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An equation characterizing multi-heavy-metal sorption onto bentonite, forest soil and spruce bark.

An empirical equation was developed to quantitatively describe heavy metal sorption in ternary systems of lead (Pb), copper (Cu) and cadmium (Cd). The three sorbants investigated were bentonite, forest soil and spruce bark. This multi-sorption equation is based on three assumptions: the relationship between sorption and initial heavy metal concentration fits a power curve; the presence of one heavy metal proportionately reduces the sorption curve of another heavy metal; and the competition between two heavy metals is independent of the presence of other heavy metals. The multi-sorption equation modeled sorption in ternary systems to a regression fit greater than 0.96. The data required for the equation were generated from a technically straightforward and quick laboratory program involving batch adsorption tests.

Adsorption↗

Characteristics and mobility of heavy metals in an MSW landfill: implications in risk assessment and reclamation.

To assess the reclamation feasibility of a landfill, the characteristics, distribution, and mobility of heavy metals in the landfill were investigated. The refuse was characterized as containing high concentrations of heavy metals, a relatively high pH, and a high ratio of NH(4)-N to total nitrogen (TN). The results of heavy metal distribution showed that relatively high levels of heavy metals were accumulated in the landfill. Sequential extraction revealed that the relative amounts of heavy metals were different in the samples. Zn demonstrated the greatest mobility compared to other heavy metals, whereas Cd was well retained in the landfill. Leaching experiments indicated that the mobility of heavy metals in the landfill was generally low under normal neutral conditions. However, release of heavy metals can be increased greatly when medium conditions become more acidic and aerobic.

Chemical Fractionation↗

[Effects of stress duration and non-toxic ions on heavy metals toxicity to Arabidopsis seed germination and seedling growth].

The study on the toxicity of heavy metals Hg2+, Cd+, Cu2+ and Pb2+ to Arabidopsis se d germination and seedling growth showed that the test heavy metals had a stronger toxicity on seedling growth than on seed germination. The toxicity on seedlings was in order of Cu2+ > Hg2+ > Cd2+ /Pb2+, while on seeds was Hg2+ > Cd2+ > Pb2+/Cu2+. Seed germination rate was decreased with increasing stress duration, and different heavy metals showed different toxicity at different stress duration. For example, Hg2+ displayed a stronger toxicity at 12 - 24 h stress, while Cd2+ was at 0 - 12 h stress. It seemed that seed coat played an important role in seed tolerance to heavy metals. The interaction between non-toxic ions and heavy metal ions on seed germination showed that Ca2+, Mg2+, K+ and Na+ at 5 mmol x L(-1) could enhance the toxicity of Hg2+, but did not affect Cd2+ toxicity. For seedling growth, Ca2+, Mg2+, K+ and Na+ might enhance the toxicity of Hg2+, Ca2+ might alleviate the toxicity of Cd2+ but enhance the toxicity of Cu2+ , and K+ might alleviate Pb2+ toxicity. The mechanism of heavy metals injury was discussed in the paper.

Arabidopsis↗

Certain antioxidant enzymes of Allium cepa as biomarkers for the detection of toxic heavy metals in wastewater.

The utility of antioxidant enzymes, viz glutathione-S-transferase (GST), glutathione reductase (GR), superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), glutathione peroxidase (GPX), monodehydroascorbate reductase (MDHAR) and dehydroascorbate reductase (DHAR), as biomarkers of heavy metal pollution in water was investigated using the Allium cepa (onion) system. These antioxidant enzymes were assayed in onion bulbs exposed to certain heavy metals taken separately, the test metals taken in combination as well as the industrial wastewater especially found to contain these metals. GST exhibited significantly enhanced activity upon treatment with individual heavy metals. However, GR, SOD and CAT did not show such a pronounced increase in activities. At higher heavy metal concentrations, GR, SOD and CAT showed a steep decline while GST activity still showed a rise. Moreover, APX, GPX and MDHAR also exhibited remarkable induction with increase in the concentration of individual heavy metals. However, there was no significant change in DHAR activity with respect to the controls. Metabolites like ascorbate (ASC) and glutathione (GSH) exhibited significant decline with increase in the concentration of individual heavy metals while the level of H(2)O(2) continued to display the rise up to a heavy metal concentration of 100 microM, after which it showed a gradual decline. A. cepa bulbs treated with wastewater sample showed enzyme activity profiles similar to that shown with heavy metals, thereby suggesting the presence of heavy metals in the test wastewater. Atomic absorption spectrophotometry also detected large amounts of Cd, Cr, Cu, Hg, Pb and Zn in the test water sample. The metal mixture, containing the amounts of heavy metals equivalent to those found in the wastewater, resulted in steep declines in GR, SOD and CAT activities in A. cepa while GST showed a rise. However, when this metal mixture was diluted to 2000-fold, GR, SOD and CAT also showed enhanced activities compared with the controls. Contrary to the above finding, APX, GPX and MDHAR exhibited the rise in activities in A. cepa exposed to the metal mixture at all dilutions. In the presence of cycloheximide, all the enzymes returned to the levels of untreated controls while chloramphenicol did not have any effect on the test enzymes, thereby suggesting de novo protein synthesis of the test antioxidant enzymes in the cytosolic compartment of the cell as a result of exposure to the heavy metals.

