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Persistent organic pollutants and heavy metals in typical seafoods consumed in Singapore.

In this study, the levels of several heavy metals and persistent organic pollutants (POPs) were measured in the edible portions of 20 different seafood types consumed in Singapore (2 < n < 12). The mean heavy metal concentrations among the seafood types ranged from below detection limits (BLD) to 14.2 microg/g wet weight (ww) for As (shark), to 0.50 microg/g ww for Cd (kunning), to 25.5 microg/g ww for Cu (gray prawn), to 0.58 microg/g ww for Hg (eel), and to 1.21 microg/g ww for Pb (salmon). Chlordane, polychlorinated biphenyls (PCBs), and p, p'-DDT [2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane] and its related metabolites (sum noted as DDTs) were the main POPs found among the seafood types, with highest concentrations in salmon fillets and green mussels. Polybrominated diphenyl ether (PBDE) concentrations in salmon fillets (2.75 ng/g ww) were one order of magnitude lower than the highest concentration of PCBs (28.5 ng/g ww). The mean daily intake of contaminants from seafood was calculated for the general population of Singapore. Daily intakes of heavy metals and POPs from seafood are below the oral reference dose set by the U.S. Food and Drug Administration (FDA), except for As, although our study did not characterize the species of As present. Daily intake of As, DDTs, heptachlor, and PCBs in seafood exceeded the conservative cancer benchmark concentrations set by the U.S. Environmental Protection Agency (EPA), suggesting that a significant number of people are potentially at risk in Singapore over a lifetime from seafood consumption.

Animals↗

Molecular mechanisms of heavy metal hyperaccumulation and phytoremediation.

A relatively small group of hyperaccumulator plants is capable of sequestering heavy metals in their shoot tissues at high concentrations. In recent years, major scientific progress has been made in understanding the physiological mechanisms of metal uptake and transport in these plants. However, relatively little is known about the molecular bases of hyperaccumulation. In this paper, current progresses on understanding cellular/molecular mechanisms of metal tolerance/hyperaccumulation by plants are reviewed. The major processes involved in hyperaccumulation of trace metals from the soil to the shoots by hyperaccumulators include: (a) bioactivation of metals in the rhizosphere through root-microbe interaction; (b) enhanced uptake by metal transporters in the plasma membranes; (c) detoxification of metals by distributing to the apoplasts like binding to cell walls and chelation of metals in the cytoplasm with various ligands, such as phytochelatins, metallothioneins, metal-binding proteins; (d) sequestration of metals into the vacuole by tonoplast-located transporters. The growing application of molecular-genetic technologies led to the well understanding of mechanisms of heavy metal tolerance/accumulation in plants, and subsequently many transgenic plants with increased resistance and uptake of heavy metals were developed for the purpose of phytoremediation. Once the rate-limiting steps for uptake, translocation, and detoxification of metals in hyperaccumulating plants are identified, more informed construction of transgenic plants would result in improved applicability of the phytoremediation technology.

Carrier Proteins↗

Microbial and heavy metal contamination of treated hospital wastewater in Thailand.

OBJECTIVES: To determine the microbial and heavy metal contamination of treated hospital wastewater MATERIAL AND METHOD: Methods of treating wastewater were acquired by questionnaires. Chlorine concentration, pH, bacteria and parasites in treated wastewater were tested in the individual hospitals. Heavy metal concentrations were measured by atomic absorption spectrophotometry. RESULTS: In 2002, 72 hospitals were included in the present study. The common methods of treating wastewater were activated sludge and oxidation ditch. Bacteria exceeded standard numbers, pathogenic bacteria and parasites were found in two-thirds of the hospitals. Heavy metals, namely lead, chromium and cadmium, in the hospital effluent did not exceed standard concentrations. CONCLUSION: Micro-organisms exceeding standard levels were found in treated wastewater in two-thirds of the hospitals. Lead, chromium and cadmium levels in hospital effluent were in an acceptable range.

