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Remediation of heavy metal polluted sediment by suspension and solid-bed leaching: estimate of metal removal efficiency.

Remediation of heavy metal polluted sediment by extracting the metals with sulfuric acid can be performed as follows: abiotic suspension leaching, microbial suspension leaching, abiotic solid-bed leaching, and microbial solid-bed leaching. Abiotic leaching means that the acid is directly added, while microbial leaching means that the acid is generated from sulfur by microbes (bioleaching). These four principles were compared to each other with special emphasis on the effectiveness of metal solubilization and metal removal by subsequent washing. Abiotic suspension leaching was fastest, but suspending the solids exhibits some disadvantages (low solid content, costly reactors, permanent input of energy, high water consumption, special equipment required for solid separation, large amounts of waste water, sediment properties hinder reuse), which prevent suspension leaching in practice. Abiotic solid-bed leaching implies the supply of acid by percolating water which proceeds slowly due to a limited bed permeability. Microbial solid-bed leaching means the generation of acid within the bed and has been proven to be the only principle applicable to practice. Metal removal from leached sediment requires washing with water. Washing of solid beds was much more effective than washing of suspended sediment. The kinetics of metal removal from solid beds 0.3, 0.6 or 1.2m in height were similar; when using a percolation flow of 20lm(-2)h(-1), the removal of 98% of the mobile metals lasted 57-61h and required 8.5, 4.2 or 2.3lkg(-1) water. This means, the higher the solid bed, the lower the sediment-mass-specific demand for time and water.

Bacteria↗

Modelling the extra and intracellular uptake and discharge of heavy metals in Fontinalis antipyretica transplanted along a heavy metal and pH contamination gradient.

Samples of the aquatic bryophyte Fontinalis antipyretica Hedw. were transplanted to different sites with the aim of characterizing the kinetics of the uptake and discharge of heavy metals in the extra and intracellular compartments. The accumulation of metals in extracellular compartments, characterized by an initial rapid accumulation, then a gradual slowing down over time, fitted perfectly to a Michaelis-Menten model. The discharge of metals from the same compartment followed an inverse linear model or an inverse Michaelis-Menten model, depending on the metal. In intracellular sites both uptake and discharge occurred more slowly and progressively, following a linear model. We also observed that the acidity of the environment greatly affected metal accumulation in extracellular sites, even when the metals were present at relatively high concentrations, whereas the uptake of metals within cells was much less affected by pH.

Aluminum↗

Modelling trace metal partitioning in forest floors of northern soils near metal smelters.

Trace metal (TM) mobility and toxicity varies with changing soil conditions. Geochemical models can account for the influence of soil characteristics on TM behaviour. We tested the effectiveness of the Stockholm humic model (SHM), and the NICA-Donnan model (NDM) to estimate partitioning coefficients (logKd) in 26 forest floor horizons of podzolic soils enriched in trace metals from deposition by metal smelters. We wanted to know if a consistent approach could be applied to model metal partitioning in forest floors without optimizing each individual soil. When optimized, the SHM reproduced the partitioning of Cd, Cu and Zn but not Pb. It was necessary to revise the affinity constants for the NDM to simultaneously simulate the partitioning of the four metals. Revised affinity constants for the NDM model based on a fixed definition of soil organic carbon, i.e., a fixed ratio of fulvic and humic acids per unit carbon, reproduced metal partitioning more effectively in an independent data set of 16 soils than the use of generic affinity constants available for these models. From the perspective of the applicability of these models to risk assessment, this result suggests geochemical models using affinity constants that have been verified and/or modified against multiple soils from a region can provide good estimates of metal partitioning on a regional scale.

Adsorption↗

Relative contribution of food and water to 27 metals and metalloids accumulated by caged Hyalella azteca in two rivers affected by metal mining.

Hyalella were caged at three sites in each of the two rivers for 17 days. Food added to the cages consisted of plant and detrital material collected from the same, or other, sites. Concentrations of some metals in Hyalella (e.g., Cd and Cu), but not others (e.g., Se), appeared to reach steady-state within 5 days in one of the rivers. Metal accumulation was minimal by day 5 in the other river, possibly due to the very low temperatures in this river for the first part of the exposure period. Both analysis of variance and analysis of covariance, using site as a categorical variable and metal in food as either a categorical or continuous variable, indicated that Cd, Cu and Se were the only metals for which concentration in food had a significant effect on concentration in Hyalella. Nevertheless, water was still a major source for these metals as well. Other metals which varied by over fivefold in food but for which concentration in food had no effect on concentration in Hyalella included Ag, As, Bi, Sb, U and Zn. Concentrations of the remaining metals varied less than fourfold in food, making it difficult to determine if these were accumulated from food.