Antioxidants↗

Heavy metals effects on forage crops yields and estimation of elements accumulation in plants as affected by soil.

Heavy metals (Cu, Cd, Pb, Zn) effect on the productivity of forage crops (clover and perennial cereal grasses) and their accumulation in plants, depending on the concentration of these elements in a soil, has been studied in micro-field experiments on three types of soil. The principle objective was to determine regularities of heavy metals migration in a soil-plant system aiming the estimation of permissible levels of heavy metals content in soils with the following elaboration of methods, which regulate the toxicants transfer to plants. Methods of field experiments, agrochemical and atomic absorption analysis were used. Results were statistically treated by Statistica 6.0, S-Plus 6. Experimental results have shown that the intensity of heavy metals accumulation in plants depends on the type of the soil, the species of plants, the physicochemical properties of heavy metals and their content in the soil. Logarithmic interdependency of heavy metals concentration in soils and their accumulation in plants is suggested. However, the strong correlation between the different heavy metals concentrations in the various soils and the yield of crops was not observed. Toxicants accumulation in crops decreased in time.

Crops, Agricultural↗

Coregionalization analysis of heavy metals in the surface soil of Inner Mongolia.

Due to potential problems associated with their deficiencies or toxicities, heavy metals in soils are of great environmental concern. To evaluate heavy metal contents and their relationships in the surface soil of Inner Mongolia, soil samples were collected from 344 sites and contents of copper, lead, zinc, cadmium, nickel, chromium, mercury, cobalt, vanadium and manganese were determined. In this article, coregionalization of these ten heavy metals is investigated using factorial kriging. Vegetation type, parent material type and soil pH, with respective characteristic ranges of 200, 400 and over 1000 km, are identified as the primary factors that control the spatial distribution of soil heavy metals. At the scale of 200 km, heavy metal relationships mainly reflect the result of biocycling. Their relationships at the intermediate scale (400 km) are thought to be derived from the atomic substitution of metals in the parent materials. Effects of soil pH on the adsorption of heavy metals by soil organic materials could explain their relationships at the large spatial scale (over 1000 km).

China↗

Interaction of polycyclic aromatic hydrocarbons and heavy metals on soil enzyme.

Actions and interactions of heavy metals (cadmium, zinc and plumbum) and polycyclic aromatic hydrocarbons (PAHs) [phenanthrene, fluoranthene, benzo(a)pyrene] on the soil urease and dehydrogenase activity were studied after 49 days exposure. The experimental approach was based on the uniform design which can cut the experiment time and improve the efficiency of experiments. Data treatment was essentially based on the multiple regression technique. The results showed that the action and interaction between heavy metals and PAHs were strongly dependent on the time of pollution. The dehydrogenase exhibits more sensitive to the combined pollution than urease. The negative interaction between Zn and Cd to hydrogenase activity and the combined stimulatory activity of Phenanthrene and Benzo(a)pyrene (or fluoranthene) to soil enzyme were observed. The interactions between Zn (Cd) and phenanthrene towards urease (dehydrogenase) were positive, and the interaction between Zn and benzo(a)pyrene to urease activity was negative. This study corresponds to exploratory phase in order to reveal interaction effects of heavy metals and PAHs on the soil enzyme and then to set up more in-depth analysis to increase progressively the understanding of the ecotoxicological mechanisms involved.

Bacteria↗

Metal-responsive transcription factor-1 (MTF-1) is essential for embryonic liver development and heavy metal detoxification in the adult liver.