Animals↗

Mechanisms of biosorption of different heavy metals by brown marine macroalgae.

The biosorption mechanisms of different heavy metallic cations (Cd, Ni, Pb) to active chemical groups on the cell wall matrix of the nonliving brown marine macroalga, Sargassum vulgaris in its natural form, were examined by the following instrumental and chemical techniques: Fourier-transform infrared (FTIR) analysis, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and extraction of alginic acid and sulfated polysaccharides, which act as metal-binding moieties present in cell wall. From the different techniques used and the known chemical composition of the algal cell wall, it was observed that biosorption of the metallic cations to the algal cell wall component was a surface process. The binding capacities of the different metal cations were between 1 and 1.2 mmol metal/g on a dry weight basis. The main chemical groups involved in the metallic cation biosorption were apparently carboxyl, amino, sulfhydryl, and sulfonate. These groups were part of the algal cell wall structural polymers, namely, polysaccharides (alginic acid, sulfated polysaccharides), proteins, and peptidoglycans. The main cadmium cation sequestration mechanism by the algal biomass was apparently chelation, while the nickel cation sequestration mechanism was mainly ion exchange. Lead cations exhibit higher affinity to the algal biomass, and their binding mechanism included a combination of ion exchange, chelation, and reduction reactions, accompanied by metallic lead precipitation on the cell wall matrix. During the ion exchange process, calcium, magnesium, hydrogen cations, and probably other cations (sodium and potassium) in the algal cell wall matrix were replaced by the tested heavy metals.

Absorption↗

Short-term variations in the occurrence of heavy metals in Antarctic snow from Coats Land since the 1920s.

Short-term variations in heavy metals concentrations in Antarctic snow have been investigated by analysing 13 metals (Al, V, Cr, Mn, Co, Cu, Zn, Ag, Cd, Ba, Pb, Bi and U) in a series of ultraclean samples collected from two snow pits in Coats Land in the Atlantic sector of Antarctica. The samples covered a approximately 70 years time period from the 1920s to 1990. They were analysed by inductively coupled plasma sector field mass spectrometry and graphite furnace atomic absorption spectrometry. The results conclusively show that there is a pronounced short-term (intra- and inter-annual) variability of heavy metal in Antarctic snow, with the highest concentrations being up to 100 times higher than the lowest ones for metal such as Cr, Mn, Pb and U. Contributions from the different possible natural and anthropogenic sources are found to be extremely variable. This is especially due to the large variability in the transport patterns of heavy metals from Southern America, Southern Africa and Australia to the Antarctic continent. Inputs from several volcanic events were identified in our samples from non-seasalt sulfate concentrations profiles. The only ones that gave clear signals for heavy metals were eruptions at Deception Island the proximity of which allowed for tropospheric transport to Coats Land.

Journal Article↗

[Species and strain sensitivity of diasotrophs to heavy metals].

The species and strain sensitivity of free and symbiotic nitrogen-fixing agents to heavy metals: cadmium, copper, lead and zinc in the gradient of concentration from 0.5 to 20.0 MPC/l has been studied under the laboratory conditions. Azotobacter (35 strains) and rhizobia (63 strains) have been tested. It has been established that zinc and copper are more toxical for free nitrogen-fixing agents than lead and cadmium. Among symbiotrophic nitrogen-fixing agents the nodule bacteria for alfalfa were most sensitive to cadmium; nodule bacteria of pea and lupine--to copper; those of galega and soya--to zinc. Lead proved to be the least toxic for rhizobia. Negative effect of the heavy-metal mix on diasotrophs was higher than that of each separate metal. The cultures resistant to the effect of heavy metals have been found which may be used when producing preparation for biological reclamation of polluted soils.

Azotobacter↗

Simulating a heavy metal spill under estuarine conditions: effects on the clam Scrobicularia plana.

