Metal Speciation Analysis Research Articles

Scanned stripping chronopotentiometry at bismuth film rotating disc electrodes: a method for quantitative dynamic metal speciation

Environmental context Electroanalytical methods have found wide application in trace metal speciation analysis in environmental systems. The need to find functional alternatives to mercury electrodes for in situ speciation studies has encouraged the use of bismuth as a solid-state electrode substrate. We demonstrate the utility of bismuth electrodes for quantitative dynamic speciation analysis. Abstract Bismuth film electrodes are employed for dynamic metal speciation analysis of PbII complexes by stripping chronopotentiometry at scanned deposition potential (SSCP). Their performance is found to be comparable to that of mercury-film electrodes. The quantitative SSCP expressions that describe the thermodynamic and kinetic complexation parameters are straightforwardly applicable to this solid electrode.

Assessment of Mobility and Bioavailability of Heavy Metals in Sewage Sludge from Swaziland through Speciation Analysis

Speciation analysis of heavy metals in sewage sludge provides a better understanding of the extent of mobility and bioavailability of the different metal fractions and helps in more informed decision making on application of sludge for agricultural purposes. Assessment of bioavailability of metals based on regulations expressed in terms of total metals alone may be conservative and restrictive from the point of view of the use of sludge for agricultural applications. Total metals may also be poor indicators of uptake by plants. Sewage sludge samples generated from seven wastewater treatment plants in Swaziland were analyzed for the four fractions of metals species, namely, exchangeable, reducible, oxidizable and residual fractions. The experimental results indicated that arsenic was predominantly associated with the residual matrix. Chromium was dominantly found in the residual fraction followed by oxidizable fraction. Lead and copper were predominantly associated with oxidizable fraction (bound to organic matter). For more polluted effluents such as Matsapha waste water treatment plant, some metals such as nickel were also found significantly in the mobile fraction. By contrast zinc and to a certain extent nickel were present in significant proportions in the more mobile (exchangeable) fraction. The experimental result indicated that the percentage immobility ranges from 10% to 70% with respect to the residual solid fraction of the metals which should be considered as an additional safety factor in the assessment of the suitability of the sludge for agricultural uses with respect to heavy metals.

Lead electrochemical speciation analysis in seawater media by using AGNES and SSCP techniques

Environmental context Metal contamination of seawater can present severe environmental problems owing to the high toxicity of metals and their persistence in the environment. This study explores the possibility of analysing lead in seawater media using two recently developed electrochemical methods. The methods are shown to be very useful tools to monitor the behaviour and fate of lead and other metals in seawater. Abstract The speciation of PbII in synthetic and real seawater is studied by absence of gradients and Nernstian equilibrium stripping (AGNES) and stripping chronopotentiometry at scanned deposition potential (SSCP). The usefulness of the combination of both techniques in the same electrochemical cell for trace metal speciation analysis is assessed at different pH values (2.7, 5.0, 6.0, 7.0 and 8.6). The AGNES (free metal ion concentrations) and SSCP (stability constants) results for synthetic seawater agree reasonably with each other and with the theoretical predictions of the software Visual MINTEQ 3.0. This is also true for real seawater media below pH 7.0. Because of the influence of natural organic matter (2.01mgL–1 total organic carbon) in the real seawater at pH 7.0 and 8.6 the SSCP signal showed that the PbII complexes became less labile and were formed by chemically heterogeneous ligands. At these pH values, free metal concentrations determined by AGNES agreed with concentrations predicted by Visual MINTEQ using a generic fulvic acid concentration.

