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PubMed1999

Mineral surfaces and bioavailability of heavy metals: a molecular-scale perspective.

There is a continual influx of heavy metal contaminants and pollutants into the biosphere from both natural and anthropogenic sources. A complex variety of abiotic and biotic processes affects their speciation and distribution, including adsorption onto and desorption from mineral surfaces, incorporation in precipitates or coprecipitates, release through the dissolution of minerals, and interactions with plants and microbes. Some of these processes can effectively isolate heavy metals from the biosphere, whereas others cause their release or transformation to different species that may be more (or less) bioavailable and/or toxic to organisms. Here we focus on abiotic adsorption and precipitation or coprecipitation processes involving the common heavy metal contaminant lead and the metalloids arsenic and selenium in mine tailings and contaminated soils. We have used extremely intense x-rays from synchrotron sources and a structure-sensitive method known as x-ray absorption fine structure (XAFS) spectroscopy to determine the molecular-level speciation of these elements at concentrations of 50 to several thousand ppm in the contaminated environmental samples as well as in synthetic sorption samples. Our XAFS studies of As and Pb in the mine tailings show that up to 50% of these contaminants in the samples studied may be present as adsorbed species on mineral surfaces, which makes them potentially more bioavailable than when present in sparingly soluble solid phases. Our XAFS studies of Se(VI) sorption on Fe2+-containing sulfates show that this element undergoes redox reactions that transform it into less bioavailable and less toxic species. This type of information on molecular-level speciation of heavy metal and metalloid contaminants in various environmental settings is needed to prioritize remediation efforts and to assess their potential hazard to humans and other organisms.

Journal Article↗

PubMed2001

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals.

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.

Biodegradation, Environmental↗

PubMed2006

Microwave enhanced stabilization of heavy metal sludge.

A microwave process can be utilized to stabilize the copper ions in heavy metal sludge. The effects of microwave processing on stabilization of heavy metal sludge were studied as a function of additive, power, process time, reaction atmosphere, cooling gas, organic substance, and temperature. Copper leach resistance increased with addition of aluminum metal powder, with increased microwave power, increased processing time, and using a gaseous environment of nitrogen for processing and air for cooling [N2/air]. The organic in the sludge affected stabilization, whether or not the organic smoldered. During heating in conventional ovens, exothermic oxidation of the organic resulted in sludge temperatures of about 500 degrees C for oven control temperatures of 200-500 degrees C. After microwave heating dried the sludge, the sludge temperature rose to 500 degrees C. The reaction between copper ions and metal aluminum in the dried sludge should be regarded as a solid phase reaction. Adding aluminum metal powder and reaction temperature were the key parameters in stabilizing copper in the heavy metal sludge, whether heated by microwave radiation or conventional oven. The mass balance indicates insignificant volatization of the copper during heating.

Aluminum↗

PubMed1996

Decomposer animal communities in forest soil along heavy metal pollution gradient.

Responses of soil decomposer animals to heavy metal contamination and to concomitant changes in organic matter quality and quantity and in soil microbial biomasses have been studied along a pollution gradient from a Cu-Ni smelter. Samples have been taken separately for nematodes, enchytraeids and microarthropods 0.5, 2 and 8 km from the smelter. Special attention has been paid to the changes in the collembolan fauna. The sampling sites have been located in homogeneous Scots pine ( Pinus sylvestris) forests with podsolic soil profiles. In addition, an experiment has been carried out in which intact soil cores have been transferred in mesh baskets between the sites 2 and 8 km from the smelter (control samples have been transferred within the sites). Although most soil animals seemed to be quite resistant to direct and indirect effects of heavy metals, results indicate that certain soil animals like enchytraeids can be useful and easy to monitor when the effects of heavy metals on soil decomposition systems are assessed.

Journal Article↗

PubMedDate not supplied

[The effect of the trematode invasion and accumulation of heavy metals onto the pond snail (Mollusca: Gastropoda: Lymnaeidae)].