We describe the effect of heavy metals Zn, Cd, Pb and Cu on the induction of methallothioneins on the clam Scrobicularia plana along a salinity gradient simulated under laboratory conditions. The clams were exposed to constant heavy metal concentrations in a dynamic estuary simulator during a 15-day assay to investigate possible induction of metal-binding proteins in them. The concentration of heavy metals in water was analysed. Clams were analysed for methallothionein concentrations. The speciation of Zn, Cd, Pb and Cu along the salinity gradient was modelled. Zn showed the highest concentrations and its prevalent species was the free ion. Intersite differences have been observed in methallothionein concentration and related to the salinity gradient. It seems that synthesis of methallothioneins is the result of physiological forces acting in concert with the changes in the chemical speciation of metals, owing to the trace metals uptake is controlled by means of an interaction of physiology and physicochemistry.

Animals↗

Induction of several acute-phase protein genes by heavy metals: a new class of metal-responsive genes.

Acute-phase reactants, metallothioneins, and heat-shock proteins are the products of three families of genes that respond to glucocorticoids and cytokines. Metallothioneins and heat-shock proteins, however, are also stimulated by heavy metals, whereas very little is known about the effect of heavy metals on acute-phase-reactant genes. We have studied the effect of heavy metals (Hg, Cd, Pb, Cu, Ni, and Zn) and Mg on the acute-phase reactants alpha 1-acid glycoprotein, C-reactive protein, alpha 1-antitrypsin and alpha 1-antichymotrypsin. alpha 1-Acid glycoprotein and C-reactive protein mRNA levels were increased severalfold in livers of heavy-metal-treated Balb/c mice. The strongest induction was mediated by Hg, followed in order of response by Cd greater than Pb greater than Cu greater than Ni greater than Zn greater than Mg. None of the metals affected the mRNA levels of albumin, alpha 1-antitrypsin, and alpha 1-antichymotrypsin. Furthermore, failure to repress albumin, a negative acute-phase reactant, indicated that the induction of these genes was not due to a metal-mediated inflammatory response. The metals also induced alpha 1-acid glycoprotein and C-reactive protein in adrenalectomized animals, indicating that induction by the heavy metals is not mediated by the glucocorticoid induction pathway. Sequence analysis has revealed a region of homology to metal-responsive elements in the alpha 1-acid glycoprotein and C-reactive protein promoters. Additionally, an alpha 1-acid glycoprotein expression vector, pAGP(-595)CAT, responded to Hg and Cd when transfected into human HepG2 cells.(ABSTRACT TRUNCATED AT 250 WORDS)

Acute-Phase Proteins↗

Seasonal fluctuation in heavy metal pollution in Iran's Siahroud River. A preliminary study.

BACKGROUND: The management of its available water resources has become a key issue for Iran. During the last few decades, the water quality of Siahroud River in the coastal plain of the Caspian Sea in Gilan Province in Northern Iran has significantly degraded. The scarcity of water has been compounded by rapid population growth and increasing pollution from fertilizers, pesticides, and municipal and industrial wastes. One of the sources of this degradation is the movement of heavy metals from the river's watershed into the various water systems supported by the river, including the water system for Rasht City. METHODS: To study the magnitude of heavy metal pollution in the Siahroud River, seven heavy metals including Zn, Cu, Pb, Cd, Mn, Fe, and Ni were measured in duplicate from replicated water samples collected over five consecutive seasons and analyzed by Atomic Absorption Spectrometry. In situ measurements of pH were taken with the samples and total organic carbon (TOC) was analyzed by IR gas measurement. RESULTS: The results demonstrated that four of the seven heavy metals including Pb, Fe, Cd, and Mn exceeded permissible safe levels as established by the United States Environmental Protection Agency. Multivariate factor analysis suggested that industrial land-use was the main contributing factor for the high levels of Fe and Mn in the Siahroud River, whereas, Cd was principly from agricultural activities in the watershed. The data also suggested that pH and TOC had an important role in the behaviour of Pb and Mn, and that the elevated levels of these two heavy metals in Siahroud River was the consequence of other anthropogenic sources. Only negligible levels of Zn, Cu and Ni were detected. Finally, all the sampling stations were subjected to cluster analysis. The results indicated that three different zones could be distinguished according to the levels of pollution. In addition, it was shown that the urban areas did not have a significant impact on the heavy metal pollution in the river. This observation stems from the fact that the data from the sampling stations before and after Rasht City were not significantly different. RECOMMENDATIONS: Preventive measures need to be undertaken in the land-use systems and watersheds of the Siahroud River to reduce the pollution levels of Pb, Cd, Mn and Fe.Cd, Mn and Fe.