Metal-responsive transcription factor-1 (MTF-1) activates the transcription of metallothionein genes and other target genes in response to heavy metal load and other stresses such as hypoxia and oxidative stress. It also has an essential function during embryogenesis: targeted disruption of Mtf1 in the mouse results in lethal liver degeneration on day 14 of gestation. Here we studied Mtf1 knockout mice at embryonic and adult stages, the latter by means of conditional knockout. Hepatocytes from Mtf1 null mutant and wild-type embryos were taken into culture on day 12.5 of gestation. Both initially appeared normal, but mutant cells were lost within a few days. Furthermore, Mtf1 null hepatocytes were poorly, if at all, rescued by cocultivation with wild-type rat embryo hepatocytes, indicating a cell-autonomous defect. When the Mtf1 gene was excised by Cre recombinase after birth in liver and bone marrow and to a lesser extent in other organs, mice were viable under non-stress conditions but highly susceptible to cadmium toxicity, in support of a role of MTF-1 in coping with heavy metal stress. An additional MTF-1 function was revealed upon analysis of the hematopoietic system in conditional knockout mice where leukocytes, especially lymphocytes, were found to be severely underrepresented. Together, these findings point to a critical role of MTF-1 in embryonic liver formation, heavy metal toxicity, and hematopoiesis.

Animals↗

Heavy metal contamination and distribution in the urban environment of Guangzhou, SE China.

Ever-increasing heavy metal accumulation in the urban environment of Guangzhou, the largest light industrial production base and one of the most rapidly developing cities in China, poses a serious threat to environment as well as to human health in the region. As a sink or source, urban deposits are good indicators of the level and extent of heavy metal accumulation in the surface environment. The aim of this preliminary study was to examine the distribution of heavy metal contamination in the urban environment of Guangzhou. It was based on a systematic sampling of road dusts and corresponding gully sediments along major roads running mainly through commercial and residential to industrial districts of the city. In addition to road dusts and gully sediments, ceiling dusts from the Pearl River Tunnel were also collected to characterize anthropogenic emissions dominated by traffic-related activities. In general, the level of Cd, Cu, Pb and Zn contaminations were more severe on the industrialized side of Guangzhou than on the western side where heavy traffic and industrial activities were limited. The primary determinants of the level of heavy metal contamination and the distribution of this contamination in the urban environment of Guangzhou were the site-specific conditions of its urban setting, particularly the types of industries, the nature of the traffic flow, sample residence times and variations in grain size of the particulate contaminants. This study highlights the complexity of the urban system and indicates that in just such a system individual urban components should be interlinked to assess the long-term environmental and health effects of heavy metal contamination. Among the heavy metals tested--Cd, Cu, Pb and Zn--the level of Zn contamination was the most severe and widespread, and thus requires immediate attention.

China↗

Study of a heavy metal biosorption onto raw and chemically modified Sargassum sp. via spectroscopic and modeling analysis.

In this study, raw and formaldehyde-modified Sargassum sp. are used for heavy metal removal. A series of experiments shows that the chemical modification by formaldehyde improves biosorption capacity by approximately 20%. Solution pH plays an important role in the metal uptake. According to X-ray photoelectron spectroscopic and Fourier transform infrared spectroscopic analysis, the possible organic functional groups in the metal binding include carboxyl, ether, alcoholic, hydroxyl, and amino functional groups. A new model that includes a series of coordination reactions among a generalized functional group, alkaline earth metal ions and heavy metal ions, is developed for simulation of biosorption process. The model well describes the single- and multiple-species metal biosorption process under different conditions such as pH. The biosorption of heavy metals is due to the ion exchange between the heavy metals and alkaline earth metals and their adsorption onto the free sites of the seaweeds. Slightly more than half of the metal uptake is due to ion exchange. The metal affinity for the functional groups follows a descending order of lead > copper > alkaline earth metal.

Biomass↗

Heavy metal content of combustible municipal solid waste in Denmark.

