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Growth-related changes in heavy metal accumulation in green turtle (Chelonia mydas) from Yaeyama Islands, Okinawa, Japan.

Concentrations of nine heavy metals (Fe, Mn, Zn, Cu, Pb, Ni, Cd, Co, and Hg) were determined in liver, kidney, and muscle of 50 green turtles (Chelonia mydas) collected from Yaeyama Islands, Okinawa, Japan, to elucidate growth-related changes in heavy metal accumulation during different growth stage. Considerably high Cu concentrations were found in the liver of smaller turtles. Mean hepatic concentration of Cu was 50.2 microg/g wet weight which varied widely (4.27-113 microg/g wet weight). Cadmium concentrations decreased with increasing the carapace length. The juvenile green turtles in the pelagic ocean are likely feed on zooplankton, while adult coastal inhabiting green turtles mainly feed on sea grasses and seaweeds. Concentrations of Cd in sea plants are lower than those in zooplankton. The specific accumulation of Cd found in the green turtle seems to be attributable to their feeding habit, which is a shift from carnivore to herbivore at different growth stages.

Aging↗

Extraction of heavy metals from soils using biodegradable chelating agents.

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.

Biodegradation, Environmental↗

Allozyme polymorphisms and heavy metal levels in the green-lipped mussel Perna viridis (Linnaeus) collected from contaminated and uncontaminated sites in Malaysia.

It has been widely reported that heavy metal contamination in coastal waters can modify the allozyme profiles of marine organisms. Previous studies have recorded elevated metal concentrations in sediments and mussel tissues off Peninsular Malaysia. In the present study, horizontal starch gel electrophoresis was carried out to estimate the levels of allelic variation of the green-lipped mussel, Perna viridis, collected from one contaminated and three relatively uncontaminated sites off Peninsular Malaysia. Fourteen polymorphic loci were observed. In addition, the concentrations of cadmium, copper, lead, mercury and zinc were determined in the sediments and in the soft tissues of the mussels. Mussels from contaminated site, evidenced by high metal pollution indices (MPI) of the sediment and the mussel tissues, showed the highest percentage of polymorphic loci (78.6%), while those collected from the uncontaminated sites had lower MPI of the sediment and mussel tissue, and exhibited lower percentages of polymorphic loci (35.7-57.1%). The population from the contaminated site showed the highest excess of heterozygosity (0.289) when compared to that of the populations from the three uncontaminated sites (0.108-0.149). Allozyme frequencies at the phosphoglucomutase (PGM; E.C. 2.7.5.1) locus also differed between the contaminated and uncontaminated populations. Previous studies have shown that exposure to heavy metals can select or counter-select for particular alleles at this locus. The present results suggest that allozyme polymorphism in P. viridis is a potential biomonitoring tool for heavy metal contamination but further validation is required.

Animals↗

Effects of heavy metal pollution on swimming and longevity in cercariae of Cryptocotyle lingua (Digenea: Heterophyidae).

Effects of heavy metal pollution on the cercariae of the marine trematode Cryptocotyle lingua (Creplin) were studied by measuring horizontal swimming rate (HSR) and longevity. These factors are important for transmission to the next host, a fish. Cercariae released by Littorina littorea (L.) collected from polluted and unpolluted sites were compared. Both HSR and longevity were significantly reduced in cercariae from the polluted environment. Cercarial quality was therefore reduced, directly or indirectly, by development within a metal-accumulating host. Cercariae released by hosts from a clean environment were subjected to nominal concentrations of 2 and 3 mg/l copper, 1 and 2 mg/l zinc, 2 and 5 mg/l iron and 2 and 4 mg/l manganese in artificial seawater. In all cases the HSRs and longevity were reduced. The effect was more pronounced in the higher concentrations. The significant HSR tests indicate that the absorption and effect of metals occurred within 1 min. The cercarial tegument, specialized for absorption in endoparasitic environments, is possibly responsible. Cercariae may therefore be excellent indicator organisms for pollution. The pollution-induced reductions in cercarial quality seem capable of producing transmission failure. Heavy metal pollution could therefore alter parasite populations and communities.

Animals↗

Retention of three heavy metals (Zn, Pb, and Cd) in a calcareous soil controlled by the modification of flow with geotextiles.