Heavy metal speciation and pollution of agricultural soils along Jishui River in non-ferrous metal mine area in Jiangxi Province, China

As a tributary of Le'an River in Jiangxi Province of China, Jishui River has been seriously polluted by non-ferrous heavy metal mining activities, and long-term irrigation using Jishui River water has caused severe heavy metal pollution of soil. We collected samples of agricultural soils along the river and determined the contents of As, Cd, Cr, Cu, Mn, Ni, Pb and Zn. The results showed that Cd and Cu were two primary pollutants in the soils with concentrations of 0.52–2.55mg·kg−1 and 27.87–426.15mg·kg−1, respectively. The mean concentrations of As, Mn, Pb and Zn in the soils were 33.99mg·kg−1, 468.70mg·kg−1, 125.32mg·kg−1 and 171.48mg·kg−1, respectively. Moreover, higher heavy metal concentrations were found in the agricultural soils closer to mines and metal smelters. The metal speciation analysis showed that Cd was mainly in the exchangeable and carbonate fraction, and the reducible fraction of Mn and Pb was a significant proportion in most soils. However, Cu and Zn were mainly in the residual fraction in all samples. Assessments of pollution levels revealed that (1) heavy metals that were mainly from anthropogenic sources, such as Cd, Cu, Pb and Zn, were much higher than their background value, (2) heavy metal pollution in the agricultural soils closer to the mines and smelters was often more severe, and (3) the environmental risk of Cd was highest and should be of special concern.

Distribution and speciation of metals (Cu, Zn, Cd, and Pb) in agricultural and non-agricultural soils near a stream upriver from the Pearl River, China

The distribution and chemical speciation of typical metals (Cu, Zn, Cd and Pb) in agricultural and non-agricultural soils were investigated in the area of Nanpan River, upstream of the Pearl River. The investigated four metals showed higher concentrations in agricultural soils than in non-agricultural soils, and the site located in factory district contained metals much higher than the other sampling sites. These observations suggested that human activities, such as water irrigation, fertilizer and pesticide applications might have a major impact on the distribution of metals. Metal speciation analysis presented that Cu, Zn and Cd were dominated by the residual fraction, while Pb was dominated by the reducible fraction. Because of the low mobility of the metals in the investigated area, no remarkable difference could be observed between upstream and downstream separated by the factory site.

New Research Development on Heavy Metals’ Speciation in Soil

The bioavailability and environmental risk of heavy metals in soil depends greatly on their speciation, not total amounts. Different speciation analysis techniques of heavy metals in soil are reviewed and the speciation schemes are considered and discussed in some detail. The present problems remained in the field of environmental science and future trends of speciation analysis of heavy metals in soil are also briefly dealt with.

Exploration of the medical periodic table: towards new targets

Metallodrugs offer potential for unique mechanisms of drug action based on the choice of the metal, its oxidation state, the types and number of coordinated ligands and the coordination geometry. We discuss recent progress in identifying new target sites and elucidating the mechanisms of action of anti-cancer, anti-bacterial, anti-viral, anti-parasitic, anti-inflammatory, and anti-neurodegenerative agents, as well as in the design of metal-based diagnostic agents. Progress in identifying and defining target sites has been accelerated recently by advances in proteomics, genomics and metal speciation analysis. Examples of metal compounds and chelating agents (enzyme inhibitors) currently in clinical use, clinical trials or preclinical development are highlighted.

Analytical Relevance of Trace Metal Speciation in Environmental and Biophysicochemical Systems

This article presents a review of the analytical relevance of trace metal speciation analysis, which must be considered in environmental and biophysicochemical systems for reliable and efficient assessment and monitoring of trace metals. Examples are given of methodological approaches used for speciation analysis. An overview of speciation analysis in sediments, aquatic ecosystems and agrosystems is also presented.

Extraction of heavy metals from e-waste contaminated soils using EDDS

Environmental contamination due to uncontrolled e-waste recycling activities is drawing increasing attention in the world. Extraction of these metals with biodegradable chelant [S,S]-ethylenediaminedisuccinic acid (EDDS) and the factors influencing extraction efficacy were investigated in the present study. Results showed that the addition of EDDS at low pH (5.5) produced higher metal extraction than that at high pH (8.0) solution. Metal speciation analysis indicated that Cu was completely complexed with EDDS at different pH conditions with various amounts of EDDS applied. For Pb and Zn, at low EDDS dose of 0.304 mol/kg soil, they were present as Pb- and Zn-EDDS. However, at high EDDS dose of 1.26 mol/kg soil, most of Pb was bound with dissolved organic matter. Ca and Al were found to be strong competitors for trace metals to EDDS at low application dose and low pH condition.