Amphipoda↗

Signaling by carcinogenic metals and metal-induced reactive oxygen species.

Epidemiological data indicate that exposure to metal and metalloid species, including arsenic(III), chromium(VI), and nickel(II), increases the risk of cancer, particularly of the lung and skin. Alterations in normal signal transduction as a result of exposure to carcinogenic metals, and to metal-catalyzed reactive oxygen species (ROS) formation, appear to play an important role in the etiology of metal-induced carcinogenesis. Signaling components affected by metals include growth factor receptors, G-proteins, MAP kinases, and nuclear transcription factors. This article reviews current literature on the effects of carcinogenic metals and metal-induced ROS on cancer-related signaling pathways. In addition, the mechanisms by which those changes occur, and the role of those changes in carcinogenesis are discussed.

Animals↗

Elastohydrodynamic lubrication analysis of metal-on-metal hip-resurfacing prostheses.

The elastohydrodynamic lubrication analysis was carried out in this study for a typical metal-on-metal hip-resurfacing prosthesis under a simple steady-state rotation. Both the Reynolds equation and the elasticity equation were coupled and solved numerically by the finite difference method. The finite element method was used to determine the elastic deformation of both the femoral and the acetabular components required for the lubrication analysis. The effect of the radial clearance between the femoral head and the acetabular cup on the predicted film thickness and pressure distribution was investigated. The predicted minimum lubricating film thickness was found to compare favourably with the prediction using the Hamrock and Dowson [J. Lubrication Technol. 100 (1978) 236] formula based on the assumption of ball-on-plane semi-infinite solids. This implies that the non-metallic materials such as bone and cement underlying the metallic components have a small effect on the predicted lubrication performance for the particular metal-on-metal hip-resurfacing prosthesis considered in this study. Under realistic physiological walking conditions, a decrease in the radial clearance from 150 to 50 microm resulted in a 137% increase in the predicted minimum film thickness from 19 to 45 nm. Consequently, given a surface roughness of 0.01 microm for both the metallic femoral and acetabular bearing surfaces, the predicted mixed lubrication regime for the larger clearance was changed to a full fluid film lubrication regime for the smaller clearance. This clearly highlighted the importance of the design and manufacturing parameters on the tribological performance of these hard-on-hard hip prostheses.

Algorithms↗

An investigation of new metal framework design for metal ceramic restorations.

STATEMENT OF PROBLEM: Metal ceramic restorations have been implicated in the discoloration of associated gingival tissues. Attempts to remedy this by altering the design of the metal frameworks for such restorations may lead to unacceptable decreases in fracture resistance. PURPOSE: This study evaluated a new metal framework design for metal-ceramic restorations. MATERIAL AND METHODS: Twenty artificial crowns were fabricated with various degrees of facial metal reduction; 0, 1, 2, and 3 mm. The study was conducted in two parts. The first part evaluated changes in light transmission into adjacent root tissue. A light box was fabricated so sample crowns could be illuminated on a mounted natural tooth. The root of the tooth remained outside the light box, and the light transmitted through the crowns into root tissue was measured with a light meter. The second part of the study evaluated changes in fracture strength. The sample crowns were subjected to a vertical load until fracture with use of an Instron machine at a crosshead speed of 1 mm per minute. The load at fracture was recorded. RESULTS: Results indicated a statistically significant increase in light transmission with 1 mm framework reduction or greater, and fracture strengths did not decrease with up to 1 mm of framework reduction. A 1 mm facial axial reduction of the metal framework may be indicated for anterior metal-ceramic restorations.

Analysis of Variance↗

[Mechanisms of damage to metal-on-polyethylene articulating surfaces of total hip prostheses: influence of intra-articulate migration of metallic debris].

