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Heavy metal ions inhibition of jack bean urease: potential for rapid contaminant probing.

The kinetics of heavy metal ions inhibition of jack bean urease was studied by progress curve analysis in a reaction system without enzyme-inhibitor preincubation. The inhibition was found to be biphasic with an initial, small inhibitory phase changing over the time course of 5-10 min into a final linear steady state with a lower velocity. This time-dependent pattern was best described by mechanism B of slow-binding inhibition, involving the rapid formation of an EI complex that subsequently undergoes slow conversion to a more stable EI* complex. The kinetic parameters of the process, the inhibition constants Ki and Ki* and the forward k5 and reverse k6 rate constants for the conversion, were evaluated from the reaction progress curves by nonlinear regression treatment. Based on the values of the overall inhibition constant Ki*, the heavy metal ions were found to inhibit urease in the following decreasing order: Hg2+ > Cu2+ > Zn2+ > Cd2+ > Ni2+ > Pb2+ > Co2+ > Fe3+ > As3+. With the Ki* values as low as 1.9 nM for Hg2+ and 7.1 nM for Cu2+, 100-1000 times lower than those of the other ions, urease may be utilized as a bioindicator of the trace levels of these ions in environmental monitoring, bioprocess control or pharmaceutical analysis.

Biological Assay↗

Heavy metal concentrations in soils and plant accumulation in a restored manganese mineland in Guangxi, South China.

Heavy metal contamination of metal-mined soils is a widespread problem in China. In the restored (over 20 years) Lipu manganese mineland, 36 plant species from 22 families were found colonizing, some of which were planted agronomic ones. Heavy metal concentrations in tailings were very high. Minesoils were basically unpolluted, but soils in the remaining mining area and in the vicinity of tailings dumps were polluted by Cd and Mn. Measurements of metal contents in dominant plants showed they were close to those of other mineland plants. Plants tended to have a higher Cd accumulation (as reflected by Biological Accumulation Coefficient) from soil, but have a higher Mn translocation (as indicated by Biological Transfer Coefficient) to aboveground parts. The Chinese chestnut and sugarcane cultivated on the reclaimed mineland were not safe for human consumption, and this agricultural restoration pattern should be carefully reconsidered.

Agriculture↗

[Determination of heavy metals in samples of herbal drugs using differential pulse polarography].

The contamination of the environment requires the content of heavy metals in medicinal plants to be limited and controlled. The present paper aims to demonstrate the possibilities of application and advantages of a modern polarographic method, differential pulse chromatography (DPP), in the identification and determination of heavy metals in the plant material. In the plant drugs Flos chamomillae and Flos calendulae, the heavy metals Pb, Cd, Ni, Zn, Cu and Fe were identified and determined. The World Health Organization (WHO) indicated Pb, Cd and Ni as dangerous toxic trace elements.

Metals↗

A clinical trial of combined anti-androgen and anti-heavy metal therapy in autistic disorders.

BACKGROUND: A medical hypothesis has suggested that some autism spectrum disorders (ASDs) may result from interactions between the methionine cycle-transsulfuration and androgen pathways following exposure to mercury. METHODS: The IRB of the Institute for Chronic Illnesses approved the present study. A novel treatment was utilized combining LUPRON (leuprolide acetate, TAP Pharmaceuticals, Inc.) and CHEMET (meso-2, 3-dimercaptosuccinic acid--DMSA, McNeil Consumer Products Company) on 11 consecutive children with ASDs. RESULTS: A significant (p<0.01) overall improvement from the 70-79th percentile of severity (median baseline score=87) at baseline to the 40-49th percentile of severity (median end of study period score=63) at the end of the study was observed for patients treated for a median of approximately 4 months. Significant improvements in sociability, cognitive awareness, behavior, and clinical symptoms/behaviors of hyperandrogenemia were also observed. Significant decreases in blood androgens and increases in urinary heavy metal concentrations were observed. Minimal drug adverse effects were found. CONCLUSION: This study provides the first clinical evidence for the benefit that combined anti-androgen and anti-heavy metal therapy may have on some children with ASDs. Additional studies should examine androgen and heavy metal mechanisms of action in ASDs, and future ASD treatment protocols should consider androgens and heavy metals.

