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Wilson disease and Menkes disease: new handles on heavy-metal transport.

Little is known at the molecular level about the homeostatic control of heavy-metal concentrations in mammals. Recently, however, two human diseases that disrupt copper transport, Menkes disease and Wilson disease, were found to be caused by mutations in two closely related genes, MNK and WND, which encode proteins belonging to the P-type ATPase family of cation transporters. The MNK and WND proteins are unique in having at their amino termini six copies of a sequence that is remarkably similar to sequences previously found in bacterial heavy-metal-resistance proteins and in a P-type ATPase that appears to form part of a bacterial copper homeostatic system. These two human ATPases are the first putative heavy-metal transporters to be discovered in eukaryotes.

Amino Acid Sequence↗

Derivation and application of a new model for heavy metal biosorption by algae.

An equilibrium model for describing the relationships between important parameters for heavy metal sorption by algae was derived through a thermodynamics approach. In this model, both the removal efficiency of heavy metal and metal adsorption per unit algal biomass are considered to be simple functions of the ratio of algal biomass concentration to the initial metal concentration for selected conditions, i.e. as at constant pH and temperature. The model was found to fit the experimental results well (judged by the correlation-regression coefficient, R2), for the adsorption of cadmium, copper, lead and zinc by two algal species, Oocystis sp. (both living and non-living) and Chlorococcum sp. The applicability of the model was also supported by the reprocessed results of experimental data given in the literature, i.e. for the metal species, Cd, Pb, Cu and Ag, the algal species, Chlorella vulgaris, Scenedesmus quadricauda and Cladophora crispata, and both batch and continuous fixed-bed reactors. It was also demonstrated that the model could be applied over a broad range of pH for cadmium and copper adsorption by Oocystis sp. However, the model was not applicable at very low and high pH levels, due to negligible adsorption and precipitation, respectively.

Adsorption↗

Testing applicability of black poplar (Populus nigra L.) bark to heavy metal air pollution monitoring in urban and industrial regions.

A comparative study of the capabilities of black poplar-tree (Populus nigra L.) bark as a biomonitor of atmospheric heavy-metal pollution is reported. Performance indicators (concentrations and enrichment factors) of heavy metal bioaccumulation of bark were compared to the corresponding indicators of epiphytic lichens Xanthoria parietina (L.) Th. Fr. and Physcia adscendens (Fr.) H. Oliver, collected simultaneously with bark samples within the Kiev urban-industrial conurbation. The concentrations of 40 minor and trace elements in the samples were measured by a combination of epithermal and instrumental neutron activation analysis (NAA) using a 10 MW nuclear research reactor WWR-M as the neutron source. Statistical analysis of the data was carried out using non-parametric tests. It was shown that for the majority of the elements determined a good correlation exists between their concentrations in bark and in the lichen species. The accumulation capability of the bark was found to be as effective as, and in some cases better, for both types of lichens. Based on the background levels and variations of the elemental concentration in black poplar-tree bark, threshold values for the enrichment factors were established. For a number of elements (As, Au, Ce, Co, Cr, Cu, La, Mn, Mo, Ni, Sb, Sm, Ti, Th, U, V, W) an interspecies calibration was performed. An optimized pre-irradiation treatment of the bark sample was employed which efficiently separated the most informative external layer from the deeper layers of the bark and thus minimized variations of the element concentrations. Results of this study support black poplar-tree bark as an alternative to epiphytic lichens for heavy metal air pollution monitoring in urban and industrial regions, where severe environmental conditions may result in scarcity or even lack of the indicator species.

Air Pollutants↗

Recovery of heavy metals and stabilization of spent hydrotreating catalyst using a glass-ceramic matrix.

Chemical analysis of spent Co/Mo/gamma Al(2)O(3) catalyst revealed the presence of carbon, molybdenum, sulfur, vanadium and cobalt at levels of 16.0, 10.9, 7.3, 4.6 and 4.0 wt.%, respectively. It was found that calcination at 500 degrees C provides an effective solution for the removal of carbon and sulfur and this generates the oxide form of the heavy metals. The removal of these heavy metals can be achieved through a two-stage leaching process. During the first stage, in which concentrated ammonia is used and it has been found that this process can be successful in removing as much as 83% (w/v) Mo. In a second stage, it was found that using 10% (v/v) of sulfuric acid, it was possible to account for up to 77% (w/v) Co and 4% (w/v) Mo removal. Leaching test results indicated that the vanadium present in the heated spent catalyst was almost stabilized but the molybdenum and cobalt were not. The combination of two solid wastes, ladle furnace slag (LFS) and treated residue of spent catalyst, could be used for making a high value-added anorthite glass-ceramic materials. Further leaching tests showed that ceramic glass materials provided a very effective method of Co, Mo and V heavy metals stabilization resulting in a product with a possible commercial value.