PURPOSE OF THE STUDY: The objective of this work was to identify the mechanisms leading to deterioration of the polyethylene acetabular surface in total hip prostheses. MATERIAL AND METHODS: We conducted an in vivo analysis of damage caused to articulating surfaces of metal-on-polyethylene total hip prostheses. This analysis was performed on three of the 45 explants of Harris-Galante prostheses available to use from our series of 1480 implantations performed between 1985 and 1996. These three pieces were selected because large-sized fibers of metallic debris were identified on the polyethylene surface and because the explants had been performed for reasons other than loosening in aseptic patients. Macroscopic examination was combined with scan electron microscopy to analyze morphological changes. RESULTS: We found that identical damage could be observed on the polyethylene explants despite the different sizes of the metallic heads and different metal-on-polyethylene combinations. Our analysis confirmed the deleterious effect of metallic foreign bodies trapped in contact with the articulate surfaces. These foreign bodies resulted in one case from rupture of a multifilament wire used for the trochanteric fixation and in two cases from the surfacing of the non-cemented Harris-Galante cups. The microscopic analysis demonstrated several successive localizations of the foreign bodies on the polyethylene surface before becoming deeply encrusted in the polyethylene where they deteriorated the femoral head surface (rough) and wore the polyethylene surface (abrasion). When the fibers came from the surfacing of the Harris-Galante cups, the metallic debris remained unrecognized during the revision procedure and were only identified later during the systematic examination of prosthetic explants. DISCUSSION AND CONCLUSION: These findings emphasize the importance of quality surface treatments for non-cemented prostheses and argue in favor of particular precautions during operative manipulation of these components. A systematic analysis of the prosthetic explants is advisable, particularly for components explanted because of wear or unexplained osteolysis. Use of multifilament trochanteric wires should be avoided because rupture raises the risk of intra-articulate migration of metallic debris. If the prosthesis involves a polyethylene acetabular surface, ceramic heads should be preferred to improve resistance to abrasion, particularly to limit the deleterious effect of a third body.

Adult↗

Heavy metals in human primary teeth: some factors influencing the metal concentrations.

Human primary teeth have been used as indicators of heavy metal exposure for several decades, but the knowledge about the influence of factors such as tooth type and the presence of caries and roots on metal concentrations is limited. Samples of tooth powder from more than 1200 Norwegian primary teeth without fillings have been analyzed for lead, zinc and cadmium content, and 554 of them for mercury. The material represents all groups of tooth types (incisors, canines and molars), carious and non-carious teeth, and teeth with and without roots. Here we investigate how tooth group and the presence of caries and roots are related to metal concentrations in the teeth. We find that carious teeth have higher metal concentrations than non-carious teeth; the difference was statistically significant for lead, mercury and zinc. Teeth with roots have higher lead and zinc concentrations than teeth without roots. We find differences in metal concentrations between the tooth groups for lead, mercury and zinc. Significant, positive correlations are found between lead and the three other metals and between mercury and zinc. We conclude that metal concentrations in primary teeth are affected by the presence of caries and roots and by tooth group.

Cuspid↗

Kinetic analysis of metal binding to the amino-terminal domain of ZntA by monitoring metal-thiolate charge-transfer complexes.

ZntA, a P(1B)-ATPase transporter from Escherichia coli, mediates resistance specifically to Pb(2+), Zn(2+), and Cd(2+) by active efflux. ZntA has a hydrophilic N-terminal domain that binds one metal ion. This domain, approximately 120 residues long, contains the GXXCXXC motif that has been shown to be the binding site for metal ions such as Cu(+) and Zn(2+) in P(1B)-type ATPases, and an additional cysteine-rich motif, CCCDGAC. We report here that binding of Pb(2+) and Cd(2+) to this domain produces changes in the absorbance spectrum in the 250-400 nm range indicative of metal-thiolate charge-transfer complexes. The spectral changes indicate that only two cysteines are ligands to Cd(2+), but three or more cysteines are involved in binding Pb(2+); this confirms earlier results that the GXXCXXC sequence is not sufficient to bind Pb(2+), which likely involves residues from the CCCDGAC motif. The absorbance changes were used to measure metal binding kinetics of the N-terminal domain using stopped-flow techniques. Binding was described by simple second-order kinetics with a rate constant, k(on), of approximately 10(6)-10(7) M(-)(1) s(-)(1), at 4 degrees C. The activation energy of binding is similar for both Pb(2+) and Cd(2+); however, the entropy change is greater for Pb(2+). The surprisingly large rate constant for metal binding to the N-terminal domain of ZntA, compared to its low turnover rate, indicates that this step is not rate limiting in the overall transport mechanism. These results, in conjunction with earlier studies, suggest that metal binding to the transmembrane site in ZntA or metal release from the transporter is the slow step in the reaction cycle.

