Evaluation and comparison of two selective extraction procedures for heavy metal speciation in sediments.

Two sequential extraction procedures (the former proposed by the Standard, Measurements and Testing-SM&T-program of European Union and the latter derived from those of Tessier and Forstner with various modifications) have been compared, by analyzing a reference material (CRM 601) certified for the content of heavy metals in the three solutions resulting from the SM&T procedure. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) was used to evaluate the composition of the residues after various extractions. Reliable results, both in terms of precision and accuracy, were obtained for the first two steps of the SM&T scheme. As regards the third step, because it was modified during this work, a direct comparison of our results with those certified is not possible. SEM analysis confirmed that the scheme previously used in the laboratory was more aggressive compared to the SM&T procedure, which has also the advantage that the only CRM available for metal partitioning in sediments is certified using this method.     

Sequential extraction for the speciation of some heavy metals in soils

The five step sequential extraction for speciation of copper and nickel originally designed for sediments has been applied to soil samples. The extractant solutions were: 1 mol/l ammonium acetate, 1 mol/l hydroxylammonium chloride in 25% acetic acid (1∶1), 0.1 mol/l hydrochlorid acid, 0.5 mol/l sodium hydroxide and 8 mol/l nitric acid. The residue was decomposed by HF and HNO₃. Using this procedure the metal fraction bound to the organic matter can be distinguished. The concentrations of analytes were determined in the soil extracts by FAAS and ETAAS. Accuracy was assessed by comparing the sum of the contents of copper and nickel in soil extracts with the total certified values of CRMs of soils. The overall recovery values for nickel was 84–105% and for copper 105–114%.     

火焰原子吸收光谱法分析沉积物中重金属元素的形态

采用原子吸收光谱法研究了金沙江攀枝花段水系沉积物中重金属的形态及分布特征。研究发现,各重金属的形态以残渣态为主,离子交换态含量很少。同时说明原子吸收光谱法完全可以用来研究重金属形态特征,在环境研究中具有重要意义。     

Fractionation and speciation analysis of heavy metals in the Azov Sea bottom sediments

The fractionation and speciation analysis of heavy metals in bottom sediment samples from the Azov Sea were performed. Seven-step sequential extraction was used to extract element species differing in physicochemical mobility and biological availability. Special attention was paid to the study of ecologically valuable mobile fractions: exchangeable, acid-soluble, readily reducible, and readily oxidizable ones. It was shown that the total concentration of mobile copper, zinc, and lead species isolated in four extraction steps was higher than the MPCs for mobile species extractable with an ammonium acetate buffer solution (1.1–3.3 PMC), which points to the technogenic contamination of bottom sediments and their potential hazard to hydrobionts. For finely dispersed silt samples taken near the Kerch Strait, elevated concentrations of zinc and copper (up to 10 and 5 mg/kg, respectively) were found in the most mobile exchangeable fraction directly available to living organisms, which indicates the presence of an active contamination source in this water area. The binding of metals to mineral phases in samples of different lithological types was studied.     

Adsorption of heavy metal ions on soils and soils constituents

The article focuses on adsorption of heavy metal ions on soils and soils constituents such as clay minerals, metal (hydr)oxides, and soil organic matter. Empirical and mechanistic model approaches for heavy metal adsorption and parameter determination in such models have been reviewed. Sorption mechanisms in soils, the influence of surface functional groups and surface complexation as well as parameters influencing adsorption are discussed. The individual adsorption behavior of Cd, Cr, Pb, Cu, Mn, Zn and Co on soils and soil constituents is reviewed.     

Electroanalytical methods for determination of the metal content and acetic-acid-available metal fractions in soils

The pseudo-total and available arsenic, cadmium, and lead content of soils have been determined by stripping voltammetry with a hanging-mercury-drop electrode and by atomic absorption spectrometry with electrothermal atomization. For determination of pseudo-total metals microwave digestion with a mixture of HNO3 and HClO4, with and without addition of HF, was investigated. The single-extraction procedure with 0.43 mol L-1 CH3COOH, proposed by BCR, was used to assess the availability of metals in soils. The results obtained were validated by analysis of a certified reference material.     

Three-stage sequential extraction procedure for metal partitioning in polluted soils and sediments

The sequential extraction procedure proposed by the Standard, Measurements and Testing program "SM&T" of the European Union has been applied to evaluate the amounts of Cr, Cu, Mn, Ni, Pb and Zn, extracted at each stage and indirectly their mobility and bioavailability in soil and sediment samples from a polluted area. Analysis of the extracts was carried out by flame atomic absorption spectrometry (FAAS). No significant matrix interferences were found except for Cr in the acetic acid and hydroxylammonium chloride extracts, which required determination by the standard additions method. Both of soils and sediments studied show similar partitioning of Mn, Ni, Cu and Cr. Mn and Ni can be considered to have significant component bound to the acido-soluble fraction, whereas, Cr and Cu occur largely in the organic and residual phases. The partitioning of Pb and Zn was different between soil and sediment. In terms of mobility and bioavailability, in soils, Ni and Mn can be regarded as moderately available followed by a lower availability of Pb while Cu, Zn and Cr have a very limited availability. In sediments, a higher availability (short-medium term) of Mn and Zn was presumed followed by a lower availability of Ni and Pb, whereas, Cu and Cr, occurring largely in the organic and residual phases, were of very limited availability.     

