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Crab shell for the removal of heavy metals from aqueous solution.

The ability of crab shell to remove heavy metals from aqueous solution was evaluated by comparing with that of several sorbents (cation exchange resin, zeolite, granular activated carbon, powdered activated carbon). All experiments were conducted using several heavy metal ion solutions (Pb, Cd, Cu, Cr). The orders of heavy metal removal capacity and initial heavy metal removal rate were found as crab shell > cation exchange resin > zeolite > powdered activated carbon>granular activated carbon. Therefore, crab shell is satisfactory as a good biosorbent for the heavy metal removal. The study indicates that the removal of these heavy metals is selective, with Pb and Cr being removed in preference to Cd and Cu. The sorption equilibrium of heavy metal ions on sorbents was modeled on the applications of Langmuir and Freundlich.

Adsorption↗

[The course of virus infection of Lycopersicon esculentum plants at high concentrations of heavy metals].

Effect of certain compositions of heavy metals on the course of the system infection of TMV in plants of tomatoes Lycopersicon esculentum L. under field conditions was investigated. It is shown that the simultaneous influence of the virus infection and heavy metals in concentration of 10 MPC (maximum permissible concentration) resulted in the decrease of the content of total chlorophyll in the investigated plants by degradation of chlorophyll A; that was more considerable decrease as compared with separate influence of each of the factors. Treatment of plants by toxical concentrations of lead and zinc led to inconsiderable delay in development of the system TMV infection together with the increase of the virus content in plants 2 and more times, that evidences for the probable synergism in the action of the given heavy metals and virus infection. On the contrary, copper, though it decreased the content of total chlorophyll, manifested the protective properties and restricted essentially the virus accumulation in a plant as a whole.

Agriculture↗

Multivariate correlations of geochemical binding phases of heavy metals in contaminated river sediment.

Distributions of geochemical binding phases of seven heavy metals (Cr, Cu, Co, Zn, Ni, Pb, and Cd) in sediment cores taken from six heavily polluted sites of the Ell-Ren River in Southern Taiwan were studied. Sequential extraction procedures (SEP) were used to determine the variations of heavy metal binding phases (exchangeable, bound to carbonates, bound to manganese-oxides, bound to iron-oxides, and bound to organic matter) in different sediment depths. Multivariate analyses were used to explore the correlations among these geochemical binding phases of heavy metals. Results showed that the total amounts of various binding phases of heavy metals significantly varied with sediment depth, but their binding behaviors in various phases did not significantly change with depth. The organic matter content in the sediments increased with increasing Fe-oxide content. In addition, the binding affinities of carbonates with Zn, Pb, and Ni were higher than the affinities of carbonates with the other heavy metals. The binding affinity of Fe-oxides with Cr was higher than the affinities of Fe-oxides with the other heavy metals. Both correlation matrixes and principal component analyses demonstrated that distributions of Cu, Zn, Ni, and Cd had significant correlations with each other in both different depth horizons and various geochemical binding phases. The results indicate that these heavy metals might be discharged from the same pollution sources in the past, and also showed stable geochemical binding behaviors with the high silt sediment. However, Co had a poor correlation with the other six heavy metals in various binding phases, except with organic matter. Binding behaviors of Pb in the phases of bound to carbonates and exchangeable were different from the other six heavy metals. Cu was inversly correlated with the other six heavy metals in its binding behavior with reducible phases (Fe-/Mn-oxides).

Carbonates↗

Functional characterization of a heavy metal binding protein CdI19 from Arabidopsis.