The cumulating of heavy metals (Cu, Cd, Pb, Zn) by the pond snail Lymnaea stagnalis from river and pond populations in a norm and under the trematode infection was examined. The copper and cadmium were accumulated by all specimens, mainly in the mantle and leg, in less content--in the hepatopancreas, and in the least content--in the shell and haemolymph. The lead was accumulated most intensively by the river specimens in the shell and mantle, while in the pond specimens it was accumulated in the mantle and leg. The greatest content of zink was found in the mantle, leg, and hepatopancreas. According to the ratio of cumulation the heavy metals by the river and pond populations the following series of ions were obtained respectively: Pb > Zn > Cu > Cd and Zn > Pb > Cu > Cd. The difference between uninfected specimens and one infected with trematodes was recorded in the ratio of cumulated heavy metals, in the ratio of benthic biological accumulation, and also based on bending force between metals compared in pairs. An intensity of differences was directly proportional to the intensity of the trematode infection.

Animals↗

PubMed2004

Concentrations of heavy metal and radioactivity in surface water and sediment of Hazar Lake (Elaziğ, Turkey).

Concentration of heavy metals and natural gross radioactivity were measured in the surface water and sediment of Hazar Lake (Elaziğ, Turkey). Eight sampling sites were pre-defined in different locations of the lake. A preliminary study on heavy metals (Zn, Fe, Mn, Ni, Cu, Cr, Co and Pb), major elements (Na, K, Ca, Mg) concentrations and natural radioactivity related to 226Ra, gross-alpha and gross-beta radiations in the surface water and deep sediments were determined. The obtained results showed that, in general, the heavy metals (Zn, Fe, Mn, Ni, Cu and Pb) and major elements (Na, K, Ca, Mg) concentrations in water did not exceed WHO (World Health Organization, 1999), EC (Europe Community, 1998), EPA (Environment Protection Agency, 2002) and TSE-266 (Turkish Standard, 1997) guidelines. Generally, heavy metals and major elements concentration of the sediments were found decrease in sequence of Fe>Mg>Ca>Mn>Zn>Ni>Cr>Cu>Co>Pb. The results of this study indicated that a general absence of serious pollution in the Hazar Lake. The results obtained from the radioactivity determination indicate that the surface water radioactivity concentration of 226Ra, gross-alpha and gross-beta were ranging from 0.52+/-0.02 to 2.02+/-0.06 Bq/l and from 0.65+/-0.03 to 2.52+/-0.07 Bq/l and from 0.01+/-0.01 to 0.14+/-0.01 Bq/l, respectively. Deep sediment radioactivity concentrations of 226Ra is ranging from 0.07+/-0.03 to 0.32+/-0.07 Bq/g.

Environmental Monitoring↗

PubMed2005

[Distribution and characters of heavy metals from municipal solid waste incinerator fly ash].

The distribution and characters of heavy metals from municipal solid waste incinerator fly ash was studied in East China. The result indicate that heavy metals in fly ash were mainly distributed in fine particles. The heavy metals including Cd, Pb, Mg, and Cu could migrate easily from fly ash while Ag and Sn would be more stable. The metal mobility changed with the pH level. For environmentally important metals such as Cd, Co, Cu, Mn, Ni, Pb, and Zn, the increase in mobility due to the decrease in pH was more pronounced and significant than for other elements, while Cr and As with the opposite condition.

Air Pollutants↗

PubMedDate not supplied

Distribution of heavy metal concentrations in surface sediments in Dubai Creeks, United Arab Emirates.

Dubai is developing rapidly and many developmental activities are concentrated around its Creek. The present study reports the lateral distribution of heavy metals and compares it with local historical record of heavy metal concentrations. For this purpose surface sediment samples were collected and analyzed for metal contents, total organic carbon content (TOC), mineralogy and grain size. The percentages of the different grain size fraction of the collected sediments were as follow 65% for sand size, 15% for silt size fraction, and the rest accounted for clay size fraction. The microscopic analyses indicate that the sediment composed mainly from carbonate and quartz with traces of rock fragments. Such mineral composition is not believed to be a potential source of heavy metal. The study found that the average recorded heavy metal concentrations in the collected sediment samples were 87, 96, 127, 38.5, and 279 ppm for Cr, Cu, Ni, Pb, and Zn, respectively. Those values were slightly higher than metal concentrations recoded in 2001 with 1.22 (Cr), 2.5 (Cu), 2.87 (Ni), 0.69 (Pb), and 2.1 (Zn) folds. However, in 2001 and 2003 the measured metal contents, along the creek, were lower than those of the average earth crust. Along the Creek most metals recorded the highest concentrations in the upper reach of the Creek. The distribution of the measured heavy metals was not affected significantly with the TOC values. The present study also documented obvious related point sources of pollution.