Adenosine Triphosphatases↗

Methodology for predicting OEL from rodent LD50 values for metals and metallic compounds.

The relationship between the occupational exposure limits (OEL) and the lethal dose 50 (LD50) values of rats or mice for metals and metallic compounds was statistically analyzed by a stepwise multivariate regression method. The OEL values were predicted from LD50 values and metallic compensation coefficients (MCC), which were developed as the regression coefficients of dummy variables that represented the metallic element contained in the substance of interest. The value of the MCC indicated the extent of the adverse health effects of the metal in the substance. Smaller values of the MCC were assigned to metals that would have the more severe adverse health effects, such as carcinogenesis, while larger values were given to the less toxic metals. The Health Index (HI) based on the OEL values was proposed as a convenient measure of the toxicity of industrial products. The prediction method could be applied to toxicity risk assessments by using the HI when a designer of consumer products wants to use substances for which OEL values have not been determined. Two case studies were conducted to estimate the potential toxicity of materials used in solders and in rechargeable batteries.

Animals↗

Metal metabolism in the red alga Cyanidium caldarium and its relationship to metal tolerance.

The unicellular red alga Cyanidium caldarium is tolerant to high levels of various metal ions. Cells of this alga cultured with divalent metal ions at 5 mM contained an elevated concentration of each metal, with the highest level for Zn followed by Mn > Ni > Cu. This order is in fair agreement with the toxicity levels reported previously, with the exception of Mn, which shows a toxicity level comparable to that of Ni. Transmission electron microscopy indicated the presence of electron-dense bodies in the algal cells, and elemental analysis by energy dispersive X-ray spectrometry showed high levels of Fe and P in these bodies. Accumulation of Zn was found in these particles in Zn-treated algal cells, whereas no such deposition was found for Cu, Ni, or Mn in cells treated with the respective metals. Although trapping of Zn in the intracellular bodies may contribute to reduction of metal activity in the cells, this effect can be overcome by high intracellular levels of Zn that result in a high degree of toxicity. The correlation between intracellular concentration and toxic levels of metal ions implies that the reduced incorporation of the metals is a major detoxification mechanism in this alga.

Electron Spin Resonance Spectroscopy↗

Dextran templating for the synthesis of metallic and metal oxide sponges.

Silver or gold-containing porous frameworks have been used extensively in catalysis, electrochemistry, heat dissipation and biofiltration. These materials are often prepared by thermal reduction of metal-ion-impregnated porous insoluble supports (such as alumina and pumice), and have surface areas of about 1 m(2) g(-1), which is typically higher than that obtained for pure metal powders or foils prepared electrolytically or by infiltration and thermal decomposition of insoluble cellulose supports. Starch gels have been used in association with zeolite nanoparticles to produce porous inorganic materials with structural hierarchy, but the use of soft sacrificial templates in the synthesis of metallic sponges has not been investigated. Here we demonstrate that self-supporting macroporous frameworks of silver, gold and copper oxide, as well as composites of silver/copper oxide or silver/titania can be routinely prepared by heating metal-salt-containing pastes of the polysaccharide, dextran, to temperatures between 500 and 900 degrees C. Magnetic sponges were similarly prepared by replacing the metal salt precursor with preformed iron oxide (magnetite) nanoparticles. The use of dextran as a sacrificial template for the fabrication of metallic and metal oxide sponges should have significant benefits over existing technologies because the method is facile, inexpensive, environmentally benign, and amenable to scale-up and processing.

Copper↗

Determination of metal-humic complexes, free metal ions and total concentrations in natural waters.