Toxicity of Metal–Ethylenediaminetetraacetic Acid Solution as a Function of Chemical Speciation: An Approach for Toxicity Assessment

The influence of complexation by ethylenediaminetetraacetic acid (EDTA) on the toxicity of Cd(II), Cu(II), Cd(II), and Ni(II) was investigated. Result of the Microtox test, which is based on measuring the decrease of light emitted by Vibrio fischeri bacterium when exposed to a toxicant, was used as an indication of toxicity. The effect of pH and EDTA molar ratio that might potentially modify the percentage of chemical species in solution on toxicity was evaluated. In general, results indicate that toxicity decreases when increasing the pH value as well as the EDTA molar ratio. Chemical modeling was used to predict metal speciation and correlation analysis to relate chemical species with the obtained toxicity results. The species that most contribute to toxicity resulted to be MeCl(+) (Me = metal), which is formed as a consequence of the presence of the bioassay medium (2 % NaCl). A model that predicts metal-solution toxicity by using the chemical species, which most contribute to toxicity is proposed as a useful tool for toxicity assessment in waters containing metal ions and EDTA.

Metal leaching along soil profiles after the EDDS application – A field study

One concern about the chelant-enhanced phytoextraction is the potential metal leaching associated with chelant application. A field study was carried out and the metal leaching along the 60-cm depth soil profiles were evaluated within 36 days after the biodegradable chelant EDDS was applied. Results showed EDDS significantly increased soluble Cu in the top 5 cm soil layer 1 day after the application, and the increase of soluble metals was generally limited in the top 20 cm soil. Metal speciation analysis indicated all Cu and Zn were in forms of Cu-EDDS and Zn-EDDS complexes in soil solution, and Ca was the major competitor with trace metals to EDDS. The soluble metals decreased quickly with time, and no significant difference was observed in the extractable Cu between EDDS treatments and the controls 22 days after the EDDS addition. The potential leaching associated with biodegradable EDDS addition may be controlled under field conditions.

Gel–water partitioning of soil humics in diffusive gradient in thin film (DGT) analysis of their metal complexes

Environmental contextMetal species can have significant toxic effects in aquatic systems, and therefore their occurrence should be reliably monitored. Although many methods to measure metal species are available, they all have limitations and are sensitive to physicochemical complications. It is shown that, in techniques based on diffusive gradients in thin films, sorption of humic acids affects metal speciation inside the diffusive gel layer and the nature of the ensuing flux response. AbstractMetal complexes of humic and fulvic acids are ubiquitous in aqueous environmental media. In metal speciation analysis by DGT (diffusive gradient in thin film) with polyacrylamide hydrogels, soil humic acid species have been shown to significantly accumulate in the diffusive gel layer. As a result, the speciation of their metal complexes inside the gel is changed with respect to that in the sample medium. In low ionic strength samples, the effects of sorption of the charged humic species are compounded by Donnan partitioning. Here we lay out the basic features that govern the partition of humic species between gel and water, and discuss their effect on the properties of the DGT metal flux.

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors

The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (∼60% of total S) and reduced organic S (∼30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed.

Speciation of heavy metals in sewage sludge after mesophilic and thermophilic anaerobic digestion

AbstractTwo types of sewage sludge anaerobic digestion were carried out: mesophilic and thermophilic. Metal speciation analysis was performed revealing some changes in the chemical form of the metals during the stabilization process of sludge. After both methane fermentation processes, a comparable level of organic matter distribution was obtained (≈ 40 %). The amount of produced methane during thermophilic and mesophilic digestion was 560 mL of CH4 and 580 mL of CH4 from 1 g of removed organic matter, respectively. Low concentration of heavy metal ions in the liquid phase of sludge was observed. Metal ions precipitated and remained bound throughout the stabilization process. No accumulation of heavy metals in the mobile fractions of sludge (exchangeable and carbonate) was observed for either digestion process. The highest increase of zinc, copper, nickel, cadmium, and chromium concentration was observed in the organic-sulfide fraction, whereas the highest increase of lead was found in the residual fraction.

