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The effects of heavy metals (in particular Pb, Cd, Cr, Mn and Hg) on pituitary, thyroid, adrenal gland, pancreas and gonads are reviewed. The effect of these metals on the CNS centers regulating endocrine function is emphasized. On this time, the reviewed data stress the importance of studying the mechanisms of preclinical damage and the biological markers of it.
ATP-driven heavy metal pumps represent a newly defined class of proteins that translocate toxic and essential metals across biological membranes. These transporters form a separate evolutionary branch of the ion-transporting P-type ATPases. We propose to call these enzymes CPx-type ATPases, based on the common novel feature of a conserved intramembranous cysteine-proline-cysteine or cysteine-proline-histidine motif.
From poisoning caused by lead-based paint on domestic buildings to groundwater contamination by naturally occurring arsenic deposits in India, heavy-metal toxicity is a global health problem. Contaminated ground water and acute cases of heavy-metal poisoning are treated with chelators to remove the heavy metals from the contaminated site or person. This review discusses the effort to generate heavy-metal chelators through peptide de novo design. De novo design entails the design of a primary sequence that will precisely fold into a predetermined secondary and tertiary protein structure. The first-generation peptide chelator used to initiate this investigation is the three-stranded coild coil containing Cys. Cys provides a potential trigonal binding site with soft thiolate ligands, which has been proposed to provide specific interactions with heavy metals. This hypothesis derives from the observation that similar sites on natural proteins show selectivity for heavy metals over other essential metals, such as Zn or Mg. A description of two systems, the TRI series and the IZ-AC peptide, is given, highlighting the interaction of these peptides with Hg, Cd, As and Pb. Arguments are also presented for the potential use of three-helix bundles as a second-generation design.
Wastewater treatment sludge contains valuable nutrients, yet represents a residue problem due to the amount of heavy metals, which is one of the factors preventing the use of sludge as fertilizer. In Sweden, the government has a declared aim of closing the ecocycles of nutrients to arable land, while at the same time the existing limit values are among the lowest in the world. This paper focuses on the opportunities for Swedish wastewater utilities (WWUs) to manage and reduce sources of heavy metals in order to get sludge approved and recycled. A case study focusing on sources of the heavy metals Cd, Cu, Hg, Ni, Pb, and Zn and the WWUs ability to influence the source by means of existing regulations was traced and categorized. A substantial fraction of the heavy metals were shown to be caused by diffuse emissions, such as the use of goods and products in society. For most sources discussed in the paper, a WWU can only manage the sources to a limited extent, if at all. This study shows that the WWUs cannot manage both recycling of nutrients and a decrease in heavy metals ending up in sludge. Diffuse emissions of heavy metals must be examined in context, not as a separate phenomenon or an issue for a single actor. The existing environmental legislation does not handle diffuse sources, yet long-term strategies for reducing the emissions to wastewater treatment must involve the reduction of diffuse emissions.
The effects of heavy metals, at sub-lethal concentrations, on activated sludge microbial ecosystem were investigated. Adsorption capacity and rate of copper, chromium, lead and zinc on microbial flocs were much faster than that of organic matters. Metals affected not only the adsorption rate of organic matters but also the COD adsorption capacity of the activated sludge. Effects of heavy metals, on wastewater treatment performance of a sequencing batch reactor were also studied. Metal-laden wastewater at sub-lethal levels affected the performance to different extents, depending on the hydraulic retention time. Metal ions acted as a strong competitor against the organic compounds for active sites on the bioflocs instead of acting as a toxic microbial inhibitor, thus hampering organic adsorption and affecting the COD removal efficiency under shorter HRTs.