Data on the heavy metal composition of outlets from Danish incinerators was used to estimate the concentration of Zn, Cu, Pb, Cr, Ni, Cd, As and Hg in combustible waste (wet as received) at 14 Danish incinerators, representing about 80% of the waste incinerated in Denmark. Zn (1020 mg kg(-1)), Cu (620 mg kg(-1)) and Pb (370 mg kg(-1)) showed the highest concentration, whereas Hg (0.6 mg kg(-1)) showed the lowest concentration. The variation among the incinerators was in most cases within a factor of two to three, except for Cr that in two cases showed unexplained high concentrations. The fact that the data represent many incinerators and, in several cases, observations from a period of 4 to 5 years provides a good statistical basis for evaluating the content of heavy metals in combustible Danish waste. Such data may be used for identifying incinerators receiving waste with high concentrations of heavy metals suggesting the introduction of source control, or, if repeated in time, the data must also be used for monitoring the impacts of national regulation controlling heavy metals. It is recommended that future investigations consider the use of sample digestion methods that ensure complete digestion in order to use the data for determining the total heavy metal content of waste.

Denmark↗

Heavy-metal regulation of thioredoxin gene expression in chlamydomonas reinhardtii

Heavy metals are highly toxic compounds for cells. In this report we demonstrate that the expression of Chlamydomonas reinhardtii thioredoxins (TRX) m and h is induced by heavy metals. Upon exposure of the cells to Cd and Hg, a strong accumulation of both messengers was observed. Western-blot experiments revealed that among these two TRXs, only TRX h polypeptides accumulated in response to the toxic cations. A biochemical analysis indicated that heavy metals inhibit TRX activity, presumably by binding at the level of their active site. Sequence analysis of the C. reinhardtii TRX h promoter revealed the presence of cis-acting elements related to cadmium induction. The origins and purposes of this regulation are discussed. Our data suggest, for the first time to our knowledge, a possible implication of TRXs in defense mechanisms against heavy metals.

Journal Article↗

Modulation of cholecystokinin concentrations in the rat hippocampus by chelation of heavy metals.

Previously, we have reported that enkephalins, cholecystokinin, and heavy metals show roughly parallel distributional patterns in the hippocampus. A substantial body of evidence indicates that cholecystokinin-octapeptide (CCK-8) and enkephalins act as neurotransmitters. A CCK-8 degrading enzyme was recently detected in brain synaptosomes. Its activity depended on free thiol groups and the presence of a heavy metal. Since the heavy metal-containing neuropil is closely related to CCK-immunoreactive nerve terminals, we have investigated the effect of metal chelation on CCK components in the rat hippocampus. In vivo treatment of rats with a single dose of the chelating agent diethyldithiocarbamate caused a reversible chelation of heavy metals in the hippocampus. This effect was paralleled by a 3-fold increase in hippocampal content of CCK-8 and a smaller increase in the intermediate forms of CCK (CCK-58, CCK-39, CCK-33). Diethyldithiocarbamate also decreased the spontaneous motility and aggressiveness of the rats. These data show reversible changes of neuronal CCK processing by a drug, and hence they provide additional evidence that CCK is involved in the regulation of neuronal activities.

Animals↗

Heavy metal displacement in EDTA-assisted phytoremediation of biosolids soil.

Chelating agents are added to soil to solubilise the metals for enhanced phytoextraction. Yet no studies follow the displacement and leaching of heavy metals in soil with biosolids following solubilisation with chelates. The objective of this work was to determine the mobility of heavy metals in biosolids in a soil from a sludge farm that had received biosolids for 25 years. The soil was placed in columns in a greenhouse. Columns either had a plant (poplar) or no plant. After the poplar seedlings had grown for 144 d, the tetrasodium salt of the chelating agent EDTA was irrigated onto the surface of the soil at a rate of 1 g per kg of soil. Drainage water was analysed for three toxic heavy metals and four essential heavy metals. Without EDTA, concentrations of the seven heavy metals in the leachate from columns with or without plants were low or below detection limits. With or without plants, the EDTA mobilised all heavy metals and increased their concentration in drainage water. Without plants, the concentrations of Cd, Cu, Fe, and Zn in the leachate from columns with EDTA were above drinking-water standards. The presence of poplar plants in the soil reduced the concentrations of Cu, Fe, and Zn in the leachate so it fell within drinking-water standards. Concentrations of Cd and Pb in the leachate remained above drinking-water standards with or without plants.

Biodegradation, Environmental↗

Studies on heavy metal accumulation in aquatic macrophytes from Sevan (Armenia) and Carambolim (India) lake systems.