Although geotextiles are increasingly employed in stormwater infiltration basins, their influence on the flow and transfer of contaminants, such as heavy metals, has not been fully investigated. Leaching column experiments were conducted to characterize the flow and transfer of three heavy metals (zinc, lead, and cadmium) in a calcareous soil with and without geotextiles under steady-state flow and close to saturation forthe soil. The influence of geotextiles was characterized for two types of geotextiles (needlepunched and thermosealed) and for two different initial saturation degrees for the needlepunched geotextile. The main results showed that, when placed wet, the needlepunched geotextile had no influence. When placed dry, it homogenized the flow in its surroundings and thus allowed better contact between heavy metals and the reactive soil, resulting in an increase of their retention. The thermosealed geotextile, placed dry, homogenized the flow and increased retention over a larger area, resulting in optimal global retention. In conclusion, geotextiles could be used in infiltration basins, provided that their effect on both flow and heavy metal retention is optimized by appropriate design--choice of geotextiles--and appropriate monitoring--control of hydric conditions.

Adsorption↗

The structure and function of heavy metal transport P1B-ATPases.

P(1B)-type ATPases transport heavy metals (Cu+, Cu2+, Zn2+, Co2+, Cd2+, Pb2+) across membranes. Present in most organisms, they are key elements for metal homeostasis. P(1B)-type ATPases contain 6-8 transmembrane fragments carrying signature sequences in segments flanking the large ATP binding cytoplasmic loop. These sequences made possible the differentiation of at least four P(1B)-ATPase subgroups with distinct metal selectivity: P(1B-1): Cu+, P(1B-2): Zn2+, P(1B-3): Cu2+, P(1B-4): Co2+. Mutagenesis of the invariant transmembrane Cys in H6, Asn and Tyr in H7 and Met and Ser in H8 of the Archaeoglobus fulgidus Cu+-ATPase has revealed that their side chains likely coordinate the metals during transport and constitute a central unique component of these enzymes. The structure of various cytoplasmic domains has been solved. The overall structure of those involved in enzyme phosphorylation (P-domain), nucleotide binding (N-domain) and energy transduction (A-domain), appears similar to those described for the SERCA Ca2+-ATPase. However, they show different features likely associated with singular functions of these proteins. Many P(1B)-type ATPases, but not all of them, also contain a diverse arrangement of cytoplasmic metal binding domains (MBDs). In spite of their structural differences, all N- and C-terminal MBDs appear to control the enzyme turnover rate without affecting metal binding to transmembrane transport sites. In addition, eukaryotic Cu+-ATPases have multiple N-MBD regions that participate in the metal dependent targeting and localization of these proteins. The current knowledge of structure-function relationships among the different P(1B)-ATPases allows for a description of selectivity, regulation and transport mechanisms. Moreover, it provides a framework to understand mutations in human Cu+-ATPases (ATP7A and ATP7B) that lead to Menkes and Wilson diseases.

Adenosine Triphosphatases↗

Evaluation of ettringite and hydrocalumite formation for heavy metal immobilization: literature review and experimental study.

The immobilization of heavy metal oxyanions like chromate, arsenate and selenate, has proven to be a challenging task as they are highly mobile in alkaline environments involving S/S of contaminated media. Ettringite, a pozzolanic phase that forms in cementitious materials, has been proposed as a viable immobilization mechanism for oxyanions, wherein the oxyanion may substitute for sulfate in the ettringite structure. A literature review on the immobilization potential of ettringite showed that the substitution potential exists from the thermodynamic point of view where the formation of substituted ettringites occurs under strictly controlled conditions. The pH control over a narrow range is essential for ettringite stability; it becomes even narrower for substituted ettringites, as competing effects with sulfate ettringite and monophases are significantly affected by pH. The presence of sulfate has a catalytic effect on oxyanion incorporation in ettringite. Rapid leaching may occur when the treated media is exposed to sulfate influx. Conversely, monophases seem to be more suitable than ettringite for oxyanion immobilization, mainly as they control oxyanion solubility to lower levels than ettringite. A shift to the thermodynamic equilibrium caused by a shift in environmental conditions may result in monophase conversion to ettringite, which may lead to catastrophic expansion, as widely demonstrated in the cement and soils literature. Overall, the sensitivity of phase equilibria in cement-like systems involving oxyanions is significant with regard to multiple parameters and it is uncertain to what extent these can be predicted and/or controlled in the field.

Calcium Compounds↗

Effect of acclimatization of microorganisms to heavy metals on the performance of activated sludge process.