Heavy metals are potentially highly toxic for organisms. Plants possess the ability to minimize damage but the underlying molecular mechanisms have yet to be detailed. Screening Cd-responsive genes in Arabidopsis, we previously identified a gene encoding a putative metal binding protein CdI19, which, upon introduction into yeast cells, conferred marked toleration of Cd exposure. Here we describe that bacterially expressed CdI19 directly interacts with Cd at its CXXC motif, as revealed by circular dichroism analysis, and that it is exclusively localized at plasma membranes, as revealed by heterologous expression of fusion product with a green fluorescent protein in BY2 cells. Northern blot analyses indicated that CdI19 transcripts were induced not only by Cd, but also by dicationic forms of Hg, Fe and Cu. Histochemical assays using transgenic Arabidopsis expressing the CdI19 promoter::GUS showed CdI19 to be expressed in petiole, hypocotyl, peduncle and vascular bundles in root tissues. Overexpression of the CdI19 cDNA conferred Cd tolerance in transgenic Arabidopsis. These results suggest that CdI19 plays an important role in the maintenance of heavy metal homeostasis and/or in detoxification by endowing plasma membranes with the capacity to serve as an initial barrier against inflow of free heavy metal ions into cells.

Adaptation, Physiological↗

The role of urban air pollutants on the performance of heavy metal accumulation in Usnea amblyoclada.

Lichens incorporate heavy metals according to a selectivity sequence; therefore, their uptake rate can be affected when elements with a high affinity for cell wall exchange sites or that provoke harmful alterations to the metabolism of lichen thalli are present in the environment. The aim of this study was to examine the effect of urban pollutants on the accumulation of some heavy metals in Usnea amblyoclada. Lichen samples were transplanted for 1 month to both a polluted and a nonpolluted area in Cordoba, Argentina. They were then collected and soaked in tridistilled water or in solutions containing different concentrations of Cu, Ni, Pb, and Zn salts. The uptake of Cu2+, Ni2+, Zn2+, and Pb2+, and other parameters indicative of lichen damage were measured in all the lichen samples. The thalli retrieved from the polluted area showed significant increases in both the malonaldehyde content and the electrical conductivity of the water in which they had been immersed. These results indicate that the atmospheric pollutants could be responsible for the significant damage to the lichen's cellular membranes, thus altering several mechanisms related to the uptake of heavy metals. Both the area of transplantation and the concentration of the metallic solutions had significant effects on the levels of Cu, Ni, and Pb measured in lichen thalli; however, no significant differences were observed in Zn concentrations. The highest uptakes corresponded to Pb and Cu, suggesting that they probably have a higher affinity with the lichen cell wall exchange sites. This study confirms the fact that, although lichens can be useful biological indicators, the physiological mechanisms involved in metal uptake should be carefully analyzed. Therefore, when estimating the heavy metal content of an environment, the competitive mechanism for cation uptake should be considered especially in areas where the presence of high levels of metals with a strong binding affinity is suspected. The presence of secondary products in the lichens could be responsible for the selective uptake of cations and for a possible tolerance to their presence.

Air Pollutants↗

[Photobacterium phosphoreum assay on the toxicity of soil contaminated by heavy metals].

The toxicity of soil artificially contaminated by heavy metals was assessed with Photobacterium phosphoreum. The results showed that the duration of optimum balance was 24 hours, and that of optimum extraction was 2 hours. Two leaching methods were compared, and data showed that optimum leaching solvent was hydrocarbon chloride with a concentration of 0.1 mol.L-1 HCL. Dose-response curve indicated that the content of heavy metals was positively related with the toxicity of soil. The general detection limit given by EC50 of soil contaminated by single heavy metal were Cd 26.12 mg.kg-1, Cu 291.48 mg.kg-1, Zn 72.46 mg.kg-1 and Pb 2174.93 mg.kg-1. This study also indicated the toxicity of complex heavy metals pollution in soil was stronger than that of individual element. The research could provide a theoretic base for the remediation of soil contaminated by heavy metals.

Cadmium↗

Simple and sequential extractions of heavy metals from different sewage sludges.

The presence of heavy metals in the sludges produced in waste-water treatment plants restricts their use for agricultural purposes. This study looks at different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) and compares the distribution of the heavy metals they contain according to the treatment that they have undergone. Some agronomic parameters necessary for characterising a sludge as suitable for use as amendment were determined. The aim of this study is to compare the availability and the localisation of heavy metals in different sewage sludges using simple (water and DTPA) extraction and the BCR (Community Bureau of Reference) sequential extraction procedure. It was confirmed that the total concentration of heavy metals did not exceed the limits set out by European legislation and that the stabilisation treatment undergone by the sludges strongly influenced the heavy metal distribution and the phases to which they were associated and their bioavailability level. The DTPA extraction procedure is cheap and easy to perform and the obtained results are similar to those obtained with the sequential procedure.