Cities↗

CzcR-CzcS, a two-component system involved in heavy metal and carbapenem resistance in Pseudomonas aeruginosa.

Pseudomonas aeruginosa is an environmental bacterium involved in mineralization of organic matter. It is also an opportunistic pathogen able to cause serious infections in immunocompromised hosts. As such, it is exposed to xenobiotics including solvents, heavy metals, and antimicrobials. We studied the response of P. aeruginosa upon exposure to heavy metals or antibiotics to investigate whether common regulatory mechanisms govern resistance to both types of compounds. We showed that sublethal zinc concentrations induced resistance to zinc, cadmium, and cobalt, while lethal zinc concentrations selected mutants constitutively resistant to these heavy metals. Both zinc-induced and stable zinc-resistant strains were also resistant to the carbapenem antibiotic imipenem. On the other hand, only 20% of clones selected on imipenem were also resistant to zinc. Heavy metal resistance in the mutants could be correlated by quantitative real time PCR with increased expression of the heavy metal efflux pump CzcCBA and its cognate two-component regulator genes czcR-czcS. Western blot analysis revealed reduced expression of the basic amino acid and carbapenem-specific OprD porin in all imipenem-resistant mutants. Sequencing of the czcR-czcS DNA region in eight independent zinc- and imipenem-resistant mutants revealed the presence of the same V194L mutation in the CzcS sensor protein. Overexpression in a susceptible wild type strain of the mutated CzsS protein, but not of the wild type form, resulted in decreased oprD and increased czcC expression. We further show that zinc is released from latex urinary catheters into urine in amounts sufficient to induce carbapenem resistance in P. aeruginosa, possibly compromising treatment of urinary tract infections by this class of antibiotics.

Carbapenems↗

Transport, fate and speciation of heavy metals (Pb, Zn, Cu, Cd) in mine drainage: geochemical modeling and anodic stripping voltammetric analysis.

The maximum concentrations (ppb) of heavy metals in the mine drainage (pH: down to 3.3) of Chonam-ri creek in the abandoned Kwangyang gold-silver mine, South Korea, are 22600 Zn, 2810 Cu, 182 Cd, and 109 Pb. A small, limestone-infused retention pond, about 440 meters downstream from the waste dump, plays an important role in the removal of heavy metals: the factors of reduction for Zn, Cu, Cd, and Pb are 12, 24, 14, and 14, respectively. This is due to the pH increase (up to >5.4) accompanying adsorption onto and/or coprecipitation with Fe- and Al-hydroxides (goethite and gibbsite). From the waste dump to the pond, heavy metal concentrations also progressively decrease due to pH increase. Geochemical modeling (using the computer code WATEQ4F) predicts that free aqueous metal ions are dominant (mostly >70% for Cu and Zn, and >60% for Pb and Cd) in samples collected upstream from the pond, whereas complexing with sulfate, carbonate and hydroxyl ions becomes important in the samples collected downstream. The comparison between the concentrations of electrochemically labile species (determined by Anodic Stripping Voltammetry) and the result of computer modeling shows that Cd and Zn are present predominantly as labile inorganic species throughout the whole range of the creek. However, Cu and Pb in the samples collected downstream from the pond largely form electrochemically inert species (possibly, metal-organic complexes). The above results indicate that the retention pond is effective in reducing the toxicity of heavy metals, especially Cu and Pb.