Aluminum Silicates↗

Diagnosis of heavy metal contamination in agro-ecology of Gujranwala, Pakistan using cattle egret (Bubulcus ibis) as bioindicator.

The present study investigated the status of heavy metals: Lead (Pb), Cadmium (Cd), Chromium (Cr), Cobolt (Co), Silver (Ag) and Nickle (Ni) residues in egg, regurgitate and sediment samples collected from two colonies of cattle egret (Bubulcus ibis) during the breeding seasons between April and August in 2004 and 2005. The mean concentration of heavy metals in eggs and regurgitates was found higher compared to the maximum residue limit (mrl) standards prescribed by Environmental Protection Agency (EPA). A further comparison was made with a similar study conducted in China. High concentrations of heavy metals have contributed to the altered breeding behaviour of the bird species studied. Based on these findings we suggested a regular monitoring of the spread of these pollutants as these have not yet reached to the sediments.

Animals↗

Trace analysis of heavy metals in groundwater samples by ion chromatography with post-column reaction and ultraviolet-visible detection.

Groundwaters originating from local and regional aquifers surrounding ash deposits produced by a coal-fired power plant were collected. These water samples were chemically analyzed for quantifying their heavy metal composition at trace levels. A highly sensitive analytical technique based on ion chromatography with a UV-Vis detector and under isocratic eluent flow-rate conditions was used. In order to quantify the major heavy metals (Pb, Cu, Cd, Co, Zn and Ni), three ionic separation column systems were evaluated: (1) a cationic column (HPIC-CS2, Dionex) tested with two eluents (10 mM oxalic acid-7.5 mM citric acid; and 40 mM D-tartaric acid-12 mM citric acid); (2) an anionic column (HPIC-AS4, Dionex) evaluated with 25 mM oxalic acid as eluent: and (3) a bifunctional ion-exchange column (Ionpac CS5, Dionex) which was also tested with two eluents (6 mM pyridine, 2,6-dicarboxylic acid; and 50 mM oxalic acid/95 mM lithium hydroxide). The lowest detection limits achieved with the Ionpac CS5 column and the 50 mM oxalic acid-95 mM lithium hydroxide eluent enabled the heavy metal analysis in groundwater samples to be reliably performed. Details of this comparative study, including the ion chromatography procedure selected and its application to heavy metal analysis of groundwater samples, are presented in this work.

Chromatography, Ion Exchange↗

[Comparative study on pesticide and heavy metal residuals of four cultivars of Chrysanthemum morifolium].

OBJECTIVE: To study organochlorine pesticide and heavy metal residuals of Chrysanthemum morifolium. METHOD: The contents of organochlorine pesticide residuals was determined by chromatography, Cu, Pb, Cd was determined by AAS, and As, Hg was determined by AFS. RESULT AND CONCLUSION: The contents of organochlorine pesticide and heavy metals residuals are up to "Green Trade Standards of Importing & Exporting Medicinal plants & Preprations" (MOFTEC, 2001), but the contents are different among four cultivars clearly.

Cadmium↗

Effects of heavy metal exposure on the condition and health of nestlings of the great tit (Parus major), a small songbird species.

In this study we examined the possible effects of heavy metal exposure on the condition and health of great tit nestlings (Parus major) at four study sites along a pollution gradient near a large non-ferrous smelter in Belgium during three consecutive breeding seasons. Our results showed that nestlings were indeed exposed to large amounts of heavy metals. Excrements contained significantly higher concentrations of several heavy metals (silver, arsenic, cadmium, mercury, lead) near the pollution source than at study sites farther away. When taking into account the number of young in the nest at the time of sampling, nestling body mass and condition were significantly reduced at the most polluted site. Nestlings at the two most polluted sites fledged significantly later than at the least polluted site. We also observed growth abnormalities of the legs near the pollution source. Tarsus length, wing length and haematocrit values did not differ significantly among study sites.

Air Pollutants↗

Mobility of heavy metals as related to soil chemical and mineralogical characteristics of Brazilian soils.