Solid-phase reagent for molecular spectroscopic determination of heavy metal speciation in natural water

A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.     

Biosampling for metal speciation

Summary Human erythrocytes (ery's) under physiological conditions are capable of a selective uptake of dissolved chromates beside Cr(III) from aqueous solutions. For sampling the mechanical stability of the red blood cells is increased by immobilization in Ca-alginate beads without loss of the biochemical activity against Cr(VI). Radiotracer studies were performed in order to determine the influence of temperature, pH, and concentration and solubility of chromates on the accumulation, which follows a Michaelis-Menten kinetics. After sampling the ery's are separated from the gel and introduced into a multiple-step clean-up procedure preceding a GFAAS measurement of chromium. The direct determination of chromium in erythrocytes (and comparable matrices) by GFAAS is supported by the use of oxygen as alternate gas during the thermal decomposition of the samples, leading to advantages in routine analysis. The statistical parameters of this method are critically reviewed. The combination of biosampling and GFAAS represents a new way for metal speciation, especially in cases where decomposition of the analyte during standard sampling procedures is likely; this is demonstrated for Cr(III)/Cr(VI) as an example in view of immission measurements of Cr(VI) in airborne particulates.Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Possibilities for the harmonization of methods of the dynamic fractionation of elements in soils and bottom sediments

The paper presents the first comparative study of the fractionation of heavy metals, arsenic, antimony, and selenium in soils, sludge and bottom sediments using two systems for dynamic extraction, rotating coiled columns (RCC) and cylindrical microcolumns (MC). It has been revealed that the results of the fractionation of the forms of elements are related with the physicochemical properties of soils, sludge, and bottom sediments and the special features of mixing the sample and eluent in RCC and MC. In particular, it has been demonstrated that, as compared to MC, RCC provides more efficient recovery of the most mobile (ecologically relevant) forms of arsenic, antimony, and selenium from samples rich with organic matter. However, in the majority of cases, despite the different efficiency of the recovery of individual fractions, RCC and MC provide comparable diagrams of the distribution of the extracted forms of elements. The influence of the rate of the eluent flow on the processes of the dynamic extraction of heavy metals, arsenic and antimony in RCC and MC has been estimated. The directions of research for the further harmonization of the methods of dynamic fractionation of forms of elements in soils, sludge, and bottom sediments with different physicochemical mobilities and potential biological availabilities are outlined.     

Trace metal speciation in coastal and off-shore sediments from Ross Sea (Antarctica)

The information on total metal concentration in sediments is not sufficient to assess the metal behaviour in the environment, while speciation studies are more effective in estimating environmental impact of contaminated sediments. Concerning metal distribution in Antarctic marine sediments, several studies reported total or extractable (by means of a unique reagent) content, but only few publications dealt with metal speciation.This work presents the total content and speciation pattern of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in 12 cm sediment cores, sampled both in coastal and off-shore sites of the Ross Sea shelf area, within the framework of the Italian National Antarctic Programme (PNRA). The total content results of metals are comparable with the background values and the speciation highlights good environmental quality of the studied areas. Only Cd and Pb, in fact, are present in significative amount in non residual phases (acid-extractable and reducible, respectively).     

川中丘陵区铁路旁土壤重金属含量及化学形态研究

对川中丘陵区成昆铁路的三圣段、吴场段和成渝铁路的五凤段3个典型路段铁路沿线土壤重金属Cd、Zn、Cu、Pb含量及其化学形态进行了研究,并运用次生相富集系数法对重金属的潜在生态风险进行评估。结果表明:铁路沿线土壤重金属Cd、Zn、Cu、Pb含量与对照点相比都有不同程度的升高。Cd不仅具有高的含量,且化学形态主要为酸可交换态和可还原态,残渣态含量很低,其有效态比例>75%,具有很强的生物活性和可迁移性。Cu、Pb、Zn的化学形态则主要为残渣态,酸可交换态比例很小,但是Pb和Zn的可还原态和可氧化态比例较高,所以有效态比例也较高,分别为51.1%~54.9%和36.2%~50%。土壤重金属Cu在各典型路段的次生相富集系数为1.4~4.2;Zn在三圣段、吴场段2个典型路段的次生相富集系数超过3.0,均具有较大的潜在生态风险。     

Comparison of the acid combinations in microwave-assisted digestion of marine sediments for heavy metal analyses.

Sediments as a tool for monitoring contamination by heavy metals in the environment has long been considered. It is therefore a necessity to produce reliable data for such purposes. Microwave-assisted acid dissolution has proved to be a suitable method for digesting complex matrices, such as sediments. However, due to the infancy of the technique, the procedures are numerous and varied in both the reagents used and microwave conditions. In this study, the efficiency of two recommended acid mixtures, a HNO3-HF mixture and an aqua regia-HF mixture, under the same microwave digestion conditions were compared using certified reference materials. It was observed that the HNO3-HF mixture showed better efficiency than the aqua regia-HF mixture in most of the heavy metals analyzed in all certified reference materials used.     