Electrochemistry↗

Study of the chemical interaction between barks and heavy metal cations in the sorption process.

The chemical mechanism displayed in the sorption of heavy metal cations on barks was discussed through a modelling study of adsorption in relation to the nature of the ligand borne by the chemical components of the bark sorbent. The adsorption isotherms of five heavy metal cations (Cr3 +, Cu2 +, Ni2 +, Pb2 +, Zn2+) on five species of barks (Sweet chestnut, Oak, Douglas fir, Norway spruce, Scots pine species) were studied. The experimental data fitted well the Langmuir model, which allowed the expression of the mathematical parameters (qmax, maximum binding capacity; b, affinity). The qmax values increased conversely to the b values. The correlation of these mathematical values (qmax and b) with the analysis of the chemical composition of barks led us to note that Cu2 + interacts preferentially with phenolic groups present in lignins and tannins and, opposite in, Pb2 + with the carboxylic acid groups in polysaccharides. These observations were explained (i) quantitatively by the amount of different types of sites and (ii) qualitatively, by the physicochemical characteristics of cations, the nature and the tridimensional structure of adsorption sites. Finally, the results allowed to define the nature of the chemical interaction (monodentate or multidentate complex) between each specified chemical component of barks and each kind of heavy metal cations.

Adsorption↗

Chemical form of cadmium (and other heavy metals) in rice and wheat plants.

Chemical forms of heavy metals such as Cd, Cu, Ni, and Pb in rice and wheat plants grown in nutrient solution containing a heavy metal were investigated. Fractionation of an extract of Cd-treated rice plants on Sephadex G-75 showed cadmium to be associated with organic compounds of high (fraction A), intermediary (fraction B), and low molecular weight (fraction C). Material A, whose molecular weight was greater than 440,000, is probably nonspecific binding of Cd to normal cell components. Materials B and C can be classified as types of metallothionein. The molecular weight of B was 33,100. This material contains 12 mg Cd/g protein. The UV-absorption spectrum of B showed absorptions at 280 and 250 nm. Material B was not eluted even at a very high ionic strength from the DEAE-cellulose column, but it was eluted at a very low ionic strength from a CM-cellulose column, indicating a highly anionic molecule which differs from metallothionein in animals. Fraction C contains two materials: one a Cd-containing material whose molecular weight was estimated to be approximately 7000 and the other an inorganic Cd salt. In addition to cadmium, copper, lead, and nickel in rice and wheat have been studied. As a result, heavy metal-containing materials whose molecular weights were estimated to be approximately 16,000 and 8900 (Ni-treated rice plants), 7000 (Pb-treated rice plants), 5000 (Cd-treated wheat plants), and 21,000 (Cu-treated wheat plants) were isolated.

Cadmium↗

Heavy metals remediation of water using plants and lignocellulosic agrowastes.

Toxic heavy metals and metalloids are constantly released into the environment, and their removal is a very difficult task because of the high cost of treatment methods. Various methods exist for the removal of toxic metal ions from aqueous solutions. Among these are adsorption using activated carbon, by far the most versatile and widely used method for the removal of toxic metals; however, it is relatively expensive and less feasible to use in developing countries. Furthermore, activated carbon loaded with toxicants is generally incinerated or disposed of on land, thereby causing environmental pollution through different routes. There is an urgent need to develop low-cost, effective, and sustainable methods for their removal or detoxification. The use of lignocellulosic agrowastes is a very useful approach, because of their high adsorption properties, which results from their ion-exchange capabilities. Agricultural wastes can be made into good sorbents for the removal of many metals, which would add to their value, help reduce the cost of waste disposal, and provide a potentially cheap alternative to existing commercial carbons. Although the abundance and very low cost of lignocellulosic wastes from agricultural operations are real advantages that render them suitable alternatives for the remediation of heavy metals, further successful studies on these materials are essential to demonstrate the efficacy of this technology.