Geologic Sediments↗

PubMed2006

Changes in carbohydrate metabolism in fine roots of the native European black poplar (Populus nigra L.) in a heavy-metal-polluted environment.

Effects of copper-smelter-related deposition of heavy metals in the soil on carbohydrate metabolism of fine roots of the native European black poplar were investigated in spring and autumn. Total soluble non-structural carbohydrates in fine roots from trees growing in the polluted habitat were lower than in a control site, but this was directly associated only with a lower raffinose concentration. Neither glucose nor fructose concentrations differed significantly between polluted and unpolluted sites. In contrast, the galactose concentration was higher in the presence of heavy metals, especially in autumn. Also the stachyose concentration was higher in the polluted site, but only in autumn, suggesting it could be an alternative way of detoxification of galactose. No difference between control and polluted stands was observed in sucrose concentration. However, estimates of sucrolytic activity revealed markedly higher activities of sucrose synthase (SuSy), soluble acid (AI) and neutral (NI) invertases in the polluted stand than in the control. In contrast, the estimated glycolytic enzyme activities were not affected by the presence of heavy metals in soil.

Glucosyltransferases↗

PubMed2004

Reaction of spruce cells toward heavy metals and the influence of culture conditions.

BACKGROUND: Plant cell cultures may serve as biosensors for the detection of heavy metals and other toxic substances. Standard culture media and protocols are frequently utilised, but in these media no care is usually taken to control the influence of hormones and nutrients on the reaction of the enzymes or m under consideration as parts of the sensor. The present paper investigates the influence of media composition on the reaction of spruce cells towards heavy metals. METHODS: Spruce cell cultures were grown in a standard medium, either i) alone, ii) containing 0.3% sucrose or iii) containing 3% sucrose and the hormones BAP and NAA. The cell cultures were then incubated in medium with fungal elicitor, H2O2, CdSO4 (50 to 500 microM), or, alternatively, with a standard heavy metal mixture containing 80 microM Na2HAsO4, 150 microM CdSO4 and 200 microM PbCl2. RESULTS: Depending on the nutrient status and hormone availability, large differences in glutathione contents and the GSH/GSSG ratio were observed. However, the cellular redox state seemed to remain more or less constant. Glutathione S-transferase activity was determined with four substrates, and high induction rates for the conjugation of three substrates were observed when hormones were omitted from the media. 1,2-epoxy-nitrophenoxy-propane conjugation was highest in starving cell in the presence of hormones, showing a transient GST induction, with highest rates occurring after 16 hrs following incubation; the induction effect was lost after 24 hrs. CONCLUSION: A medium containing 3% sucrose and both hormones (BAP and NAA) appears to be most favourable for cellular growth as well as the expression of a basis level of detoxification enzymes and antioxidants. With this combination, early responses towards heavy metals at low concentration can be monitored. RECOMMENDATIONS AND PERSPECTIVE: Plant cell cultures are valuable tools for the bioindication of heavy metals and toxic xenobiotics. If standard media and protocols are utilised, the influence of hormones and nutrients on the reaction of the biosensor have to be evaluated thoroughly.

Cell Culture Techniques↗

PubMed2004

Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES.

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.

Chemistry Techniques, Analytical↗

PubMed1994

Modulation of synaptic events by heavy metals in the central nervous system of mollusks.