In order to better understand the relationship between soil characteristics and mobility of some heavy metals, correlation studies were conducted in samples of unlimed and limed A, B and C horizons of three Brazilian soils, representative of the majority of the tropical soils. A number of chemical and mineralogical characteristics of one Oxisol and two Ultisols were related to the retardation factors (Rf) for zinc (Zn), cadmium (Cd), copper (Cu) and lead (Pb). The retardation factors, obtained in leaching column experiments, were used as an estimate of solute movement in the profile. Soil types and soil horizons were found to influence metal retardation factors which, in turn, correlated better with the chemical than the mineralogical soil characteristics. For the unlimed soil samples, the soil characteristics that significantly correlated with Zn-Rf and Cd-Rf were the sum of exchangeable bases (SB), and soil exchangeable (Ca-KCl) and non-exchangeable (Ca-HCl) calcium contents. These results showed the strong influence of the cation exchange phenomenon on the retention and mobility of these two metals. For Cu and Pb, not only SB, cation exchange capacity (CEC) and Ca-KCl and Ca-HCl but also the organic matter correlated well with the Rf, showing that complex or chelate formation may play an important role in the movement of these elements. The important soil chemical characteristics related to the retardation factors in the limed soil samples were SB for Cd, and Ca-HCl for Cu and Pb, suggesting that precipitation may also influence the mobility and retention of the latter two heavy metals in these soil samples. Soil pH influenced the heavy metals adsorption and movement as shown by the significant correlation with the retardation factors when the combined data for the unlimed and limed soil samples was considered.

Adsorption↗

Evaluation of heavy metal acute toxicity and bioaccumulation in soil ciliated protozoa.

Laboratory toxicity tests, using ciliated protozoa, are scarce and they have been carried out usually with freshwater species. In this study, we have analysed the acute cytotoxicity of Cd, Zn and Cu in five different strains of very common soil ciliate species (Colpoda steinii, Colpoda inflata and Cyrtolophosis elongata), which were isolated from very different soil samples (polluted or not with heavy metals). Soil ciliates are quite resistant to heavy metals pollution with regard to ciliates from other habitats. The toxicity sequence was Cd>Cu>>Zn. Results from Cd+Zn mixtures indicated that Cd cytotoxicity decreases in the presence of low or moderate Zn concentrations. A broad heavy metal resistance level diversity exists among isolates of colpodid ciliates and it is seen to be a genetic feature rather than a habitat dependence. Bioaccumulation is seen to be the main mechanism involved in the metal resistance, except for Cu. For the first time in ciliates, a fluorescent method has been applied to detect Zn intracellular deposits. This methodology might be an useful tool for monitoring heavy metal pollution in soils.

Animals↗

Cloning of a heavy-metal-binding protein derived from activated-sludge microorganisms.

A gene of the heavy-metal-binding protein (HMBP) was newly isolated from a genetic DNA library of activated-sludge microorganisms. HMBP was produced by transformed Escherichia coli, and the copper-binding ability of HMBP was confirmed. HMBP derived from activated sludge could be available as heavy metal adsorbents in water and wastewater treatments.

Adsorption↗

Regulation of essential heavy metals (Cu, Cr, and Zn) by the freshwater prawn Macrobrachium malcolmsonii (Milne Edwards).

Despite the low concentrations of heavy metals in the surrounding medium, aquatic organisms take them up and accumulate them in their soft tissues to concentrations several fold higher than those of ambient levels (Bryan 1979; Rainbow et al. 1990). Knowledge of accumulation patterns of a particular trace metal is a prerequisite for understanding the significance of an observed metal concentration in a particular animal, especially from the aspect of biomonitoring. Many marine invertebrates accumulate heavy metals without any regulation and the accumulation necessarily being associated with mechanisms to store the metals in a detoxified form. Two detoxification mechanisms have been described, both of which may occur in one specimen. Heavy metals can either be bound up in insoluble metalliferous 'granules' (Mason and Nott 1981), or are bound to soluble metal-binding ligands, such as metallothioneins (Roesijadi 1992). Some marine decapod crustaceans have an innate ability to regulate the internal concentrations of essential but potentially toxic metals within a constant level, presumably to meet their metabolic demands (Rainbow 1985, 1992). However, at present, there is no such information relating to freshwater decapod crustaceans, especially shrimps which occupy a totally different environment. Macrobrachium malcolmsonii (Milne Edwards), a potential aquaculture species for freshwater is found in abundance in one of the major Indian rivers, the Cauvery. In the present study, an attempt was made to determine whether the freshwater prawn, M. malcolmsonii, is able to regulate the three essential elements, copper, chromium and zinc, over a wide range of dissolved concentrations. These three metals were chosen because the Cauvery River receives pollutants containing these metals (Vijayram et al. 1990).

Animals↗

Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials.

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.

Hydrogen-Ion Concentration↗

[Study on the baseline contents and reference maximum limit standard of heavy metals and harmful element of 23 Chinese herbs in Northern China].