Agriculture↗

Biological treatment of heavy metals in acid mine drainage using sulfate reducing bioreactors.

The uncontrolled release of acid mine drainage (AMD) from abandoned mines and tailing piles threatens water resources in many sites worldwide. AMD introduces elevated concentrations of sulfate ions and dissolved heavy metals as well as high acidity levels to groundwater and receiving surface water. Anaerobic biological processes relying on the activity of sulfate reducing bacteria are being considered for the treatment of AMD and other heavy metal containing effluents. Biogenic sulfides form insoluble complexes with heavy metals resulting in their precipitation. The objective of this study was to investigate the remediation of AMD in sulfate reducing bioreactors inoculated with anaerobic granular sludge and fed with an influent containing ethanol. Biological treatment of an acidic (pH 4.0) synthetic AMD containing high concentrations of heavy metals (100 mg Cu(2+)l(-1); 10 mg Ni(2+)l(-1), 10 mg Zn(2+)l(-1)) increased the effluent pH level to 7.0-7.2 and resulted in metal removal efficiencies exceeding 99.2%. The highest metal precipitation rates attained for Cu, Ni and Zn averaged 92.5, 14.6 and 15.8 mg metal l(-1) of reactor d(-1). The results of this work demonstrate that an ethanol-fed sulfidogenic reactor was highly effective to remove heavy metal contamination and neutralized the acidity of the synthetic wastewater.

Acids↗

[Intoxication and detoxication of heavy metals by humic acids].

Humic acids are naturally occurring phenol body polymerisates which form chelate compounds with heavy metals. Their wide occurrence in soils and surface waters has made them a major reactant to toxic and essential heavy metals in the biosphere. Humic acids, by ways of fixation or solution of trace elements or change of their own toxicological parameters, may exercise influence on ecological circulation, depending on both pH and ion strength of the medium concerned. While the detoxicating action of humic acids is likely to play the major role in natural ecosystems, their effects on heavy metal ion toxicity to experimental animals were found to depend on the technique of application. Enzymatically synthesized phenol body polymerisates are considered to be appropriate model substances for further studies into correlations between humic acids, on the one hand, and heavy metals, on the other.

Animals↗

[Effect of heavy metal cations on the activity of membrane Na+, K+ -ATPase in embryos of loach (Misgurnus fossilis L.)].

The activity of membrane Na+, K+ -ATPase of embryos of loach (Misgurnus fossilis L.) at early stages of development in the normal conditions and under the influence of heavy metal cations has been investigated. It was established, that the influence of such heavy metal cations as Ni2+, Co2+, Sn2+, Zn2+, Mn2+ and Cd2+ in concentrations 10(-6) - 10(-4) M results in reduction of activity of membrane Na+, K+ -ATPase of loach embryos. It was shown, that the inhibition effect is more expressed with the increase of concentrations of heavy metal cations in the incubation medium. The definition of inhibition constants Io.5 has allowed to analyze the sensitivity of Na+, K+ -ATPase to influence of various cations of heavy metals at different stages of blastomer division. Possible mechanisms of influence of heavy metal cations on the activity of membrane Na+, K+ -ATPase of loach embryos have been considered.

Animals↗

The adsorption of heavy metals by different sorbents under various incineration conditions.

The emission of heavy metals can be controlled by adding solid sorbents into the combustion chamber during incineration processes. The objective of this work was to experimentally study the adsorption efficiency of different sorbents for heavy metals under various incineration conditions. Each sorbent has its optimum operating temperature. Kaolinite and aluminum oxide have the best adsorption efficiency at 800 degrees C, and bauxite is at 700 degrees C. The adsorption efficiencies of the three sorbents for the four heavy metals all follow the sequence of Pb > Cu > Cr > Cd. The presence of inorganic chloride (NaCl) and sulfate (Na2SO4) increases the adsorption efficiency of the sorbents, but organic chloride PVC decreases the adsorption efficiency.

Adsorption↗