Although selected heavy metals (HMs) stimulate biological reactions at low concentrations, all HMs are toxic to microorganisms (MOs) at moderate concentrations and can cause inhibitory effects on the biological processes. Therefore, MOs must be acclimated to HMs or other toxic substances present in wastewaters (WWs) before they are used in an activated sludge process (ASP). In this study, combined effect of Cu(2+) and Zn(2+) ions in a synthetic WW on the efficiency of a laboratory-scale ASP without recycle was investigated using acclimated MOs at different extents.A synthetic feed solution of 1222 mg L(-1) proteose-peptone (corresponding to 1300 mg COD L(-1)) served as a source of carbon. Cu(2+) and Zn(2+) ions at different concentrations (1.5, 4.5 and 9, 27 mg L(-1), respectively) were introduced in the feed to a continuously stirred activated sludge reactor at different hydraulic residence times (2-40 h) keeping pH, temperature and stock feed composition constant. The combined effects of copper and zinc ions were determined by mixing these metallic ions at the specified combinations of concentrations such as "1.5 mg L(-1) of Cu(2+)+9 mg L(-1) of Zn(2+)" and "4.5 mg L(-1) of Cu(2+)+27 mg L(-1) of Zn(2+)". It was observed that using seed MOs acclimatized to two times of the combined threshold concentration of these HMs for an unduly long period of time (1-4 months) caused adverse effects on the ASP performance. Besides, it was found that usual inhibition effects of these HMs were enhanced with increasing period of acclimation. Substantially lower substrate removal efficiencies were obtained with acclimatized MOs than those obtained with non-acclimatized MOs. At the higher initial substrate concentration of 2500 mg COD L(-1), substrate-inhibition occurred causing a decrease in the specific growth rate constant (k); however, HM inhibition was suppressed, resulting to about 20% increase in treatment efficiency of the ASP. It can be concluded that the time period necessary for acclimatization of seed MOs must be adjusted carefully with concentrations of HMs lower than their threshold concentrations to achieve an optimal operation of an aerobic biological process.

Adaptation, Physiological↗

The effect of heavy metals on nitrogen and oxygen demand removal in constructed wetlands.

The objective of this study is to investigate the respective effects of Zn, Pb and Cd as well as the combined effect of Zn, Pb, Cd and Cu on the removal of nitrogen and oxygen demand in constructed wetlands. Four laboratory-scale gravel-filled subsurface-flow constructed wetland units planted with cattails (Typha latifolia) were operated outdoors and fed with primary-treated domestic wastewater at a constant flow rate of 25 ml/min. After 6 months, three of the wetland units were fed with the same type of wastewater spiked with Zn(II), Pb(II) and Cd(II), respectively, at 20, 5 and 1 mg/l for a further 9 months. The remaining unit was fed with the same type of wastewater spiked with a combination of Zn(II), Pb(II), Cd(II) and Cu(II) at concentrations of 10, 2.5, 0.5 and 5 mg/l, respectively, over the same period. The chemical oxygen demand (COD) and ammoniacal nitrogen (AN) concentrations were monitored at the inlet, outlet and three additional locations along the length of the wetland units to assess the performance of the wetland units at various metal loadings. At the end of the study, all cattail plants were harvested for the determination of total Kjeldahl nitrogen and metal concentrations. The results showed that the COD removal efficiency was practically independent of increasing metal loading or a combination of metal loadings during the duration of the study. In contrast, the AN removal efficiency deteriorated progressively with increasing metal loading. The relative effect of the heavy metals was found to increase in the order: Zn<Pb<Cd and the synergistic effect of metals was not observed. The metals seem to exhibit some inhibitory effect on nitrogen uptake by cattail plants as indicated by lower nitrogen uptake rates in comparison to rates recorded in wetland systems treating domestic wastewater only.

Ecosystem↗

Relevance of joint action toxicity evaluations in setting realistic environmental safe limits of heavy metals.