A comparison of two systems for the quantitation of metal-humic complexes and free metal ions, consisting of the separation by coupled ion exchange columns followed by detection by inductively coupled plasma mass spectrometry or cold vapour atomic fluorescence spectrometry, is presented. The systems evaluated comprised the serially coupled anion and cation exchangers, Sephadex A-25/Chelex 100 and Dowex 1X8/Chelamine Metalfix. Separation and preconcentration of the species studied were accomplished with both systems, elution being carried out using 2 M HNO3. Total concentrations, metal-humic complex fractions and free metal ion fractions of Al, Ba, Cd, Co, Cu, Fe, Hg, Mn, Pb, Sr, U and Zn in nine natural waters were determined. Statistical evaluation of the data from the two cation exchange materials, including results for additional elements, showed better precision (for Al, Ba, Cr, Cu and Mo) and higher recoveries (Al, Ba, Cd, Fe, Sr and Zn) for Chelex 100 than Chelamine Metalfix for free metal ions. On the other hand, Chelamine Metalfix recovered a significantly greater amount of Ni. The amounts of metal-humic complexes were compared with modelled distributions of these species, and one advantage of the preferred Sephadex A-25/Chelex 100 system is that the elements studied are all correctly classified with respect to their binding strengths to humic substances, which is not the case with the Dowex 1X8/Chelamine Metalfix pair. With the preferred system, metal-humic complexes can be reliably determined, as indicated by the results of equilibrium speciation modelling. However, comparison with the total concentrations showed statistically significant, non-quantitative recoveries of Al, Cu, Hg, Mn, U and Zn from some samples. Thus a combination of speciation and total concentration measurements is required to obtain a complete representation of the distribution of trace elements in natural waters.

Environmental Monitoring↗

Visible absorption spectra of metal-catecholate and metal-tironate complexes.

Interactions between metals and catechol (1,2-dihydroxybenzene) or other ortho-dihydroxy moieties are being found in an increasing number of biological systems with functions ranging from metal ion internalization to biomaterial synthesis. Although metal-catecholate interactions have been studied in the past, we present the first systematic study of an array of these compounds, all prepared under identical conditions. We report the ultraviolet-visible absorption (UV-vis) spectra for catecholate and tironate complexes of the first row transition elements. Generation and identification of these species were accomplished by preparing aqueous solutions with varied ligand:metal ratios and subsequently titrating with base (NaOH). Controlled ligand deprotonation and metal binding resulted in sequential formation of complexes with one, two, and sometimes three catecholate or tironate ligands bound to a metal ion. We prepared the mono-, bis- and tris-catecholates and -tironates of Fe(3+), V(3+), V(4+)and Mn(3+), the mono- and bis-catecholates and -tironates of Cu(2+), Co(2+), Ni(2+), Zn(2+), Cr(2+) and Mn(2+), and several Ti(4+) and Cr(3+) species. The UV-vis spectra of each complex are described, some of which have not been reported previously. These data can now be applied to characterization of biological metal-catecholate systems.

Catechols↗

Catalysis of the ethanolysis of aryl methyl phenyl phosphinate esters by alkali metal ions: transition state structures for uncatalyzed and metal ion-catalyzed reactions.

This paper reports on a spectrophotometric kinetic study of the effects of the alkali metal ions Li+ and K+ on the ethanolysis of the aryl methyl phenyl phosphinate esters 3a-f in anhydrous ethanol at 25 degrees C. Rate data obtained in the absence and presence of complexing agents afford the second-order rate constants for the reaction of free ethoxide (k(EtO-)) and metal ion-ethoxide ion pairs (k(MOEt)). The sequence k(EtO-) < k(MOEt) is established for all the substrates, contrary to the generally observed reactivity order in nucleophilic substitution processes. The quantities deltaG(ip), deltaG(ts) and DeltaG(cat), which quantify the observed alkali metal ion effect in terms of transition state stabilization through chelation of the metal ion, give the order deltaG(ts) > deltaG(ip) for Li+ and K+. Hammett plots show significantly better correlation of rates with sigma and sigma(o) substituent constants than with sigma-, yielding moderately large rho(rho(o)) values that are consistent with a stepwise mechanism in which formation of a pentacoordinate (phosphorane) intermediate is the rate-limiting step. The range of the values of the selectivity parameter, rho(n) (= rho]/rho(eq)), 1.3-1.6, obtained for the uncatalyzed and alkali metal ion catalyzed reactions indicates that there is no significant perturbation of the transition state (TS) structure upon chelation of the metal ions. This finding is relevant to the mechanism of enzymatic phosphoryl transfer involving metal ion co-factors. The present results enable one to compare structural effects for nucleophilic reactions of several series of organophosphorus substrates. It is shown that the order of reactivity of the substrates: 4-nitrophenyl dimethyl phosphinate (2) > 3a > 4-nitrophenyl diphenyl phosphinate (1) is determined mainly by the steric effects of the alkyl/aryl substituents around the central P atom in the TS of the reaction.

