as Cd, Cu, Ni, and Zn. Special focus is given to proline, but certain other amino acids and oligopeptides, as well as betaine, polyamines, and nicotianamine are also addressed. Particularly for proline a large body of data suggests significant beneficial functions under metal stress. In general, the molecules have three major functions, namely metal binding, antioxidant defence, and signalling. Strong correlative and mechanistic experimental evidence, including work with transgenic plants and algae, has been provided that indicates the involvement of metal-induced proline in metal stress defence. Histidine, other amino acids and particularly phytochelatins and glutathione play a role in metal binding, while polyamines function as signalling molecules and antioxidants. Their accumulation needs to be considered as active response and not as consequence of metabolic dys-regulation.

Acclimatization↗

Megalin mediates renal uptake of heavy metal metallothionein complexes.

Although several heavy metal toxins are delivered to the kidney on the carrier protein metallothionein (MT), uncertainty as to how MT enters proximal tubular cells limits treatment strategies. Prompted by reports that MT-I interferes with renal uptake of the megalin ligand beta(2)-microglobulin in conscious rats, we tested the hypothesis that megalin binds MT and mediates its uptake. Three lines of evidence suggest that binding of MT to megalin is critical in renal proximal tubular uptake of MT-bound heavy metals. First, MT binds megalin, but not cubilin, in direct surface plasmon resonance studies. Binding of MT occurs at a single site with a K(d) approximately 10(-4) and, as with other megalin ligands, depends on divalent cations. Second, antisera and various known megalin ligands inhibit the uptake of fluorescently labeled MT in model cell systems. Anti-megalin antisera, but not control sera, displace >90% bound MT from rat renal brush-border membranes. Megalin ligands including beta(2)-microglobulin and also recombinant MT fragments compete for uptake by megalin-expressing rat yolk sac BN-16 cells. Third, megalin and fluorescently labeled MT colocalize in BN-16 cells, as shown by fluorescent microscopic techniques. Follow-up surface plasmon resonance and flow cytometry studies using overlapping MT peptides and recombinant MT fragments identify the hinge SCKKSCC region of MT as a critical site for megalin binding. These findings suggest that disruption of the SCKKSCC motif can inhibit proximal tubular MT uptake and thereby eliminate much of the renal accumulation and toxicity of heavy metals such as cadmium, gold, copper, and cisplatinum.

Amino Acid Sequence↗