The evaluation of types of toxicological interactions existing between heavy metals, which are prominent in effluents of some industrial establishments in Lagos State, Nigeria and the Lagos lagoon sediment was carried out against benthic animals, Tympanotonus fuscatus, Clibanarius africanus and Sesarma huzardi of the Lagos lagoon. In order to determine the type of interactions existing between the metals, acute toxicity tests of the metal compounds when acting singly and in joint action studies, by adopting mixture ratios that depict (i) the proportions of the concentrations of the metal ions in the sediment of the Lagos lagoon and (ii) equitoxic mixtures, i.e. based on the 96 hLC(50) values of the metal compounds under single action studies were carried out in laboratory biotests. The joint action evaluations of the test metal mixtures, prepared on the basis of the proportion of the availability of the metals ions in lagoon sediment and equitoxic ratio against the test animals agreed mainly with the model of antagonism (reduction in toxicity) except for test mixtures prepared on the basis of equitoxic ratio and tested against T. fuscatus, where interactions between the test metals was in conformity with the model of synergism, indicating that the toxicity of the constituent metals in the mixture was enhanced. Furthermore, on the basis of classification of synergistic ratio model, the toxic effect of Pb compound which was the least toxic metal compound in the single action toxicity studies was found to be enhanced (synergised) in the presence of other metals when tested jointly. The significance of the results in setting water quality criteria aimed at protecting aquatic biota was discussed.

Animals↗

Biosorption of heavy metals using whole mold mycelia and parts thereof.

Biosorption of heavy metals was carried out using whole mycelia and selected components of Aspergillus niger, Rhizopus oryzae and Mucor rouxii. Binding of copper, cadmium, nickel and zinc was considerably improved by treating the cell wall fraction with 4 M NaOH at 121 degrees C. Chitosan contributed most to the biosorptive capacity. 0.96 mmol copper was bound by 1 g of the treated mycelium of M. rouxii DSM 1191.

Aspergillus niger↗

Separation of heavy metals from water solutions at the laboratory scale.

Separation of heavy metals from water may be done by sulphide precipitation. In order to make the metal sulphides more valuable for reuse, they should be as pure as possible. To separate the metals from each other during the precipitation process different parameters as pH, sulphide concentration and redox potential may be controlled. Adjustment of the redox potential to specific values results in separation of copper from cadmium even at the same pH. In the copper precipitation step 98.7 +/- 0.5% was precipitated and the remaining part was transferred to the cadmium precipitation step where 0.7 +/- 0.5% of the copper precipitated. The main part of cadmium (95.6 +/- 1.3%) was precipitated in the second step. These results show that it is possible to separate copper from cadmium by the use of redox potential control.

Cadmium↗

Stenotrophomonas maltophilia D457R contains a cluster of genes from gram-positive bacteria involved in antibiotic and heavy metal resistance.

A cluster of genes involved in antibiotic and heavy metal resistance has been characterized from a clinical isolate of the gram-negative bacterium Stenotrophomonas maltophilia. These genes include a macrolide phosphotransferase (mphBM) and a cadmium efflux determinant (cadA), together with the gene cadC coding for its transcriptional regulator. The cadC cadA region is flanked by a truncated IS257 sequence and a region coding for a bin3 invertase. Despite their presence in a gram-negative bacterium, these genetic elements share a common gram-positive origin. The possible origin of these determinants as a remnant composite transposon as well as the role of gene transfer between gram-positive and gram-negative bacteria for the acquisition of antibiotic resistance determinants in chronic, mixed infections is discussed.

Anti-Bacterial Agents↗

Extracellular heavy-metal ions stimulate Ca2+ mobilization in hepatocytes.

Populations of hepatocytes in primary culture were loaded with fura 2 and the effects of extracellular heavy-metal ions were examined under conditions that allowed changes in fura 2 fluorescence (R340/360, the ratio of fluorescence recorded at 340 and 360 nm) to be directly attributed to changes in cytosolic free [Ca2+] ([Ca2+]i). In Ca2+-free media, Ni2+ [EC50 (concentration causing 50% stimulation) approximately 24+/-9 microM] caused reversible increases in [Ca2+]i that resulted from mobilization of the same intracellular Ca2+ stores as were released by [Arg8]vasopressin. The effects of Ni2+ were not mimicked by increasing the extracellular [Mg2+], by addition of MnCl2, CoCl2 or CdCl2 or by decreasing the extracellular pH from 7.3 to 6.0; nor were they observed in cultures of smooth muscle, endothelial cells or pituitary cells. CuCl2 (80 microM), ZnCl2 (80 microM) and LaCl3 (5 mM) mimicked the ability of Ni2+ to evoke Ca2+ mobilization. The response to La3+ was sustained even in the absence of extracellular Ca2+, probably because La3+ also inhibited Ca2+ extrusion. Although Ni2+ entered hepatocytes, from the extent to which it quenched fura 2 fluorescence the free cytosolic [Ni2+] ([Ni2+]i) was estimated to be <5 nM at the peak of the maximal Ni2+-evoked Ca2+ signals and there was no correlation between [Ni2+]i and the amplitude of the evoked increases in [Ca2+]i. We conclude that extracellular Ni2+, Zn2+, Cu2+ and La3+, but not all heavy-metal ions, evoke an increase in [Ca2+]i in hepatocytes by stimulating release of the hormone-sensitive intracellular Ca2+ stores and that they may do so by interacting with a specific cell-surface ion receptor. This putative ion receptor may be important in allowing hepatocytes to contribute to regulation of plasma heavy-metal ions and may mediate responses to Zn2+ released into the portal circulation with insulin.