Adolescent↗

Evaluation of distribution, mobility and binding behaviour of heavy metals in surficial sediments of Louro River (Galicia, Spain) using chemometric analysis: a case study.

Contents of total and extractable heavy metals, carbonates, MnO and Fe2O3, organic matter, and matrix components such as SiO2, Al2O3, CaO, Na2O, MgO, TiO2, K2O and P2O5 are used along with principal component analysis (PCA) for studying distribution, mobility and binding behaviour of Cd, Cr, Cu, Ni and Pb in the Louro River (Galicia, Spain). Eleven surficial sediment samples were taken along the beds of the river course. Total metal concentrations were obtained after microwave-assisted digestion whilst extractable metal contents were obtained following a three-stage sequential extraction scheme (i.e. soluble, reducible and oxidisable fractions). Loading plots of heavy metals bound to carbonates, Fe-Mn oxides, organic matter and aluminosilicates allowed determination of binding behaviour. Correlations found indicate that Pb and Cu are mainly discharged from urban wastes, whereas Cr and Ni are from electroplating and galvanizing industries. The occurrence of diffuse pollution sources along the river can account for the binding behaviour of Cd. Metal mobility decreased in the order: Cd > Pb > Cu > Ni > Cr. Despite total contents indicating moderate-to-high heavy metal pollution in this river, metals are mostly distributed in the residual fraction, hence showing a low risk of mobility.

Journal Article↗

Characterisation of mineralogical forms of barium and trace heavy metal impurities in commercial barytes by EPMA, XRD and ICP-MS.

This study was carried out to characterise the mineralogical forms of barium and the trace heavy metal impurities in commercial barytes of different origins using electron probe microanalysis (EPMA), X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). Qualitative EPMA results show the presence of typically eight different minerals in commercial barytes including barite (BaSO4), barium feldspar, galena (PbS), pyrite (FeS2), sphalerite (ZnS), quartz (SiO2), and silicates, etc. Quantitative EPMA confirms that the barite crystals in the barytes contain some strontium and a little calcium, whereas trace heavy metals occur in the associated minerals. Analysis of aqua regia extracts of barytes samples by ICP-MS has shown the presence of a large number of elements in the associated minerals. Arsenic, copper and zinc concentrations correlate closely in all 10 samples. The findings suggest that barytes is not, as traditionally thought, an inert mineral, but is a potentially toxic substance due to its associated heavy metal impurities, which can be determined by an aqua regia digest without the need for complete dissolution of the barite itself. X-ray powder diffraction was not informative as the complex barite pattern masks the very weak lines from the small amounts of associated minerals.

Barium↗

Mass-balance estimation of heavy metals and selected anions at a landfill receiving MSWI bottom ash and mixed construction wastes.

An estimation of the heavy metal and anion mass-balance was made for municipal solid waste incinerator bottom ash deposited at a construction and industrial waste landfill. The mass-balance was found by comparing the content of metals and anions in the landfill leachate to the metal and anion content in the deposited bottom ash. The discharge of heavy metals ranged from 0.001% for Pb to 0.55% for Cr, which is approximately at the same level as in regular municipal solid waste (MSW) landfills. Landfilled organic material and silicates from construction waste might have contributed to the retention of metals. Chloride, and to a lesser extent sulphate, appeared to be readily released from the landfill. It was estimated that a mass corresponding to 80% of the Cl- and 18% of the SO(4)2- in the bottom ash was discharged annually. Low retention, especially of chloride, may lead to a rapid decline in the discharge of this ion in the future when the landfilling of bottom ash is discontinued.

Anions↗

Effects of bacterial activities on the release of heavy metals from contaminated dredged sediments.