Water-soluble salts of several heavy metals were examined for their ability to stain polypeptides resolved by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Brief gel exposure (5 min or less) to cobaltous acetate or chlorides of copper, nickel, and zinc produced negatively stained protein patterns that were qualitatively indistinguishable from those of parallel gels stained with Coomassie blue R-250. Protein patterns could be visualized less than 1 min after treatment of gels with zinc chloride; the threshold of detection was estimated at about 10-12 ng protein on standard-size slab gels. Test samples including human erythrocyte membranes, sialoglycoprotein (glycophorin) extracts, and commercial molecular weight protein standards were used to establish the scope of these stains. Protein patterns visualized by the heavy metal salts were compared and contrasted with profiles seen with three widely used silver stains. Proteins from gels treated with copper or zinc chloride could be easily recovered by simple diffusion; this makes feasible both analytical and preparative electrophoretic applications of the staining procedure. A mechanism is proposed to explain the observed protein staining by heavy metal salts.
Changes in soil heavy metal extractability following the cessation of biosolids applications were studied in a long-term field experiment. Two anaerobically digested biosolids from wastewater treatment plants in Madrid (Sur and Viveros) were applied to cropland from 1983 to 1990. Soil samples were collected in the 1st, 5th and 9th year after the last biosolids application. Soil pH did not vary significantly after biosolids applications. Organic matter and total heavy metals (Zn, Pb, Cd, Ni, Cr and Cu) concentrations initially increased but then declined over time, mostly after the first 5 years following biosolids application. Metal extracted with DPTA increased in Sur treatments during the 1st year and diminished thereafter. However, in Viveros treatments, heavy metals extracted increased during the 1st year, declined in 1995, and showed a slight increase in 1999. These changes in heavy metal extractability were widely observed in the percentage of extractable metal recovery (EMR). The differences observed in the pattern of the two sources of biosolids applied could be due to the different rates of decomposition of their organic matter.
The sintering process is used to stabilize the heavy metal in fly ash from municipal solid waste incinerator (MSWI). Migration characteristics of 6 targeted heavy metals (Cd, Pb, Cu, Ni, Cr and Zn) in the sintering process of MSWI fly ash were investigated by experiments. Effect of several factors including sintering temperature, residence time, molding pressure and particle diameter on the migration of heavy metals were discussed in details. The results show that cadmium and lead are volatile metals, while nickel, copper, chromium and zinc belong to involatilizable metals. The effects of sintering temperature, residence time, molding pressure and particle diameter on the stabilizing efficiency differ from each other. The study shows that most of heavy metals are stabilized during the sintering process. The stabilizing efficiency of heavy metals was different for different elements.
The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.
Heavy metals, such as iron and manganese, are involved in neurologic disease. Most often these diseases are associated with abnormal environmental exposures or abnormal accumulations of heavy metals in the body. There is increasing recognition that heavy metals normally present in the body also may play a role in disease pathogenesis through free radical formation. When a part of the brain known as the basal ganglia is affected, movements become disordered. Parkinson's disease is one of the most common movement disorders and is related to destruction of neurons in the substantia nigra pars compacta (SNpc) of the basal ganglia. The combination of high concentration of iron and the neurotransmitter, dopamine, may contribute to the selective vulnerability of the SNpc. Dopamine can auto-oxidize to produce free radicals particularly in the presence of iron and other heavy metals.
Amphibian populations appear to be declining around the world. Although there is no single cause, one factor may be pollution from heavy metals. As a result of mining in the Silver Valley of Idaho, heavy metals have been released into habitats containing many species of sensitive organisms, including spotted frogs (Rana luteiventris). While the gross extent of pollution has been well documented, the more subtle behavioral effects of heavy metals such as lead, zinc, and cadmium are less well studied. We tested the effects of heavy metals on the short-term survival (LC50) of spotted frog tadpoles. Compared to single metals, metals presented together were toxic at lower doses. We also raised the tadpoles in outdoor mini-ecosystems containing either a single heavy metal or soil from an EPA Superfund site in the Silver Valley known to be composed of numerous heavy metals. Exposure to Silver Valley soil resulted in delayed metamorphosis. We tested the ability of metal-exposed tadpoles to detect and respond to chemical cues emanating from predacious rainbow trout. We found that high levels of Silver Valley soil, medium levels of zinc, and medium and high levels of lead resulted in a decreased fright response. Low levels of cadmium, zinc, and lead did not cause a significant effect, but low levels of soil did result in a decreased fright response. Heavy metals may alter interactions between tadpoles and their predators.
