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Determining rates of change and evaluating group-level resiliency differences in hyporheic microbial communities in response to fluvial heavy-metal deposition.

Prior field studies by our group have demonstrated a relationship between fluvial deposition of heavy metals and hyporheic-zone microbial community structure. Here, we determined the rates of change in hyporheic microbial communities in response to heavy-metal contamination and assessed group-level differences in resiliency in response to heavy metals. A controlled laboratory study was performed using 20 flowthrough river mesocosms and a repeated-measurement factorial design. A single hyporheic microbial community was exposed to five different levels of an environmentally relevant metal treatment (0, 4, 8, 16, and 30% sterilized contaminated sediments). Community-level responses were monitored at 1, 2, 4, 8, and 12 weeks via denaturing gradient gel electrophoresis and quantitative PCR using group-specific primer sets for indigenous populations most closely related to the alpha-, beta-, and gamma-proteobacteria. There was a consistent, strong curvilinear relationship between community composition and heavy-metal contamination (R(2) = 0.83; P < 0.001), which was evident after only 7 days of metal exposure (i.e., short-term response). The abundance of each phylogenetic group was negatively affected by the heavy-metal treatments; however, each group recovered from the metal treatments to a different extent and at a unique rate during the course of the experiment. The structure of hyporheic microbial communities responded rapidly and at contamination levels an order of magnitude lower than those shown to elicit a response in aquatic macroinvertebrate assemblages. These studies indicate that hyporheic microbial communities are a sensitive and useful indicator of heavy-metal contamination in streams.

DNA, Bacterial↗

Correlations of extractable heavy metals with organic matters in contaminated river sediments.

In southern Taiwan, almost all the main rivers have been contaminated by anthropogenic heavy metals and organic matters. The main pollution sources include agricultural, industrial, and domestic activities. River sediments potentially have large capacities to accumulate heavy metals and organic matters when the river water flows through it. The sediments sampled from high contaminated river (the Yenshui River) and moderately contaminated rivers (the Tsengwen, Chishui, Potzu, and Peikang Rivers) were used to realize correlations between each kind of aqua regia extractable heavy metals (Co, Cr, Cu, Zn, Ni, Pb, Mn, and Fe) and organic matters in vertical sediment cores. Organic matters and aqua regia extractable heavy metal concentrations, analyzed by strong acid-digested extraction, were determined in vertical profile segments from downstream sediments of the five rivers. Sum of six aqua regia extractable heavy metals (Co, Cr, Cu, Zn, Ni, and Pb) were below 3,000 mg/kg in sediments of the Yenshui River, and below 500 mg/kg in the other four rivers' sediments. Strongly positive correlations (r = 0.83-0.95) between each kind of aqua regia extractable heavy metals and organic matters (concentration range between 0.6 to 3.8%) were observed in sediments of the Yenshui River. The slopes of the linear regressive lines approximated the average metal complexation ratios with organic matters in the sediments. In sediments of the other four rivers, smaller positive correlation coefficients between aqua regia extractable heavy metals and organic matters (below 2.6%) were observed. The complexation ratios derived from the four moderately polluted river sediments were smaller than those derived from the highly contaminated river sediments, indicating that the importance of organic matters in the accumulation of heavy metals in river sediments.

Environmental Monitoring↗

Animal hair as biological indicator for heavy metal pollution in urban and rural areas.

Animal hair is a good biomonitoring tool for heavy metals assessment and reflects the content of heavy metals in the forage and soil. Heavy metals Fe, Mn, Co and Ni as well as toxic metals Cd and Pb were determined in goat, sheep and camel hair, forage and soil collected from four different environmental urban and rural regions. These regions are Aswan city farms, Allaqi desert pasture, Kalabsha farms and Halaiub desert pasture at far south of Egypt. The results reveal that sheep hair contains the highest levels of Fe and Mn (879 and 55 microg/g, respectively), camel hair contains the highest Pb, whereas for goat Cd and Ni were the highest. Heavy metal concentrations in the studied hair reflect the presence of these metals in the surrounding forage and soil and vary from one area to another, and give knowledge of pollution in the area. Correlation statistics analysis and cluster analysis show a good and significant value between metals in hair and plants.

Animals↗

A review of the biochemistry of heavy metal biosorption by brown algae.