The potential impact of indigenous bacterial processes on the release of heavy metals from dredged sediment deposits was investigated. Batch re-suspension experiments were conducted in order to investigate the release of Zn, Cd, Cu and Pb from a polluted anoxic sediment submitted to oxidative perturbations. The concentrations of heavy metals, sulphate and dissolved organic carbon (DOC) were periodically recorded, and cell counts were performed to follow the evolution of several bacterial species. The specific effects of microbial processes were quantified by performing re-suspension assays on sterilised samples. Moreover, the effect of an initial acidification of the system was studied. The results showed that metal release was mainly due to oxidation of sulphide minerals contained in the sediment. Sulphur-oxidising bacteria such as Acidithiobacillus thiooxidans were identified to play a major role in the process, by enhancing the oxidation kinetic. However, the acid production resulting from these reactions was almost totally buffered by the dissolution of the calcite present in the sediment. Copper was released to a lesser extent, and a strong association with organic matter was observed. Lead was not observed in solution, because of its low solubility at neutral conditions and of its re-adsorption on the solid phase. The initial acidification of the system resulted in an faster growth of the acidophilic A. thiooxidans. A subsequent pH drop originating from microbial processes was then observed during the first stages of the experiment. As a consequence, drastic increases in metal (Zn, Cd) release were observed.

Acidithiobacillus thiooxidans↗

A washing procedure to mobilize mixed contaminants from soil: II. Heavy metals.

We conducted a laboratory study to assess the efficiency of nonionic and anionic surfactants in combination with a sparing quantity of ethylenediaminetetraacetate (EDTA) to simultaneously extract heavy metals (HMs) and polychlorinated biphenyl (PCB) compounds from a field-contaminated soil. A soil wash that mobilized both HMs and PCBs was combined with back-extraction with hexane to remove PCBs from the aqueous wash. The aqueous washing suspension was then regenerated by precipitation of the HMs induced by corrosion and hydrolysis of zero-valent Mg to provide a cleaned soil and innocuous extract. Finally, the washing suspension was recycled twice to mobilize more contaminants from the soil particulate fraction. After ultrasonic equilibration, EDTA in admixture with a nonionic surfactant did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe Mn, Ni, and Zn), but did increase the recovery of Cu and Pb. The release of EDTA from HM complexes was efficient for most metals (99%) but was influenced by the chemical characteristics of the surfactant. The EDTA recovery (62-65%) after three cycles of soil washing, hexane back-extraction, and Mg(0) treatment was similar for all reagent combinations. In toto, these studies demonstrate that after treatment with ultrasound, selected heavy metals can be coextracted efficiently from soil with a single washing suspension containing EDTA and a nonionic surfactant.

Adsorption↗

Pilot study on road traffic emissions (PAHs, heavy metals) measured by using mosses in a tunnel experiment in Vienna, Austria.