Speciation Analysis of Heavy Metals in Electroplating Sludge and the Effect of Composting

Electroplating sludge is always listed as hazardous waste due to the high content of heavy metals. The most economical and available way for disposal of sludge is soil application of sludge compost, and the major limitation in agriculture utilization is the total heavy metal contents and their bioavailability to the soil–plant system. The effect of composting on the speciation of heavy metals in an electroplating sludge was studied, and the potential environmental impacts were also assessed. The electroplating sludge was composted with rice straw and sawdust by static aerobic method at high temperature with forced ventilation. Results showed that the exchangeable species of copper and nickel were significantly decreased after the compost procedure, and the other kinds of species were increased differently. Data in this research indicated that composting can reduce the activity of heavy metals to some extent to achieve the agricultural use.

Metal speciation and toxicity of Tamar Estuary water to larvae of the Pacific oyster, Crassostrea gigas

As part of the PREDICT Tamar Workshop, the toxicity of estuarine waters in the Tamar Estuary (southwest England) was assessed by integration of metal speciation determination with bioassays. High temporal resolution metal speciation analysis was undertaken in situ by deployment of a Voltammetric In situ Profiling (VIP) system. The VIP detects Cd (cadmium), Pb (lead) and Cu (copper) species smaller than 4 nm in size and this fraction is termed ‘dynamic’ and considered biologically available. Cadmium was mainly present in the dynamic form and constituted between 56% and 100% of the total dissolved concentration, which was determined subsequently in the laboratory in filtered discrete samples. In contrast, the dynamic Pb and Cu fractions were less important, with a much larger proportion of these metals associated with organic ligands and/or colloids (45–90% Pb and 46–85% Cu), which probably reduced the toxicological impact of these elements in this system. Static toxicity tests, based on the response of Crassostrea gigas larva exposed to discrete water samples showed a high level of toxicity (up to 100% abnormal development) at two stations in the Tamar, particularly during periods of the tidal cycle when the influence of more pristine coastal water was at its lowest. Competitive ligand-exchange Cu titrations showed that natural organic ligands reduced the free cupric ion concentration to levels that were unlikely to have been the sole cause of the observed toxicity. Nonetheless, it is probable that the combined effect of the metals determined in this work contributed significantly to the bioassay response.

Environmental hazard of cadmium, copper, lead and zinc in metal-contaminated soils remediated by sulfosuccinamate formulation

Accumulation of metals in soil at elevated concentrations causes risks to the environmental quality and human health for more than one hundred million people globally. The rate of metal release and the alteration of metal distribution in soil phases after soil washing with a sulfosuccinamate surfactant solution (Aerosol 22) were evaluated for four contaminated soils. Furthermore, a sequential extraction scheme was carried out using selective extractants (HAcO, NH(2)OH·HCl, H(2)O(2) + NH(4)AcO) to evaluate which metal species are extracted by A22 and the alteration in metal distribution upon surfactant-washing. Efficiency of A22 to remove metals varied among soils. The washing treatment released up to 50% of Cd, 40% of Cu, 20% of Pb and 12% of Zn, mainly from the soluble and reducible soil fractions, therefore, greatly reducing the fraction of metals readily available in soil. Metal speciation analysis for the solutions collected upon soil washing with Aerosol 22 further confirmed these results. Copper and lead in solution were mostly present as soluble complexes, while Cd and Zn were present as free ions. Besides, redistribution of metals in soil was observed upon washing. The ratios of Zn strongly retained in the soil matrix and Cd complexed with organic ligands increased. Lead was mobilized to more weakly retained forms, which indicates a high bioavailability of the remaining Pb in soil after washing. Comprehensive knowledge on chemical forms of metals present in soil allows a feasible assessment of the environmental impact of metals for a given scenario, as well as possible alteration of environmental conditions, and a valuable prediction for potential leaching and groundwater contamination.