The cell-permeant heavy metal chelator N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine(TPEN) was found to counteract phorbol ester-induced actin reorganization in PTK2 and Swiss 3T3 cells. By using fluorescence and the higher resolution technique of photoelectron microscopy to monitor actin patterns, 15-min pretreatment with 25-50 microM TPEN was found to dramatically reduce actin alterations resulting from subsequent phorbol ester treatment in PTK2 cells. Similar results were obtained with Swiss 3T3 cells using 50 microM TPEN for 1.5 h. Phorbol ester-induced actin alterations are thought to depend on activation of protein kinase C (PKC). In contrast to the phorbol ester effect, the PKC-independent actin cytoskeletal disruption caused by staurosporine and cytochalasin B was unaffected by TPEN pretreatment. TPEN did not block phorbol ester-induced activation of PKC in Swiss 3T3 cells, as observed by the phosphorylation of the 80K PKC substrate protein (MARCKS protein). TPEN also did not inhibit partially purified PKC from Swiss 3T3 cells in an in vitro PKC-specific commercial assay. To establish that the effect of TPEN is the removal of metal ions and not some other nonspecific effect of TPEN, a series of transition metal ions was added at the end of the TPEN pretreatment. The results indicate that the transient but dramatic phorbol ester-induced reorganization of the actin cytoskeleton in cultured cells depends on an interaction of PKC with a heavy metal, probably zinc.
The heavy metal uptake of ten plant species was studied under different soil and climatic conditions. Effects of soil pH, temperature, plant species and phenophase on the heavy metal content of stems and leaves were determined in pot experiments. Plants and soil samples were collected from a lead/zinc mine ore (Gyöngyösoroszi, Hungary) and characterised by high contents of Pb, Zn, As, Cd, Cu. The possibility of an adapted phytoremediation technology was indicated by different bioconcentration factors (BCF). The BCF depended markedly (10- to 100-fold) on plant species and environmental conditions. Based on our results a "season-adapted" phytoextraction technology with different plant species (utilising their different temperature requirements and/or harvest time) is suggested.
The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.
Agricultural and industrial activities cause heavy metal pollution of the aquatic environment. The sensitivity of crustaceans to heavy metals is well documented. However, the hormonal and metabolic target of physiological functions affected by sublethal toxicity and stress responses have been scarcely investigated. Exposure of Palaemon elegans to increasing concentrations of heavy metals dissolved in artificial sea water resulted in an order of toxicity tested by LC(50) for 96 h in intact and eyestalkless animals in which Hg is the most toxic, followed by Cd, Cu, Zn, and Pb. Eyestalkless animals were found to be more sensitive than intact individuals. Heavy metals affect the blood glucose levels, yet manipulative stress does not. The intermediate sublethal concentrations of Hg, Cd, and Pb produced significant hyperglycemic responses within 3 h, while the highest concentrations elicited no hyperglycemia in 24 h. In contrast, animals exposed to Cu and Zn showed hyperglycemia even at high concentrations. This difference in response between Cu or Zn and the nonessential heavy metals Cd, Hg, or Pb can probably be explained by the physiological roles of the former in crustaceans and by tolerance adaptations. Involvement of the crustacean hyperglycemic hormone (cHH) was tested by routine bioassay on eyestalkless individuals; each group was injected with a two-eyestalk-equivalent extract from control animals or from shrimp exposed to high concentrations of Cd, Hg, Pb, or low concentrations of Cu or Zn. All showed a hyperglycemic response within 2 h. In contrast, extracts of eyestalk removed from animals that had developed a full hyperglycemic reaction after exposure to low concentrations of Hg, Cd, Pb, or high concentrations of Cu and Zn were depleted of cHH as shown by the attenuation of the response after injection of the extracts into eyestalkless animals. This generalized and predictable sublethal response can be used as a quantitative physiological biomarker for water quality monitoring assessment.