The passive removal of toxic heavy metals such as Cd(2+), Cu(2+), Zn(2+), Pb(2+), Cr(3+), and Hg(2+) by inexpensive biomaterials, termed biosorption, requires that the substrate displays high metal uptake and selectivity, as well as suitable mechanical properties for applied remediation scenarios. In recent years, many low-cost sorbents have been investigated, but the brown algae have since proven to be the most effective and promising substrates. It is their basic biochemical constitution that is responsible for this enhanced performance among biomaterials. More specifically, it is the properties of cell wall constituents, such as alginate and fucoidan, which are chiefly responsible for heavy metal chelation. In this comprehensive review, the emphasis is on outlining the biochemical properties of the brown algae that set them apart from other algal biosorbents. A detailed description of the macromolecular conformation of the alginate biopolymer is offered in order to explain the heavy metal selectivity displayed by the brown algae. The role of cellular structure, storage polysaccharides, cell wall and extracellular polysaccharides is evaluated in terms of their potential for metal sequestration. Binding mechanisms are discussed, including the key functional groups involved and the ion-exchange process. Quantification of metal-biomass interactions is fundamental to the evaluation of potential implementation strategies, hence sorption isotherms, ion-exchange constants, as well as models used to characterize algal biosorption are reviewed. The sorption behavior (i.e., capacity, affinity) of brown algae with various heavy metals is summarized and their relative performance is evaluated.

Adsorption↗

[Tolerance of Arundo donax to heavy metals].

This paper studied the tolerance of Arundo donax grown in a simulated heavy metals polluted wetland, and determined the biological characters and chlorophyll contents of the plant at its different growth stages as well as the changes of soil heavy metals contents. The results showed that Arundo donax could survive in the wetland when the concentrations of Cu2+, Pb2+, Cd2+, Zn2+, Ni2+ and Hg2+ were 100 mg x kg(-1) and Cr6+ concentration was 50 mg x kg(-1). During 40 days growth period, the chlorophyll content decreased by 20%-56% and the leaf became soft with its tip withered, but the plant still grew. Compared with control, Arundo donax in the polluted wetland was slight and yellow-green, but the impact on plant height was inconspicuous. Arundo donax treated with 100 mg x kg(-1) Cr6+ grew slowly with its root stock rotted, and its leaves withered in a short time, indicating that the plant could not tolerate the pollution of high concentration Cr6+. The concentrations of soil heavy metals declined with the growth of the plant, probably due to the translocation of heavy metals from peripheral soil to rhizosphere and the phytoextraction and phytovolatilization, because the heavy metals contents in rhizosphere were much higher than those in the bulk soil in the test jar. The characters of large biomass, exuberant root and good adaptability of Arundo donax suggested its great potential in remediation of polluted soils. The study on the application of Arundo donax to phytoremediation is of realistic significance.

Biodegradation, Environmental↗

Vertical distribution and mobility of arsenic and heavy metals in and around mine tailings of an abandoned mine.

In the present study, the vertical distributions (0-220 cm) of arsenic and heavy metals in mine tailings and nearby paddy fields, and their mobility through water-leach experiments were investigated. For the study, the area of Jingok mine located in Bongwha, Korea has been selected. The concentrations of arsenic and heavy metals in the mine tailings were extremely high compared to the paddy fields and control sites, i.e., up to 6675 mg/kg for As, 25 mg/kg for Cd, 22 mg/kg for Cr, 383 mg/kg for Cu, 11,135 mg/kg for Pb, 3600 mg/kg for Zn, 5.73 wt% for Fe, and 3.05 wt% for Mn. The concentrations of As and heavy metals in the paddy fields decreased sharply with increasing distance from the mine tailings, with values still higher than those in the control sites, indicating the contamination of the paddy fields by heavy metals released from the mine tailings. The vertical distributions of Cd, Cu, Pb, Al, Fe, and Mn showed the following common pattern: the highest values in the upper part of mine tailings (0-20 cm), rapid decrease with increasing depth, and then nearly constant values below the depth of 50 cm. Significant correlations were found between total Fe and heavy metals (Cd, Cu, and Pb), and between total Mn and heavy metals (Cd, Cu, Pb, and Zn) in the mine tailings, indicating that minerals containing Fe and Mn play an important role in the mobility of heavy metals such as Cd, Cu, Pb, and Zn. The fraction of As(V) ranged from 63 to 100% of total arsenic in the samples of the mine tailings. The high concentrations of total As, heavy metals, sulfate. hydrogen ion, and As(V) in the leachates of mine tailings suggest that sulfide minerals containing arsenic and heavy metals in the mine tailings were actively oxidized.

Agriculture↗

Effect of remineralization on heavy-metal leaching from cement-stabilized/solidified waste.