Speciation analysis, bioavailability and risk assessment of trace metals in herbal decoctions using a combined technique of in Vitro digestion and biomembrane filtration as sample pretreatment method

Sample preparation is the first crucial step in the speciation analysis, bioavailability and risk assessment of trace metals in plant samples such as herb and vegetables. Two bionic technologies titled 'in vitro digestion' and 'extraction with biomembrane' were developed for pre-treatment of herbal decoction. The decoctions of Aconiteum carmichaeli and Paeonia lactiflora were digested at body temperature, at the acidity of the stomach or intestine and with inorganic and organic materials (digestive enzymes were included for whole-bionic and excluded for semi-bionic) found in the stomach or intestine. Being similar to the biomembrane between the gastrointestinal tract and blood vessels, monolayer liposome was used as a biomembrane model. Affinity-monolayer liposome metals and water-soluble metals were used for speciation analysis and bioavailability assessment of copper and zinc in herbal decoction. In the decoction of Aconiteum carmichaeli and Paeonia lactiflora, Zn was mainly absorbed in the intestine and Cu was mainly absorbed by both stomach and intestine. The safe dosage for males and females is below 257.1 g/day Aconiteum carmichaeli and 529.4 g/day Paeonia lactiflora.

Optimization of an anion-exchange high performance liquid chromatography-inductively coupled plasma-mass spectrometric method for the speciation analysis of oxyanion-forming metals and metalloids in leachates from cement-based materials

A method was developed for the speciation analysis of the oxyanions of As(III), As(V), Cr(VI), Mo(VI), Sb(III), Sb(V), Se(IV), Se(VI) and V(V) in leachates from cement-based materials, based on anion-exchange HPLC coupled with ICP-MS. The method was optimized in a two-step multivariate approach: the effect of sample pH and mobile phase composition on resolution, peak symmetry and analysis time was studied. Optimum conditions were then identified for the significant experimental factors by studying their interdependence. A mobile phase composition of 20 mM ammonium nitrate, 50 mM ammonium tartrate and pH 9.5 was found to be a compromise optimum for the separation of the target analytes using isocratic elution. The optimum condition provided separation of the analytes in less than 6 min, at a mobile phase flow rate of 1.0 mL/min. The signal intensities of the analytes were improved by adding 1% methanol to the mobile phase. The limit of detection of the method was in the range 0.2–2.2 μg/L for the various species. The effect of sample constituents was studied using spiked concrete leachates. The method was used to determine the target oxyanionic species in leachates generated from a concrete material in the pH range 3.5–12.4; CrO 4 2−, MoO 4 2− and VO 4 3− were detected in most of the leachates.

DGT/DET Gel Partition Features of Humic Acid/Metal Species

Gel layer based sensors are increasingly employed for dynamic trace metal speciation analysis in aquatic and soil media, in which humic and fulvic acid species are generally known to be relevant. In DGT (diffusive gradient in thin film), polyacrylamide hydrogels are commonly used for the diffusive gel layer. Various effects of the presence of humic species on the amount of metal detected by DGT have been observed, but the role of the different metal/humic species is still unknown. Recently it was shown that in the absence of metal, humic acid accumulates significantly in the polyacrylamide hydrogel. Here we analyze the extent of this accumulation in the presence of cadmium under various conditions of ionic strength and total humic and fulvic acid concentrations. At millimolar ionic strength level, DET data show significant accumulation of cadmium(II) in the gel phase, on top of some Donnan enrichment. The results are essential for the interpretation of DGT/DET data on metals in the presence of humics, especially in freshwaters.