Aerobiosis↗

Biomarkers of renal effects in children and adults with low environmental exposure to heavy metals.

The health effects of chronic exposure to heavy metals such as lead, cadmium, and mercury are widely documented, yet few data exist about the renal impact of low environmental exposure to these metals, particularly in children. The aim of this study was to assess renal parameters in children and adults living in an environment known for its past heavy metal contamination around two nonferrous smelters in northern France (Noyelles-Godault and Auby) and to compare their results with age and gender-matched controls living in neighboring municipalities with unpolluted soil (total: 400 children, 600 adults, sex ratio = 1). The integrity of renal function was assessed by measuring the urinary excretion levels of total protein, albumin, transferrin, beta(2)-microglobulin, retinol-binding protein, brush border antigen, and the enzyme N-acetyl-beta-D-glucosaminidase (NAG). The mean blood concentrations of lead (Pb-B, children </=42.2 micro/L, adults </=71.3. micro/L) and of cadmium (Cd-B, children </=0.52 microg/L, adults 0.86 microg/L) were all relatively low, indicating a low uptake of these heavy metals from the environment despite relatively high levels in soil (between 100 and 1700 ppm for lead and 0.7 to 233 ppm for cadmium). Pb-B levels were, however, significantly increased in boys, girls, and women--but not men--living in the polluted area. Boys, men, and women living in the polluted area had also on average higher Cd-B levels. The concentrations of mercury in urine (Hg-U) were by contrast similar in control and exposed groups. None of the renal parameters studied showed a significant difference between control and exposed groups. The influence of heavy metals on renal parameters was further assessed by stepwise multiple regression, testing Pb-B, Cd-B, Hg-U, age, gender, body mass index (BMI), urinary creatinine levels, and area of residence as predictors in both children and adults, including first-order metal interaction terms, smoking habits, and alcohol consumption in adults. The only positive correlation was found between the urinary excretion of NAG activity (standardized for BMI and urinary creatinine) and Cd-B levels when taking the whole children population, indicating that even low cadmium burdens may produce subtle effects on the proximal tubule in children, although deleterious consequences are unlikely should exposure not increase. However, in the absence of other positive findings even after studying the smaller subgroups with higher levels of heavy metals, these results are clearly indicative of the minimal renal impact of living around nonferrous smelters that are currently complying with pollution regulations, even when soil contamination is still high.

Adult↗

[Phytochelatin and its function in heavy metal tolerance of higher plants].

The biosynthesis pathway of phytochelatins (PC) and its function in heavy metal tolerance of higher plants were summarized in this paper. The toxic heavy metal accumulation in soil would deteriorates crop growth and yield components, and threaten the agro-products security. There were significantly differences in the accumulation and tolerance to heavy metals among plant species and genotypes. The formation of PC in response to the stress caused by heavy metals was one of the truly adaptive responses occurred commonly in higher plants. In the heavy metal tolerant genotypes, there was a much higher accumulation of PC than the non-tolerant lines. Glutathione (GSH) was the substrate for the synthesis of PC, which chelated the metals. The inactive toxic metal ions of metal--PC chelatins were subsequently transported from cytosol to vacuole before they could poison the enzymes of life-supporting metabolic routes, and transiently stored in vacuole to reduce the heavy metal concentration in cytosol, thus, heavy metal detoxification was attained. The break through of genetic mechanism and bio-chemical pathway of PC synthesis induced by heavy metals would depend on the further study on molecular biology in this field. The isolation of Cd-sensitive cad1 and cad2 mutants of Arabidopsis thaliana, that was deficient in PC, demonstrted the importance of PC for heavy metal tolerance. The effect of PC on food security and on phytoremediation of soil and water contaminated by heavy metals was also discussed in this paper.

Glutathione↗

[Chemical hazards induced by heavy metals refining processes].