Crushed samples of stabilized/solidified (s/s) waste were leached at constant leachate pH in the pH range 4-7 with nitric acid solutions to evaluate the influence of remineralization on metal release. The s/s waste consisted of synthetic heavy-metal sludge containing 0.1 mol L(-1) copper nitrate, 0.1 mol L(-1) zinc nitrate, and 0.1 mol L(-1) lead nitrate mixed with ordinary Portland cement. Unleached and leached particles were characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry. Two consecutive leaching fronts advancing from the surface of the particles toward the center were identified: the first front was associated with the dissolution of portlandite and partial reaction of the calcium silicate hydrate gel, while the second front was associated with the dissolution of calcium-aluminum hydroxy sulfates such as ettringite and monosulfate. At pH 4 and 5, a remineralization zone rich in heavy metals formed immediately behind the second leaching front. The shell extending from the remineralization zone to the surface of the particles was depleted in calcium, sulfate, and heavy metals. As a result of remineralization, heavy-metal releases to the leachate were reduced by factors ranging between 3.2 and 6.2 at pH 4 and between 74 and 193 at pH 5. At pH 6 and 7, remineralization of Pb and Zn occurred further behind the second leaching front and closer to the surface of the particles. The amount of heavy-metal release depended on both the leachate pH and the remineralization factor.

Construction Materials↗

Ultrasound to decontaminate heavy metals in dredged sediments.

Sediments contaminated with heavy metals due to past disposal practices threaten the environment and require remediation. This study was an attempt to develop a technology to decontaminate heavy metals in dredged sediments using ultrasound coupled with vacuum pressure. A set of laboratory scale experiments were conducted using dredged sediments obtained from New York/New Jersey harbor. This sediment sample is considered as category III, a material that failed to meet USEPA requirements for toxicity or bioaccumulation, and required secure disposal. Acoustic cavitation due to ultrasound energy coupled with vacuum pressure was used to facilitate the removal of chromium (the selected metal contaminant) from the sediments. Full factorial experimental designs were performed to evaluate the above treatment technique and to optimize the processes. Two coupled processes were used to separate and to treat both coarse (Process #1) and fine (Process #2) fractions of sediments. Selected variables for evaluation of Process #1 were ultrasound power, soil-to-water ratio, vacuum pressure and dwell time, and for Process #2 were ultrasound power, soil-to-water ratio and dwell time. Laboratory scale experiments were carried out with various combinations of these parameters according to the factorial design. The optimum removal was found to be 92% with the parameter levels at 1200W power, 1:15 soil-to-water ratio, 15 psi vacuum pressure and 15 min of dwell time. After the application of Process #2 for fine sediments it was found that the fines were separated into silt and clay. Only the silt faction had a considerable metal removal while the clay fraction was insensitive to the treatment. A maximum removal of 83% was obtained for silt fraction when factor levels were at 1200W power, 1:50 soil-to-water ratio and 90 min of dwell time. Further analysis of clay fraction showed that the chromium in clay is immobile and stable. The toxicity characteristic leaching procedure (TCLP) test on clay fraction confirmed that the treated clay fraction is safe to dispose. The study showed that the proposed treatment technique is effective and economical for sediments with lower clay contents.

Cost-Benefit Analysis↗

Interactions between arbuscular mycorrhizae and heavy metals under sand culture experiment.

A sand culture experiment was established to determine interactions between arbuscular mycorrhizae and heavy metals. Mycorrhizal infection rates, spore densities, maize root and shoot weights, and heavy metal contents in maize were as indexes of responses of arbuscular mycorrhizal fungi (Acaulospora laevis, Glomus caledonium and Glomus manihotis) to heavy metals (Cu and Cd). The mycorrhizal infection rates of G. caledonium were the highest among these three mycorrhizal fungi, but the sporulating ability of G. caledonium was the poorest in the heavy metal treatments. The shoot and root weights of non-mycorrhizal plants were usually greater than those of mycorrhizal plants when the Cu concentrations in solutions are less than 3 mg l(-1) or Cd concentrations less than 1 mg l(-1). When Cd concentrations were 0.5 and 1 mg(-1), the root and shoot weights of plants inoculated with A. laevis were significantly (p < 0.05) lower than those of other treatments. Copper concentrations in shoots of mycorrhizal plants were higher than those of non-mycorrhizal ones at all Cu concentrations in solution, especially at low Cu concentrations. As to A. laevis, Cu concentrations in roots and shoots of the host were higher than those of non-mycorrhizal plants in these treatments. Thus A. laevis was sensitive to Cu and Cd, especially Cd, and G. caledonium was more tolerant to these two heavy metals. It is suggested that G. caledonium might be a promising mycorrhizal fungus for bioremediation of heavy metal contaminated soil.