Catalysis↗

Phosphorylation is involved in the activation of metal-regulatory transcription factor 1 in response to metal ions.

We have studied the role of phosphorylation in the activation of metal-regulatory transcription factor-1 (MTF-1) and metallothionein (MT) gene expression. We showed that MTF-1 is phosphorylated in vivo and that zinc stimulates MTF-1 phosphorylation 2-4-fold. Several kinase inhibitors were used to examine the possible involvement of kinase cascades in the activation of MTF-1. Metal-induced MT gene expression was abrogated by protein kinase C (PKC), c-Jun N-terminal kinase (JNK), phosphoinositide 3-kinase, and tyrosine-specific protein kinases inhibitors, as assayed by Northern analysis and by cotransfection experiments using a metal regulatory element-luciferase reporter plasmid. The extracellular signal-activated protein kinase and the p38 kinase cascades did not appear to be essential for the activation of MT gene transcription by metals. By using dominant-negative mutants of PKC, JNK, mitogen-activated kinase kinase 4 (MKK4), and MKK7, we provide further evidence supporting a role for PKC and JNK in the activation of MTF-1 in response to metals. Notably, increased MTF-1 DNA binding in response to zinc and MTF-1 nuclear localization was not inhibited in cells preincubated with the different kinase inhibitors despite strong inhibition of MTF-1-mediated gene expression. This suggests that phosphorylation is essential for MTF-1 transactivation function. We hypothesize that metal-induced phosphorylation of MTF-1 is one of the primary events leading to increased MTF-1 activity. Thus, metal ions such as cadmium could activate MTF-1 and induce MT gene expression by stimulating one or several kinases in the MTF-1 signal transduction pathway.

Animals↗

Comparative study of the formation of oxidative damage marker 8-hydroxy-2'-deoxyguanosine (8-OHdG) adduct from the nucleoside 2'-deoxyguanosine by transition metals and suspensions of particulate matter in relation to metal content and redox reactivity.

An association between exposure to ambient particulate matter (PM) and increased incidence of mortality and morbidity due to lung cancer and cardiovascular diseases has been demonstrated by recent epidemiological studies. Reactive oxygen species (ROS), especially hydroxyl radicals, generated by PM, have been suggested by many studies as an important factor in the oxidative damage of DNA by PM. The purpose of this study was to characterize quantitatively hydroxyl radical generation by various transition metals in the presence of H2O2 in aqueous buffer solution (pH 7.4) and hydroxylation of 2'-deoxyguanosine (dG) to 8-hydroxy-2'-deoxyguanosine (8-OHdG) under similar conditions. The order of metals' redox reactivity and hydroxyl radical production was Fe(II), V(IV), Cu(I), Cr(III), Ni(II), Co(II), Pb(II), Cd(II). Then, we investigated the generation of hydroxyl radicals in the presence of H2O2 by various airborne PM samples, such as total suspended particulate (TSP), PM10, PM2.5 (PM with aerodynamic diameter 10 and 2.5 microm), diesel exhaust particles (DEP), gasoline exhaust particles (GEP) and woodsmoke soot under the same conditions. When suspensions of PMs were incubated with H2O2 and dG at pH 7.4, all particles induced hydroxylation of dG and formation of 8-OHdG in a dose-dependent increase. Our findings demonstrated that PM's hydroxyl radical (HO radical) generating ability and subsequent dG hydroxylation is associated with the concentration of water-soluble metals, especially Fe and V and other redox or ionizable transition metals and not their total metal content, or insoluble metal oxides, via a Fenton-driven reaction of H2O2 with metals. Additionally, we observed, by Electron paramagnetic resonance (EPR), that PM suspensions in the presence of H2O2 generated radical species with dG, which were spin-trapped by 2-methyl-2-nitroso-propane (MNP).

8-Hydroxy-2'-Deoxyguanosine↗