BACKGROUND: Processes of refining heavy metals consist in removing impurities, which can be found in metals produced on industrial scale. People involved in heavy metals refining processes are primarily exposed to metals (Pb, Cd, Cu), metalloids (As, Se) and metal compounds. Exposure to dusts (from 2 to 50% SiO2) and sulfuric acid is an additional hazard. MATERIALS AND METHODS: The air concentrations of harmful chemical agents at heavy metals refining stations in two Polish Plants are presented. Several tens of workers employed in the processes of copper, lead, nickel sulfate, zinc, cadmium and silver production were examined. Concentrations of Cd, Ni, Se, Cu, Pb, Ag, As and Sb were determined by atomic absorption spectrometry (AAS) with a graphite tube, whereas Fe, ZnO oxide (as Zn), MgO (as Mg) and CaO (as Ca) by AAS with air-acetylene flame, and sulfuric acid by method described in PN-91/Z-04056/02. RESULTS: Lead concentrations in the samples collected in both Plants were often high (significantly exceeding Polish MAC values at some workstations). Arsenic concentrations ranged from very low in all processes in one Plant to very high, exceeding Polish MAC values, at some workstations in the other. In general, air concentrations of other agents were not high (fraction of MAC). The occurrence of antimony and magnesium oxide was not determined. CONCLUSIONS: The risk created by metals and metalloids at the workstations in two Plants was diversified. There is no need to determine Sb and MgO in further studies. Lead should be determined at all workstations, other agents can be determined at workstations with concentrations exceeding the determinability of relevant methods.

Air Pollutants, Occupational↗

Microbial heavy-metal resistance.

We are just beginning to understand the metabolism of heavy metals and to use their metabolic functions in biotechnology, although heavy metals comprise the major part of the elements in the periodic table. Because they can form complex compounds, some heavy metal ions are essential trace elements, but, essential or not, most heavy metals are toxic at higher concentrations. This review describes the workings of known metal-resistance systems in microorganisms. After an account of the basic principles of homoeostasis for all heavy-metal ions, the transport of the 17 most important (heavy metal) elements is compared.

Bacteria↗

[Accumulation of heavy metals in the sediments of Shenzhen Bay, south China].

Heavy metals concentrations in marine sediment cores of Shenzhen Bay were measured, and the profile distribution characteristic of heavy metals was discussed. Combined with the 210 Pb dating results, the contamination history of heavy metals was studied in high resolution records, and the metal accumulation processes were also analyzed. The results indicated that the concentrations of heavy metals was relatively low compared with other area in the world, but the elements of Pb, Cu and Zn were obviously contaminated by anthropogenic impact. The rapid economical development of Shenzhen in the last 20 years and Hong Kong in 1960-1970s contributed much on accumulation of heavy metals in the sediments.

Geologic Sediments↗

Heat and heavy metal stress synergize to mediate transcriptional hyperactivation by metal-responsive transcription factor MTF-1.

Mammalian cells react to heavy metal stress by transcribing a number of genes that contain metal-response elements (MREs) in their promoter/enhancer region; this activation is mediated by metal-responsive transcription factor-1 (MTF-1). Well-known target genes of MTF-1 are those encoding metallothioneins, small, cysteine-rich proteins with a high affinity for heavy metals. The response to heat shock, another cell stress, is mediated by heat shock transcription factor 1 (HSF1), which activates a battery of heat shock genes. Little is known about the cross-talk between the different anti-stress systems of the cell. Here we report a synergistic activation of metal-responsive promoters by heavy metal load (zinc or cadmium) and heat shock. An obvious explanation, cooperativity between MTF-1 and HSF1, seems unlikely: transfected HSF1 boosts the activity of an Hsp70 promoter but hardly affects an MRE-containing promoter upon exposure to metal and heat shock. A clue to the mechanism is given by our finding that heat shock leads to intracellular accumulation of heavy metals. We propose that the known anti-apoptotic effect of heat shock proteins allows for cell survival despite heavy metal accumulation and, consequently, results in a hyperactivation of the metal response pathway.