Adaptation, Physiological↗

Kinetic study of heavy metal salt effects on the activity of L-lactate dehydrogenase in solution or immobilized on an oxygen electrode.

A sensitive and convenient biosensor for detection of heavy metal salts has been developed. The method is based on the effects of heavy metal salts on the catalytic activity of L-lactate dehydrogenase (LDH) in solution or coimmobilized with L-lactate oxidase (LOD) on an oxygen electrode. At metal concentrations below 100 microM, the kinetic behavior, with the LDH substrate NADH, showed a competitive inhibition with high affinity during the first 10 s. With increased incubation time, irreversible first order inactivation with respect to enzyme concentration was observed. This irreversible inactivation of LDH in solution was dose dependent. The efficiencies obtained for the different heavy metal salts were: HgGl2 > AgNO3 > Pb(COOCH3)2 > CuSO4 > ZnCl2. HgCl2 and AgNO3 were effective in the nanomolar range while the other metal salts acted at the micromolar level. LDH is protected by saturating amounts of substrate NADH against the effects of the heavy metal salts studied. The pKs for LDH catalytic activity and inactivation by heavy metal salts were similar. The results suggest binding of the heavy metal salts to the enzyme active site. Except for lead acetate, all heavy metal detection was in the range of European norms. For AgNO3, CuSO4 and HgCl2, the sensor limit of detection reached the European norm values whereas with ZnCl2 it was well below. The immobilization of LDH considerably decreased the amount of enzyme consumed by permitting repetitive assays. The efficiency of inactivation by the heavy metal salts was reduced in comparison with LDH in solution. Restoration of activity of the inactivated immobilized enzyme was obtained with DTT, EDTA, KCN and NADH treatment. This opens up possibilities for detection of toxic compounds using simple procedures suitable for assays in a variety of monitoring conditions in environmental and food pollution control.

Biosensing Techniques↗

Distribution of heavy metals in contaminated river sediment.

Sediment was collected from the Ell-Ren River for analysis, to assess the influence of geochemical components in the sediment on remobilization of heavy metals into pore water and on distribution of each heavy metal in five geochemical phases (exchangeable, carbonates, Mn-oxides, Fe-oxides, and organic matters (OM)) in the sediment. Average distribution coefficients, the ratio of heavy metal in pore water to total extractable heavy metal (TEHM), were found in the decreasing order of Co, Zn, Cd, Ni, Pb, Cr, and Cu. Each of the seven heavy metals in five geochemical phases correlated positively with OM but, except for Cd, did not correlate with Fe-oxides. Pb, Zn, Ni, and Cr in pore water correlated negatively with carbonates and Mn-oxides in the sediment, and again did not correlate with Fe-oxides. Significant correlations were also observed between Zn, Cd, Ni, Pb, and Cr in pore water and OM. Principal component analysis results illustrate that the geochemical behavior of different forms of Zn, Pb, Cr, Cu, Ni, and Cd (TEHM, heavy metal in five geochemical phases, and heavy metal in pore water) in association with OM is similar.

Fresh Water↗

Waste water bacterial isolates resistant to heavy metals and antibiotics.

Sewage water of Casablanca, an industrial city in Morocco, was studied for microorganisms resistant to heavy metals. Isolates were purified and collected on agar slants to be screened for resistance to heavy metals, including mercury in vitro. The strains that showed high resistance to heavy metals were also studied for their resistance to antibiotics and aromatic hydrocarbons. Results indicated that the strains most resistant to all tested products belonged to Ps. fluorescens, Ps. aeruginosa, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus sp. These strains exhibit high minimal inhibitory concentrations for heavy metals such as cadmium (2 mm) or mercury (1.2 mm). Growth of Ps. fluorescens and Klebsiella pneumoniae in the presence of heavy metals was also determined, and the growth curves indicated that mercury, copper, and zinc present a slight inhibitory action, while cadmium and silver could have a potent inhibitory action on growth compared with the controls. These studies also investigated growth in media containing aromatic compounds as the sole source of carbon. The results demonstrate that these strains could be good candidates for remediation of some heavy metals and aromatic compounds in heavily polluted sites.