BACKGROUND, AIMS AND SCOPE: Over the last few years there has been extensive research for new indicators providing information about deposition resulting from road traffic and tunnel experiments received special attention in emission research. Mosses have been used for the estimation of atmospheric heavy metal and PAH depositions for more than three decades, although they were used only a few times for estimating ambient air pollution caused by traffic. In the current study, the suitability of using a moss species for monitoring road traffic emissions inside a tunnel was evaluated. This was a first-time ever attempt to use plants (mosses) as bioindicators in a tunnel experiment. Specifically, two relevant questions were examined: 1) Do mosses accumulate toxic substances derived from road traffic emissions under the extremely adverse conditions which can be found in a tunnel, and 2) Which substances can mainly be attributed to road traffic emissions and therefore be taken as efficient and reliable indicators for motor vehicles? METHODS: For the first time a biomonitor (the moss species Hylocomium splendens (Hedwig) B.S.G.) was used in a road tunnel experiment to analyse emissions from road traffic. Moss samples were exposed for four weeks in wooden frames (size 10 cm x 10 cm), covered by a thin plastic net with a mesh size of 1 cm x 1 cm. 17 elements, mainly heavy metals, and the 16 EPA-PAHs together with coronene were analysed by ICP-AES, AAS and GC-MSD. RESULTS: Enrichment factors, calculated by comparing post-experiment concentrations to those of a background site, were high for most PAHs, especially benzo(g,h,i)perylene (150.7), coronene (134.7), benzo(a)anthracene (125.0), indeno(1,2,3-c,d)pyrene (79.8), chrysene (78.1), pyrene (69.6) and benzo(b)-fluoranthene (67.4), and among the other elements for Sb (73.1), Mo (59.6), Cr (33.9), As (24.1), Cu (19.6), and Zn (17.1). All these substances can thus be taken as indicators for road traffic pollution. Concentrations were also significantly higher in the tunnel mosses for all investigated substances than along busy roads outside tunnels. Cluster analysis revealed groups of substances which could sensibly be attributed to various sources (abrasion processes, Diesel combustion) and enrichment in the various particle size classes. DISCUSSION: The extreme high concentrations in the analysed moss samples from inside the tunnel were due to higher concentrations in the ambient tunnel air, and the fact that already deposited chemical substances are not lost by rain, as well as efficient uptake capacities even under the extremely adverse conditions in a tunnel. In accordance with previous studies our results suggest that PAHs are better indicators for emissions from the burning process than heavy metals. CONCLUSIONS: As in open fields, mosses are suitable indicators for monitoring traffic emissions in tunnels. In addition to biomonitoring in open fields, in tunnel experiments mosses are even better indicators, because the confounding effects of other sources of pollution and the 'noise' in the accumulation process (e.g. washout through wet deposition) are minimised. The results of our study demonstrate the usefulness of mosses for surveying heavy metals and PAH emissions and deposition arising from road traffic sources, even under the extremely adverse conditions of the tunnel environment. RECOMMENDATION: It can be considered that biomonitors like mosses are a suitable alternative to technical particle filters inside tunnels. They are easy to handle, low in costs and valuable information regarding traffic emissions can be obtained. PERSPECTIVE: The results of this pilot-study proved the feasibility of the method, however, should be corroborated by further investigations based on a sample set that allows for generalization of the findings and might even include other moss species. A comparison of technical measurements with the biomonitoring method could lead to a more general acceptance of the results.

Air Pollutants↗

Characterization of an indigenous iron-oxidizing bacterium and its effectiveness in bioleaching heavy metals from anaerobically digested sewage sludge.

The objective of the present study was to isolate the indigenous iron-oxidizing bacterium and compare its effectiveness in bioleaching of heavy metals from fresh anaerobically digested sludge and aged sludge which had undergone a storage period in a sludge holding tank. An acidophilic iron-oxidizing bacterium Acidithiobacillus ferrooxidans strain ANYL-1 was successfully isolated from the sludge collected from a wastewater treatment plant at Yuen Long district in Hong Kong. It was a Gram negative, non-motile rod shaped bacterium which used ferrous iron, elemental sulfur or thiosulfate as energy source, but did not utilize tetrathionate or glucose as energy source. The optimal temperature and pH for its growth and iron oxidation were 30-35 degrees C and pH 2.0-2.5, respectively. When it was used in the bioleaching of anaerobically digested sewage sludge, an inhibition on metal solubilization was observed in fresh sludge except for Zn whose dissolution was solely a chemical process. Compared to the 3 and 4 days required for solubilization of Cu and Cr respectively from the sludge sample collected after the sludge holding tank (Sludge SHT), 6 days were required to bioleach Cu and Cr from fresh sludge (Sludge AD). The fresh sewage sludge posed an unfavorable condition for bioleaching of heavy metals from anaerobically digested sludge as reflected by the prolonged bioleaching time. Therefore, further studies were needed to understand the inhibitory effects in the fresh anaerobically digested sludge and develop measures to remove it in order to improve the heavy metal bioleaching efficiency.