Adenosine Triphosphate↗

Use of nonionic poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X-1 00) surfactant mobile phases in the thin-layer chromatography of heavy-metal cations.

The analytical potential of poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X-100), a nonionic surfactant, is used as a mobile phase in the thin-layer chromatographic separation of heavy-metal cations. The surfactant concentration below its critical micellar concentration (CMC) as well as above the CMC value is used to investigate the migrational behavior of some heavy-metal ions on silica gel layers. The mobility of the metal ions is found to change marginally with the increase of surfactant concentration from 0.001M (below CMC) to 0.1M (above CMC). The influence of the pH of the medium, nonelectrolyte organic (urea and alkanols), and inorganic electrolyte (NaCI) additives in the surfactant containing mobile phase on the mobility of heavy metals on the silica gel layer is examined. For separating metal ions, surfactant must be used in the presence of buffers. Triton X-100 (0.02M) at pH 2.3 is found to be the best mobile phase for the separation of heavy-metal cations. In general, the presence of alcohol in aqueous surfactant solutions results in a decrease in the mobility of metal ions. Besides Cu2+ and Fe3+, all of the metal ions show a trend of increasing the retardation factor beyond a minima at 0.1 or 0.3M of added urea or NaCl. The proposed method is successfully applied for the simultaneous detection of Zn2+ and Cd2+ from a spiked human blood sample.

Journal Article↗

Sulfhydryl-reactive heavy metals increase cell membrane K+ and Ca2+ transport in renal proximal tubule.

The cellular mechanisms by which nephrotoxic heavy metals injure the proximal tubule are incompletely defined. We used extracellular electrodes to measure the early effects of heavy metals and other sulfhydryl reagents on net K+ and Ca2+ transport and respiration (QO2) of proximal tubule suspensions. Hg2+, Cu2+, and Au3+ (10(-4)M) each caused a rapid net K+ efflux and a delayed inhibition of QO2. The Hg2(+)-induced net K+ release represented passive K+ transport and was not inhibited by barium, tetraethylammonium, or furosemide. Both Hg2+ and Ag+ promoted a net Ca2+ uptake that was nearly coincident with the onset of the net K+ efflux. A delayed inhibition of ouabain-sensitive QO2 and nystatin-stimulated QO2, indicative of Na+, K(+)-ATPase inhibition, was observed after 30 sec of exposure to Hg2+. More prolonged treatment (2 min) of the tubules with Hg2+ resulted in a 40% reduction in the CCCP-uncoupled QO2, indicating delayed injury to the mitochondria. The net K+ efflux was mimicked by the sulfhydryl reagents pCMBS and N-ethylmale-imide (10(-4) M) and prevented by dithiothreitol (DTT) or reduced glutathione (GSH) (10(-4) M). In addition, both DTT and GSH immediately reversed the Ag(+)-induced net Ca2+ uptake. Thus, sulfhydryl-reactive heavy metals cause rapid, dramatic changes in the membrane ionic permeability of the proximal tubule before disrupting Na+, K(+)-ATPase activity or mitochondrial function. These alterations appear to be the result of an interaction of the metal ions with sulfhydryl groups of cell membrane proteins responsible for the modulation of cation permeability.

Animals↗

Effects of heavy metals on methane production in tropical rice soils.

In a laboratory incubation study, the effect of select heavy metals on methane (CH(4)) production in three rice soils was investigated under flooded conditions. Heavy metals behaved differently in their effect on methanogenesis in different soils and methane-producing bacteria. Cd, Cu, and Pb inhibited CH(4) production in all the soils. Zn stimulated CH(4) production in the alluvial soil, but inhibited it in laterite and acid sulfate soils. Cr effectively inhibited CH(4) production in the alluvial soil, but stimulated it in laterite and acid sulfate soils. The stimulatory effect of Zn and the inhibitory effect of Cr on methanogenesis in alluvial soil were attributed to their stimulation or inhibition of methanogenic bacterial population.

Bacteria↗