Adsorption of heavy metals and redox reactions of Cr(W) ions on Fe-Mn nodules from five soils of China were investigated by chemical analysis, equilibrium adsorption/redox, and X-ray photoelectron spectroscopy (XPS). Results show that Mn is mainly present as Mn(3+) and Mn(4+) forms in Fe-Mn nodules. The maximum adsorption amounts for different heavy metal ions follow the order Pb(2+) approximately Cu(2+)>Zn(2+)>Co(2+)>Ni(2+)>Cd(2+). The adsorption capacity for heavy metals by Fe-Mn nodules from calciaquert in Shandong province (N5-1) is the highest, while that from hapludalf in Shandong province (N6-1) is the lowest. About 44-100% of the heavy metals adsorbed on Fe-Mn nodules were dissolved in 0.1 mol/L hydroxylamine hydrochloride (HAHC). The maximum amounts of Cr(VI) production by Fe-Mn nodules follow the order of N1-1 (69 mmol/kg)>N4-1 (57 mmol/kg)>N2-1 (52 mmol/kg)>N5-1 (44 mmol/kg). Based on the content of MnO(2) in Fe-Mn nodules dissolved in HAHC, the amount of Cr(VI) production by Mn oxides in N1-1, N2-1, N4-1, and N5-1 is 326, 624, 726, and 482 mmol/kg (MnO(2)), respectively. We propose that the amounts of Cr(VI) production through oxidation Cr(III) by Mn oxides are related to the types of Mn oxides in Fe-Mn nodules.
This study investigates the partition of heavy metals in both solid and gas phases in the flue gas from municipal solid waste (MSW) incinerators. Six MSW incinerators in Taiwan were examined and heavy metals in the flue gas at the inlets and outlets of air pollution control devices (APCDs) were analyzed. Heavy metals including Hg, Pb, Cd, Zn, Cu and Cr were sampled by USEPA Method 29 and further analyzed using inductively coupled plasma-mass spectroscopy (ICP-MS) and cold vapor atomic absorption spectrometry (CVAAS). Experimental results revealed that the removal efficiencies of the APCDs for the heavy metals Pb, Cd, Zn, Cu and Cr greatly exceeded 90%, but that of Hg did not. Two groups of heavy metals upstream of APCDs were observed. Pb, Cd, Zn, Cu and Cr were present mainly in the solid phase with a solid to gas ratio (S/G) of over 12.3. However, in most cases, mercury appeared mainly in the gas phase with an S/G ratio from 0.15 to 1.04, because it has a low boiling point. Additionally, treatment with the APCDs increased the S/G ratio of mercury because gaseous mercury could be removed by injecting powdered activated carbon (PAC) into the flue gas. Moreover, the distribution of particle sizes in the solid phase was bimodal. Finer particles (d(p) 2.5 microm) contained more Cr and Hg.
We assessed the capacity for heavy metals accumulation in Talorchestia ugolinii by standard methods of heavy metals analysis. To compare the bioaccumulation in syntopic sandhopper species, we collected samples of T. ugolinii and Talitrus saltator living on the same and on different beaches in Corsica. There was a marked difference in the zonal distribution of the two species along the sea-land axis of the beach: T. ugolinii was distributed nearer the water line than T. saltator. The bioaccumulation capacity of T. ugolinii only partly matched that of the Mediterranean T. saltator: while Hg, Zn, Cu, and Cd were accumulated by both species, Al and Fe were accumulated by T. saltator but not by T. ugolinii. Pb was accumulated only by T. ugolinii, while Cr did not seem to be accumulated by either species. The bioaccumulation in sympatric T. saltator and T. ugolinii specimens collected on the same beach reflected the general trend of the two species on the Tyrrhenian and Corsican coasts, respectively. Moreover, six of the eight heavy metals considered (Hg, Pb, Zn, Fe, Al, Cu) were present in higher quantities in T. ugolinii than in T. saltator, independently of whether the trace elements were accumulated by the two species. Thus, there are some differences between T. ugolinii and T. saltator, even when the two species live in the same locality. These differences involve their zonation within the damp belt of sand, the bioaccumulation of some heavy metals (Al, Pb, Fe), and the quantity of each heavy metal in the body, independent of the bioaccumulation capacity.