Cell Line↗

Evaluating heavy metal contents in nine composts using four digestion methods.

The production and application of compost potentially contaminate the environment with heavy metals. The heavy metal contents of composts must be exactly determined. Therefore, this study aims to understand the heavy metal contents in composts, using different digestion methods and to recommend the most appropriate digestion method making this measurement. Nine composts from different sources, including swine manure, poultry litter, food waste, municipal sewage sludge, soybean meal, wood residues, flesh-bone dust, fish-bone meal and guano, were selected to be digested by four methods to determine the contents of Cd, Cr, Cu, Mn, Ni, Pb and Zn by AAS. The four digestion methods were nitric acid, dry ashing, nitric-perchloric acid and sulfuric acid methods. Analytical results indicated that the nitric acid procedure was the most efficient for recovering Cd, Mn and Ni from most compost samples. The sulfuric acid procedure yielded the lowest recovery of Pb from the certified reference material (BCR 146) and the compost samples, especially from the composts with high pH and EC values potentially high in Ca. The nitric acid procedure was recommended as the method for digesting the composts herein, based on recovery analysis, cost and time taken. Dry ashing was recommended as a flexible method. Nitric-perchloric acid procedure was not recommended because perchloric acid is potentially hazardous during digestion and it recovers relatively little heavy metal.

Chemistry Techniques, Analytical↗

[Distribution and migration of heavy metals in soil profiles by high-resolution sampling].

The vertical distribution of heavy metals in soils profiles is a result of heavy metals accumulation and migration under combining influence of edaphic factors and environmental conditions. It's an important basis for evaluation of heavy metals pollution and remediation of contaminated soils. By traditional sampling methods, i.e., soils were sampled according to pedogenetic horizons, only very general information about element migration can be learned. In the current study, three sites near a steel factory were selected to represent three types of land use, i.e. forest, dry land for vegetable cultivation and rice paddy field. Soils were sampled horizontally by high-resolution sampling method. In the top of 40 cm soils were sectioned in 2 cm intervals, then 5 cm intervals in next 40 cm, and 10 cm intervals in the last 20 cm of profile. Total content of Cu, Zn, Pb, Cr and Cd were determined, and the vertical distribution of Cu, Zn, Pb, Cr, Cd in every profile was analyzed. The results indicated that enrichment of heavy metals appeared in the upper most layer of the natural forest soil that without any anthropic disturbance, and this phenomenon proved that heavy metals were coming from atmospheric deposition. We found that Cu, Zn and Pb moved downward in a short distance, Cd migrated relatively faster than Cu, Zn and Pb, while Cr had no recognizable location of migration front. In the soil profiles of dry land and paddy field, there were influences of agricultural practice, the distribution and movement of metals were thus different form those of the forest soil. In cultivated layer heavy metals were evenly distributed because soils in the upper layer were mixed by cultivation, however, bellow the cultivated layer obvious migration took place again. It is concluded that different heavy metals have different mobility and there is such a relative order: Cd>Cu>Zn>Pb. The study shows that the distribution pattern can be obtained with the currently adopted high-resolution sampling method, than traditional horizon sampling, and more precise migration distance and rates can be estimated.

Cadmium↗

Pilot scale study on the ex situ electrokinetic removal of heavy metals from municipal wastewater sludges.

In order to remove toxic heavy metals from municipal wastewater sludges, the ex situ electrokinetic technique was studied at pilot scale. This study focused on the feasibility of the electrokinetic removal of heavy metals from sludge and the effectiveness of this technique on the variations of abiotic (physicochemical) and biotic (intracellular and extracellular) speciations of heavy metals using several analytical methods. Even though the sludge used was taken from a municipal wastewater treatment plant, the sludge contained relatively high concentrations of target metal contaminants (Cd = 6.8 mg/kg, Cr = 115.6 mg/kg, Cu = 338.7 mg/kg, and Pb = 62.8 mg/kg). The removal efficiencies of heavy metals were significantly dependent on their speciations in the sludge matrices. The electrokinetic removal efficiencies of abiotic heavy metals exceeded 70% for the mobile and weakly bound fractions, such as, the exchangeable and carbonate fractions and were lower than 35% for the strongly bound fractions, such as, the organic/sulfide and residual fractions. In the case of the biotic heavy metals, the removal efficiencies of the extracellular fractions were slightly higher than those of the intracellular fractions.