Aquatic macrophytes are unchangeable biological filters and they carry out purification of the water bodies by accumulating dissolved metals and toxins in their tissue. In view of their potential to entrap several toxic heavy metals, 45 macrophytes belonging to 8 families collected from two different physiographic locations (36 from Sevan Lake, Armenia; 9 from Carambolim Lake, Old Goa, India) were studied for estimation of 14 heavy metals. The study was aimed at understanding the importance of these macrophytes in accumulation of toxic metals and controlling the heavy metal pollution and suggesting the remedial measures, if any, for the preservation and restoration of lake ecosystem. Inductively Coupled Plasma-Atomic Emission Spectrometric (ICP-AES) analyses of these aquatic macrophytes have shown the importance of aquatic macrophytes in accumulation of heavy metals and maintaining the clarity of water bodies beside their role in trophic systems. Accumulation of most of the heavy metals was higher in root system. The representative macrophytes from two different physiographic locations show similar trends and order in accumulating different metals generally. Of the 14 metals investigated, 9 (Ca, Fe, Al, Cr, Cu, Ba, Ti, Co and Pb) showed higher rates of accumulation in the root whereas 3 (Mn, Zn and Mg) showed more accumulation in stem and 1 (Ca) showed higher accumulation in the leaves. In most of the samples Cu was accumulated more in the roots (50+/-47.15 microg/g) and less in flowers (9.52+/-3.97 microg/g). Occurrence of heavy metal was much higher in macrophytes of Sevan Lake than that of the Carambolim Lake. The accumulation of 14 elements was in order of Ca>Mg>Fe>Al>Mn>Ba>Zn>Ti>Cu>Cr>Co>Ni>Pb>Cd. The present study revealed that the aquatic macrophytes play a very significant role in removing the different metals from the ambient environments. They probably play a major role in reducing the effect of high concentration of heavy metals. Therefore, the macrophyte community of the Sevan Lake area needs to be protected and restored on a priority basis. Accumulation of highly toxic metals like--Cr, Cd, Pb and Ni was lower as compared to the essential metals like Ca, Fe and Mn in all the macrophytes from both the lake systems, consequently high metal concentrations observed in both the areas may not directly reflect on the pollution level.

Armenia↗

Removal of heavy metals from sewage sludge by acid treatment.

Sludge samples were found to contain significant amounts of heavy metals (Cr, Cu, Ni, Pb and Zn) and were subjected to acid treatment using either hydrochloric, sulfuric, nitric or phosphoric acid. The optimum combination, in terms of metal removal efficiency and environmental impacts was sought through a variety of tests by applying a ratio of 1:5 of sludge quantity (g) per volume of acid (ml). The concentrations of the different acids used, were in the range of 5%-20% and the contact times ranged between 15 and 60 minutes. The optimum combination was achieved when the sludge samples were in contact with H2SO4 20% v/v for 60 minutes. In order to estimate the metal leachability, the heavy metal content as well as the metal distribution in the residue were investigated and it was found that most of the heavy metal content was extracted while the remaining was removed from the initial mobile phases to the more stable ones.

Acids↗

Heavy metal transporters in Hemiascomycete yeasts.

We have compiled all known heavy metal transporters of the yeast Saccharomyces cerevisiae and identified their orthologs in four other species spanning the entire Hemiascomycete phylum. The 213 transporters belong to 27 distinct phylogenetic families distributed within the three classes: channels, secondary porters (permeases) and transport ATPases. They are present in all cellular membranes: plasma membranes, vacuoles, mitochondria, endoplasmic reticulum, nucleus, Golgi and various cytoplasmic vesicles. The major physiological heavy metals transported are: iron, manganese, zinc, copper, arsenite and cadmium. The major subfamilies that comprise the highest number of transporters are Siderophore-Iron Transporters (SIT) and CT2 (conjugated ABC transporters). They transport heavy metals (iron or cadmium, respectively) conjugated to organic chelators such as siderophores or glutathione. Both subfamilies are considerably amplified in the yeast Yarrowia lipolytica. The pattern of expansion and restriction of the subfamilies during the evolution of the different species is highly variable. The phylogenetic trees of the major transporters subfamilies distinguish homogenous clusters of transporters suggesting that possible different physiological or mechanistic functions evolved independently. We also validated the use of the Hemiascomycetes heavy metal transporters for identification of orthologs transporters in the pathogenic Basidiomycetes Cryptococcus neoformans.

Ascomycota↗

Chelant extraction of heavy metals from contaminated soils.

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique.

Chelating Agents↗