1. The effects of heavy metals (Pb2+, Hg2+, and Zn2+) on synaptic transmission in the identified neural network of Helix pomatia L. and Lymnaea stagnalis L. (Gastropoda, Mollusca) were studied, with investigation of effects on inputs and outputs as well as on interneuronal connections. 2. The sensory input running from the cardiorenal system to the central nervous system and the synaptic connections between central neurons were affected by heavy metals. 3. Lead and mercury (10(-5)-10(-3) M) eliminated first the inhibitory, then the excitatory inputs running from the heart to central neurons. At the onset of action lead increased the amplitude of the excitatory postsynaptic potentials, but blockade of sensory information transfer occurred after 10-20 min of treatment. 4. The monosynaptic connections between identified interneurons were inhibited by lead and mercury but not by zinc. Motoneurons were found to be less sensitive to heavy metal treatment than interneurons or sensory pathways. 5. The treatment with Pb2+ and Hg2+ often elicited pacemaker and bursting-type firing in central neurons, accompanied by disconnection of synaptic pathways, manifested by insensitivity to sensory synaptic influences. 6. Zn2+ treatment also sometimes induced pacemaker activity and burst firing but did not cause disconnection of the synaptic transmission between interneurons. 7. A network analysis of heavy metal effects can be a useful tool in understanding the connection between their cellular and their behavioral modulatory influences.

Animals↗

PubMed2006

Heavy metal distribution in tissues and eggs of Chinese alligator (Alligator sinensis).

Chinese alligator (Alligator sinensis) is a critically endangered species endemic to China. Concentrations of heavy metals (As, Fe, Mn, Cu, Pb, Cd, Cr, Zn, and Hg) were examined in the tissues of Chinese alligators to elucidate the background distribution of these metals in the alligator body. Generally, within the body compartments, metal concentrations were high in liver, kidney, and heart, and low in pancreas and gonad. Study of heavy metal levels in the feces and eggs of Chinese alligator suggested that Chinese alligators could reduce body burden of toxic substances by excreting them to feces and/or sequestrating them into eggs to a lesser extent. In addition, to test whether eggshell or egg membrane could be used as surrogates to measure heavy metal load in egg contents, the correlation of metal concentrations between three egg compartments was determined. Of the nine elements analyzed, concentrations of iron, copper, and zinc in the shell membrane were highly correlated with the levels in egg contents, whereas no metal was significantly correlated between eggshell and egg contents. This suggested that the shell membrane could be a useful bioindicator for Fe, Cu, and Zn contaminations in the eggs of Chinese alligator. In a comparison of metal contents in the eggs of individuals from the Anhui captive population, the wild population in Anhui Province, and those of the Changxing captive population, higher Cu, Zn, and Cd levels and a lower Pb level were found in the Changxing individuals, indicative of specific pollutants in different areas. In addition, the majority of metal elements in the muscles of Chinese alligators and American alligators are in the same ranges. As a result of the data found in the eggs of the two alligator species, the Chinese alligators may be exposed to a higher level of metal pollutants. The study provided measurement of the heavy metal distribution in the endangered Chinese alligator for the first time and could serve as the background for the monitoring of possible heavy metal contaminations in the alligator habitats.

Alligators and Crocodiles↗

PubMed2003

[Effects of solid adsorbents on the emission of heavy metals during coal combustion].

Experiments were carried out on laboratory-scale pulverized coal combustion with different adsorbents. Three solid adsorbents (calcium sulfate, limestone and bauxite) were used to control the emission of heavy metals (Pb, Cd, Cu, Co, Ni) during coal combustion. Sequential extraction procedure was developed for partitioning of metals species in coal ash into five fractions: absorbable metals, exchangeable metals, metals bound to carbonate, metals bound to sulfate, residual metals. The adsorbents showed a certain adsorptive ability to heavy metals, and different adsorbent had different ability. It can be proved from the distribution of heavy metals between coarse ash residues and fine particles and also from the increment of stable speciation of heavy metals in fine particles. Calcium sulfate was effective sorbent for removal of Pb, Cd and Cu, limestone for removal of Pb, Cd, Cu, Ni, and bauxite for removal of these five heavy metals. Fine adsorbents have higher adsorptive ability than coarse adsorbents.

Adsorption↗

PubMed2004

Three-step extraction procedure for determination of heavy metals availability to vegetables.