Acidithiobacillus↗

Beneficial effect of saprobe and arbuscular mycorrhizal fungi on growth of Eucalyptus globulus co-cultured with Glycine max in soil contaminated with heavy metals.

The effects of saprobe and arbuscular mycorrhizal (AM) fungi on growth, chlorophyll and N, P and K content of Eucalyptus globulus Labill. growing in soil contaminated by heavy metals in the presence or absence of Glycine max were investigated. Glomus mosseae and Glomus deserticola increased dry weight, shoot length, total N, P and K concentration and the quantity of chlorophyll in E. globulus shoots. The protection of Eucalyptus by AM fungi against the action of the heavy metals was more evident when this plant grew as an intercrop with soybean than as a monoculture. The presence of the saprobe fungi Fusarium concolor and Trichoderma koningii further enhanced shoot dry weight, N, P and K content of AM Eucalyptus. The co-inoculation of Eucalyptus with Glomus deserticola and T. koningii was more effective for Cd uptake. In addition, Glomus deserticola enhanced the amount of Pb absorbed by Eucalyptus plants. We showed that it is important to select the most efficient AM and saprobe fungi to stimulate plant growth in heavy-metal-contaminated soil and that the combination of both plays an important role in metal tolerance of Eucalyptus plants.

Biological Availability↗

Understanding heavy metal and suspended solids relationships in urban stormwater using simulated rainfall.

Urban stormwater from simulated rainfall on three different landuses in Queensland State, Australia (residential, industrial, commercial) was analysed for heavy metals and physico-chemical parameters such as Dissolved Organic Carbon (DOC) and Total Suspended Solids (TSS). Rainfall events were simulated using a specially designed rainfall simulator for paved surfaces. Event mean concentration samples were separated into five different particle sizes and analysed individually for eight metal elements (Zn, Fe, Cr, Cd, Cu, Al, Mn and Pb). Multivariate data analysis was carried out for the data thus generated. It was found that DOC and TSS influence the distribution of the metals in the different particle size classes. Zn was correlated with DOC at all three sites. Similarly, Pb, Fe and Al were correlated with TSS at all sites. The distribution of Cu was found to vary between the three sites, whilst Cd concentrations were too low to assess any relationships with other parameters. No correlation between Electrical Conductivity (EC), pH and heavy metals was found at the three sites. The identification of physico-chemical parameters influencing the distribution process kinetics of heavy metals in urban stormwater will significantly enhance the efficiency of urban stormwater management systems.

Carbon↗

Effect on uptake of heavy metal ions by phosphate grafting of allophane.

The effect of phosphate grafting on the uptake of various heavy metal ions was investigated using allophane, a clay mineral having a chemical composition of 1-2SiO2Al2O3.5-6H2O with hollow nanoparticles 3.5-5 nm in size. Phosphate grafting was performed on allophane with an atomic ratio Si/Al=0.85 using the orthophosphates (NH4)2HPO4, Na2HPO4 and CaHPO4 and the triphosphate Na5P3O10. The cations in the phosphates were partially retained in the samples, along with the grafted phosphate. Uptake experiments were performed with various heavy metal ions (Cu2+, Zn2+, Ni2+, Co2+, and Mn2+) and alkaline earth ions (Mg2+ and Ca2+) using a batch method. With increasing amounts of grafted phosphate, the Cu2+ uptake capacity increases to about double of that of ungrafted allophane. Although part of the grafted phosphate is released during the uptake experiments, this can be largely suppressed by heat-treating the samples at 200-500 degrees C. The Cu2+ uptake ability of the (NH4)2HPO4-grafted sample showed a steep decrease with higher heating temperature according to the thermal decomposition of NH4+. The ratios of cations released from the samples to cations removed from solution (2Na/Cu and Ca/Cu) are close to unity. From these results, the replacement reaction is thought to be the main uptake mechanism of heavy metal ions in the present samples. The uptake abilities of the present samples for various cations are explained with respect to the solubilities of the corresponding metal phosphates.