Anti-Bacterial Agents↗

Heavy metal pollution in sediments of the Pasvik River drainage.

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.

Environmental Monitoring↗

Further investigation of the heavy metal content of the teeth of the bank vole as an exposure indicator of environmental pollution in Poland.

The content of heavy metals in mineralised dental tissues is an indicator of the exposure of their mineral phase to heavy metals during the time of tooth development and dental tissue formation. Therefore, teeth have been used as bio-indicators which accurately reflect the environmental or dietary exposure of animals and humans to heavy metals. This study follows from the earlier work in which it was demonstrated that the teeth from bank voles inhabiting various environmentally polluted and non-polluted forests in Southern Poland were reliable indicators of exposure to heavy metals. Using analytical techniques employed in the earlier study heavy metal concentrations were obtained in the teeth of bank voles trapped in 1998-2000 to determine if efforts to clean up the environment could be detected in changes in heavy metal concentrations in the teeth. The results show that these efforts are reflected in lower concentrations of heavy metals in the teeth but that cross border contamination remains a problem.

Animals↗

Characterisation of heavy metal discharge into the Ria of Huelva.

The Ria of Huelva estuary, in SW Spain, is known to be one of the most heavy metal contaminated estuaries in the world. River contribution to the estuary of dissolved Cu, Zn, Mn, Cr, Ni, Cd, and As were analysed for the period 1988-2001. The obtained mean values show that this contribution, both because of the magnitude of total metals (895.1 kg/h), composition, toxicity (8.7 kg/h of As+Cd+Pb) and persistence, is an incomparable case in heavy metal contamination of estuaries. The amount and typology of heavy metal discharge to the Ria of Huelva are related to freshwater flow (and, consequently, to rainfall); as a result, two different types of heavy metal discharge can be distinguished in the estuary: during low water (50% of the days), with only 19.3 kg/h of heavy metals, and during high water or flood (17% of the days), where daily maximum discharge of 72,475 kg of heavy metals were recorded, from which 1481 kg were of As, 470 kg of Pb, and 170 kg of Cd. In the most frequent situation (77% of the days), the Odiel River discharges from 90% to 100% of the freshwater received by the estuary. Despite this, the high concentration of heavy metals in the Tinto River water causes this river to discharge into the Ria of Huelva 12.5% of fluvial total dissolved metal load received by the estuary.

Environmental Monitoring↗

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge.

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.

Aerobiosis↗

Philometra ovata (Nematoda: Philometroidea): a potential sentinel species of heavy metal accumulation.

To assess the bioindicator value of parasites, the concentrations of six heavy metals (Cr, Cu, Pb, Cd, Ni and Zn) were analyzed by atomic absorption spectrometry in gravid females of the nematode Philometra ovata, body cavity parasites of gudgeon (Gobio gobio) and muscle samples of infected and uninfected hosts. The concentration of heavy metals was significantly higher in specimens of P. ovata compared to the host muscle tissue. The parasite-to-muscle ratio of heavy metals varied from 3.2 to 121.7, in increasing concentrations for Cr, Cd, Cu, Pb, Ni and Zn. The presence of parasites did not influence the heavy metal content of the hosts, and no significant differences were found between muscle tissues of parasitized and non-parasitized fishes. The bioconcentration factor (BF = Cparasite/Csediment)varied between 0.4 and 25.8, in increasing order for Cd, Zn, Cu, Pb, Ni and Cr. These results indicate that P. ovata may serve as sensitive indicator species of heavy metal pollution in freshwater ecosystems.

Animals↗

Heavy metal removal by novel CBD-EC20 sorbents immobilized on cellulose.

Heavy metals are major contributors to pollution of the biosphere, and their efficient removal from contaminated water is required. Biosorption is an emerging technology that has been shown to be effective in removing very low levels of heavy metal from wastewater. Although peptides such as metallothioneins or phytotchelatins are known to immobilize heavy metals, peptide-based biosorbents have not been extensively investigated. In this paper, we describe the construction and expression of bifunctional fusion proteins consisting of synthetic phytochelatin (EC20) linked to a Clostridium-derived cellulose-binding domain (CBD(clos)), enabling purification and immobilization of the fusions onto different cellulose materials in essentially a single step. The immobilized sorbents were shown to be highly effective in removing cadmium at parts per million levels. Repeated removal of cadmium was demonstrated in an immobilized column. The ability to genetically engineer biosorbents with precisely defined properties could provide an attractive strategy for developing high-affinity bioadsorbents suitable for heavy metal removal.

Adsorption↗