A three-step sequential extraction procedure was used to determine the concentration of heavy metal speciation forms in soil. The procedure allows one to identify the pool of heavy metals that can be potentially mobilised under changes in soil pH value or redox potential. It has been shown that similar portions of heavy metals are present in reducible, oxidisable and residual fractions. It was found that soil chemical properties significantly affected the distribution of heavy metals among different fractions and their uptake by vegetables. Cadmium was a dominant element which occurred in the exchangeable fraction-the most bioavailable and potentially toxic.

Biological Availability↗

PubMed2006

Neutralization of an extremely acidic sludge and stabilization of heavy metals in flyash aggregates.

An extremely acidic, heavy metal-rich sludge (pH=-1.2) was scrubbed with a Class-F fly ash in order to simultaneously neutralize the acidity and stabilize the heavy metals contained in both wastes. This paper outlines the leaching behavior of the aggregate material generated by scrubbing. For proper fly ash/sludge ratios, the fly ash acted as an outstanding neutralizer for the acidic waste. Leaching of heavy metals from the aggregate samples was below the environmental limits within a pH range between 3 and 9. Subsequent washing of the leached aggregate with acidic CALWET solutions did not result in an additional release of heavy metals. It is proposed that coordinative bonding of the metal cations onto neutral surface sites and electrostatic adsorption led to stabilization of the heavy metals within the aggregate structure below hydrolysis pHs.

Adsorption↗

PubMed2005

Heavy metals in zooplankton from the Southern Baltic.

Samples of zooplankton and suspended matter were collected using a Bongo net (0.33/0.50 mm mesh net), and Nucleopore filters, respectively, from the Southern Baltic off Poland. Major classes of zooplankton, and selected heavy metals (Fe, Co, Ni, Mn, Pb, Cd, Cu, Zn, Cr) were determined in the collected samples. Concentrations of heavy metals in zooplankton were corrected for metals contributed by particulate matter adhering to zooplankton organisms. Heavy metals levels measured in nearshore samples (Bay of Gdańsk, Pomeranian Bay) were higher than those in the samples from the open sea. The only exception was cadmium exhibiting larger concentrations in the offshore as compared to the nearshore samples (0.8 vs. 1.3 microg/g d.w.). This was attributed to decreased concentrations, of both dissolved and particulate cadmium, caused by algal bloom. Larger concentrations of heavy metals in the Bay of Gdańsk in comparison with the Pomeranian Bay (e.g. Cd-1.3 vs. 0.8 microg/g, Cu-20.5 vs. 8.3 microg/g, Pb-12.9 vs. 1.2 microg/g, Cr-12.4 vs. 1.4 microg/g) were attributed to the direct discharge of the Vistula river to the Bay of Gdańsk, while the Pomeranian Bay receives the Odra river runoff indirectly, via the Szczecin Lagoon. The nonlinear estimation of the data set was used to evaluate concentrations of heavy metals in Copepoda and Cladocera. Copepoda proved to be enriched with heavy metals in comparison with Cladocera.

Animals↗

PubMed2003

[Advances in the research of soil microorganisms and their mediated processes under heavy metal stress].

More and more evidence from both laboratory and field experiments suggested that soil microbes were more sensitive to heavy metal stress than soil animals or plants living in the same soil. This understanding has been gradually accepted as a common point in this field. The history and the latest advances in soil microorganisms and its mediated processes under heavy metal stresses in soils were reviewed in this paper. It is difficult to do any comparison among the results from laboratory, field toxicological experiment and environmental monitoring. So far, a relevantly 'accurate' control soil was rarely available in the environmental monitoring. Much of evidence has indicated that not only microbial population/biomass was changed under heavy metal stress, but also its structure was varied. Although many molecular methods, such as PLFA, BIOLOG and DNA, have been developed to detect this microbial structural change, they always need many expensive instruments and accessories, and only could be done in laboratory. Therefore, some rapid and easy methods are expected to develop to substitute the traditional plate count. The speciation in the solution phase, ion effect and rhizospheric effect of heavy metal on the toxicity to soil microorganisms and its mediated processes need extent studies and discussion. Finally, the microbial indicator system of assessing heavy metal toxicity to soil microorganisms and its mediated processes need to be established.

Bacteria↗