OBJECTIVE: This study was carried out to obtain the baseline contents and establish the reference maximum limits of heavy metals and harmful element in China. METHODS: According as Chinese standard methods of heavy metals and harmful element, 254 Chinese herbs were determined. RESULTS: The contents of lead, cadmium, mercury and arsenic in different Chinese herbs were (1.78 +/- 1.98), (0.17 +/- 0.24), (0.04 +/- 0.06) and (0.72 +/- 0.69)mg/kg, respectively. In the process of establishing the reference maximum limit standards of these harmful substances, the dietary intakes which including the intakes from food, beverage and drinking water were necessarily considered. The intakes including dietary and Chinese herbs of per person per day (and the percent of ADI) of lead, cadmium, mercury and inorganic arsenic were 102.9 microg (45.7%), 21.4 microg (34.0%), 5.7 microg (5.7%) and 81.0 microg (60.5%), respectively. We recommended the reference maximum limit standards of lead, cadmium, mercury and arsenic which in Chinese herbs were 5.0 mg/kg, 0.3 mg/kg, 0.2 mg/kg and 2.0 mg/kg, respectively. CONCLUSION: The survey of baseline level of heavy metals and harmful element was successful. The intakes of these harmful substances were safe to human health. The maximum level standards of lead, cadmium, mercury, arsenic in plant Chinese herbs submitted by our coordinated group have been accepted by Chinese Herbs Codex, 2005 version. This standard is suitable for quality standards in plant Chinese herbs.

Arsenic↗

Heavy metal contamination from geothermal sources.

Liquid-dominated hydrothermal reservoirs, which contain saline fluids at high temperatures and pressures, have a significant potential for contamination of the environment by heavy metals. The design of the power conversion cycle in a liquid-dominated geothermal plant is a key factor in determining the impact of the installation. Reinjection of the fluid into the reservoir minimizes heavy metal effluents but is routinely practiced at few installations. Binary power cycles with reinjection would provide even cleaner systems but are not yet ready for commercial application. Vapor-dominated systems, which contain superheated steam, have less potential for contamination but are relatively uncommon. Field data on heavy metal effluents from geothermal plants are sparse and confounded by contributions from "natural" sources such as geysers and hot springs which often exist nearby. Insofar as geothermal power supplies are destined to multiply, much work is required on their environmental effects including those caused by heavy metals.

Air↗

Heavy metals in the vicinity of a chlor-alkali factory in the Upper Negro River ecosystem, Northern Patagonia, Argentina.

A study on heavy metal contents was performed in sediments and biota of the Upper Negro River (Alto Valle) aquatic system, Northern Patagonia, Argentina. The irrigation system of the Neuquén and Negro Rivers runs alongside these rivers for 150 km, supporting intensive agricultural and economical activities, mainly related to fruit production. A mercury cell chlor-alkali factory operated between 1951 and 1995. Close attention was given to the surroundings of the plant, located next to the Main Irrigation Channel, and to the PII drainage channel which received the plant's effluents between 1951 and 1979. From 1979 until its closure, the effluents were pumped above a ravine to a series of evaporation and decantation pools. Mercury and other heavy metals and metalloids (Ag, As, Ba, Co, Cr, Cs, Ni, Sb, Se, U and Zn) contents were measured for bottom sediments of the river and irrigation and drainage channels, for two widespread species of macrophytes (Potamogeton pectinatus and Myriophyllum brasiliensi), and for liver and muscle of native fish Odontesthes microlepidotus. River bed sediments show no evidence of heavy metal accumulation, however, biota might indicate that contaminants are entering the rivers. Mercury was the only element accumulated in the Main Irrigation channel sediments, the highest contents occurring in the surroundings of the nowadays shut-down chlor-alkali plant, returning to background values approximately 40 km downstream the plant. At the plant site, sediments from the center of the channel showed a decrease in Hg content in the upper 10 cm layer, ranging from 0.8 to 3.4 microg g(-1), and from 2.8 to 13.7 microg g(-1) in the next 10 cm lower layer. Conversely, the PII drainage channel sediments showed accumulation of Hg (2-4 microg g(-1)), distributed uniformly at different depths and along the channel, until its mouth at Negro river. Mercury contents of macrophytes downstream the chlor-alkali plant are higher than the baseline for the area, and macrophytes and fish liver from the PII drainage channel present the highest content in this element. The drainage channel system showed different degrees of impact, those channels flowing through densely populated areas being the most affected.

Animals↗

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions.

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.

Journal Article↗