Journal Article↗

The homogeneity of heavy metal deposition on glass fibre filters collected using a high-volume sampler in the vicinity of an opencast chrome mine complex at Kemi, Northern Finland.

The homogeneity of heavy metal (Cr, Ni, Cu, Fe and Cd) distribution on glass fibre filters (Munktell MG 160, 203 x 254 mm, 75 g m(-2)) collected using a high-volume sampler (Wedding & Associates) at an opencast chrome mine complex at Kemi, Northern Finland was studied. The heavy metals in the total suspended particulate (TSP) material were analysed by inductively coupled plasma atomic emission spectrometry (ICP-AES) or graphite furnace atomic absorption spectrometry (GFAAS). The glass fibre filters were digested in a microwave oven using a mixture of aqua regia+HF acids. There was significant non-uniform distribution of heavy metals on glass fibre filters. The TSP material containing chromite was very difficult to dissolve by acid digestion. The results from X-ray fluorescence spectrometry (XRF), and from energy filtering transmission electron microscope (EFTEM) equipped with energy dispersive X-ray spectrometer (EDS), showed that insoluble residue left after microwave oven digestion with aqua regia+HF acids was probably partly due to chemical reactions occurring during microwave heating.

Air Pollutants↗

Limited effects of heavy metal pollution on foraging and breeding success in the curlew (Numenius arquata).

We examined the effect of heavy metal pollution on the foraging success and breeding performance of the curlew (Numenius arquata) along a documented pollution gradient from a point source, and also by comparing foraging and breeding parameters between the polluted site and two non-polluted areas. Prey biomass and abundance, and foraging success did not vary along the pollution gradient, and were no less at the polluted site than in the non-polluted areas. Furthermore, there was no difference in adult weight during incubation between the polluted and non-polluted areas. There were also no differences in measures of breeding success along the pollution gradient, or between areas, which could be attributed to pollution per se. Egg shells from the polluted area had higher concentrations of heavy metals than in the non-polluted areas, and egg shells close to the pollution source were contaminated more than those further from it. However, there was no difference in calcium concentrations of egg shells or egg-shell thickness between areas. We conclude that in this study there were minimal immediate effects of heavy metal pollution on foraging and breeding success in the curlew.

Journal Article↗

Heavy metal levels in two biennial pine insects with sap-sucking and gall-forming life-styles.

The concentrations of cadmium, copper, nickel and lead were studied in two biennial pine insects in relation to the deposition of heavy metals in the environment around the industrialised town of Harjavalta in southwestern Finland. Sap-sucking pine bark bugs, Aradus cinnamomeus (Heteroptera, Aradidae), and gall-forming pine resin gall moths, Petrova resinella (Lepidoptera, Tortricidae) were collected on sample plots located at logarithmic distances along 9 km-long transects from the distinctive emission source. The responses of these insects representing different life-style were compared. Heavy metal concentrations in A. cinnamomeus were highest (Cd 17 microg g(-1), Cu 1900 microg g(-1), Ni 220 microg g(-1), Pb 32 microg g(-1)) in the vicinity of the factor complex, and lowest in the outermost zones. This trend followed a linear regression model. The pattern was less clear in P. resinella, the concentrations being only one-tenth of those recorded in A. cinnamomeus. Correlations between metal levels in A. cinnamomeus and previously examined Sphagnum moss bags proved to be highly significant in every case. The differences in the heavy metal concentrations of these two insect species, which occupy the same trophic position, would appear to be due to the differences in their feeding characteristics. Heavy metals accumulate in the posterior bulb of the midgut in the discontinuous alimentary system of A. cinnamomeus, while P. resinella is likely to secrete most of the metals into the walls of the galls. The almost total absence of these two insect species near the factory complex seems to be associated with the high concentrations of metals.

Journal Article↗