Electricity↗

Experimental research on heavy metal wastewater treatment with dipropyl dithiophosphate.

In view of the existing technical problems about treatment of heavy metal pollution, a new organic heavy metal chelator-dipropyl dithiophosphate has been developed. This paper focuses on the mechanism about the laboratory synthesis of dipropyl dithiophosphate and chelate heavy metal, discusses the effects of pH value, added quantity of chelator, reactive time and coexistence of several heavy metal ions on the treatment effectiveness, and compares the stability of chelate complex with conventional neutral precipitation method. The results of the experiment show that, within the scope of pH 3-6, for the wastewater with the concentration of lead, cadmium, copper and mercury being 200 mg/L, dipropyl dithiophosphate enjoys a removal rate about these elements up to over 99.9%, and the concentrations of the lead, cadmium, copper and mercury in the wastewater after treatment are less than 1, 0.1, 0.5 and 0.05 mg/L, respectively, which meet the limit value of concentration stipulated in the Integrated Wastewater Discharge Standard (GB8978-1996). And the treatment effectiveness are not affected by pH value and coexistent heavy metal ions, which makes up the deficiency that neutral precipitation must be used under the condition of high alkalinity. The optimum quantity of dipropyl dithiophosphate chelator added is 1.2 times as much as stoichiometric amount and the optimum reactive time is 20 min for lead, cadmium and copper, and 30 min for mercury. Within the scope of pH 3-9, each heavy metal ion release of chelate complex will decrease along with increased pH value. But under any pH conditions, the release of heavy metal ions in hydroxide is far higher than that in chelate complex, therefore reducing the risk of polluting the environment again.

Chelating Agents↗

Heavy metal toxicity testing in environmental samples.

The toxicity of heavy metals in the environment depends on a number of physicochemical and biological factors. The complexity of these relationships has encouraged the use of bioassays for direct measurement of the [table: see text] impact of toxic metals on selected test species. Fish and daphnid bioassays are well accepted by the scientific and regulatory communities, but their length (48 h or more) and the considerable time and effort needed to culture the test organisms make their application to sample screening problematical. Microbial and biochemical assays based on the inhibition of bioluminescence, enzyme activity, enzyme biosynthesis, growth, respiration, and heat production are typically faster and less expensive than the traditional and fish bioassays. Some of these tests approach or equal the sensitivity of daphnids to heavy metals. Since the soil acts as a sink for airborne and waste-applied metals, the uptake of metals by plants and the associated toxic impacts are important. Growth inhibition, enzyme induction, and production of stress proteins have been considered as toxicity end points. Enzymatic tests have been developed that are specific for heavy metal toxicity. Such tests can facilitate toxicity reduction evaluations. Detection of individual metals in the environment may eventually be possible using biosensors consisting of genetically engineered microorganisms. Direct solid-phase tests for soil, sediment, or sludge toxicity, using bacterial bioluminescence or enzyme activity as end points, have been developed. Such tests may complement traditional solid-phase toxicity tests using nematodes or earthworms as indicator organisms. Based on the work reviewed, we draw the following conclusions: 1. The Microtox assay is sensitive to mercury but would fail to detect the toxicity of certain metals, such as cadmium. Among all the microbial assays reviewed, the bioassay based on growth inhibition of the alga Selenastrum capricornutum appears to give the lowest EC50s, similar to those seen for daphnid bioassays. 2. Biosensors, using genetically engineered microorganisms, offer an elegant means of detecting the presence of specific heavy metals in environmental samples. However, at the present time, they are not designed for assessing heavy metal toxicity. 3. The use of bioassays specific for heavy metal toxicity can be useful for directly assessing the bioavailability of these toxicants in environmental samples, thus avoiding the need for fractionation.+4

Animals↗