Effect of chloride on heavy metal mobility of harbour sediments

To evaluate the environmental impact of polluted sediments, several operationally defined sequential extraction procedures (SEPs) have been described. Salinity has long been recognised as an important variable determining the physicochemical behaviour of heavy metals in marine sediments. Thus, in the present paper, the modified BCR-SEP has been applied to harbour sediments in order to assess to what extent trace metal mobility (Cd, Cr, Cu, Ni, Pb and Zn) could be influenced by chloride content in sediments. For this, washed (W) and non-washed (NW) sediments were compared. The relative mobility order observed for the six trace metals studied was not seen to be influenced by the presence of chloride in the sediments, but an increase of mobility was observed for Cd and Zn (the most mobile metals) when chloride was present in the sediments. Characterisation of the sediments and of the pseudo-total metal contents by means of an aqua regia extraction was also assessed.     

Chemical speciation of heavy metals in soils by use of XAFS spectroscopy and electron microscopical techniques

Pb-contaminated soil samples were investigated using XAFS spectroscopy and SEM/EDX as tools for the analysis of chemical binding forms. The soils originated from the vicinity of a battery factory in Hannover (Germany) and had Pb-contents between 50 g/kg and 140 g/kg. PbCO₃, PbSO₄, PbO and basic PbCO₃ could be identified as the main constituents in the samples by XAFS spectroscopy (EXAFS as well as XANES). This result is consistent with the results of the SEM/EDX investigations on the same soil samples, which showed, that almost all of the lead contained in the soils appears in the form of discrete particles of lead compounds. The EDX analysis of these particles consistently shows the presence of Pb, C, O and S.     

Chemical speciation of heavy metals in soils by use of XAFS spectroscopy and electron microscopical techniques

Pb-contaminated soil samples were investigated using XAFS spectroscopy and SEM/EDX as tools for the analysis of chemical binding forms. The soils originated from the vicinity of a battery factory in Hannover (Germany) and had Pb-contents between 50 g/kg and 140 g/kg. PbCO₃, PbSO₄, PbO and basic PbCO₃ could be identified as the main constituents in the samples by XAFS spectroscopy (EXAFS as well as XANES). This result is consistent with the results of the SEM/EDX investigations on the same soil samples, which showed, that almost all of the lead contained in the soils appears in the form of discrete particles of lead compounds. The EDX analysis of these particles consistently shows the presence of Pb, C, O and S. Rececived: 1 September 1998 / Revised: 15 December 1998 / Accepted: 18 December 1998     

Chemical analyses of heavy metal contamination in sediments of the Venice Lagoon and toxicological implications

Heavy metals are extracted from sediments using 1 M HCl; then, solutions are neutralised with 1 M NaOH, to fit the conditions suitable for the Vibrio Fischeri test. In the neutralised solutions different percentages of initial metal concentration are present, depending on the individual solubilities. The chemical investigation of the metal fraction extracted from the sediment with this procedure and the different metal bioavailability depending on the presence of natural complexing agents are the subject of this work. The results obtained confirm the good agreement between heavy metal fraction extracted using 1 M HCl and the anthropogenic component in the sediment. The use of voltammetric techniques, and the addition of low molecular weight humic acids into extracts show the ability of natural complexing agents in affecting heavy metal bioavailability and toxicity.     

Comparison of microwave-assisted acid leaching techniques for the determination of heavy metals in sediments, soils, and sludges

Microwave-assisted EPA method 3051 for nitric acid leaching of environmentally key elements from sediments, soils, and sludges was tested, and the influence of leaching temperature and time on element recovery for an estuarine sediment (CRM 277) was investigated. The extraction efficiencies for four certified reference materials applying EPA method 3051, an optimized nitric acid procedure, and an aqua regia (HCl/HNO₃ 3:1) procedure were compared. Digestions were carried out in a high-pressure microwave system offering simultaneous temperature and pressure control for all digestion vessels employed. Eight elements (Cd, Co, Cr, Cu, Hg, Ni, Pb, and Zn) were determined by ICP-AES and ICP-MS. Extraction efficiency strongly depended on the applied leaching parameters and varied for certain elements among different materials when a nitric acid procedure was applied. In general, element recoveries obtained from the aqua regia procedure were superior to those obtained from nitric acid procedures and showed good agreement with the 95% confidence interval of the certified value for most of the elements investigated. Received: 27 March 1998 / Revised: 29 June 1998 / Accepted: 3 July 1998     

Arsenic speciation in contaminated soils

A method for arsenic speciation in soils is developed, based on extraction with a mixture of 1 mol l(-1) of phosphoric acid and 0.1 mol l(-1) of ascorbic acid, and further measurement with the coupling liquid chromatography (LC)-ultraviolet (UV) irradiation-hydride generation (HG)-inductively coupled plasma mass spectrometry (ICP/MS). The stability of the arsenic species in the extracts is also studied. The speciation method applied to several Spanish agricultural contaminated soils from the Aznalcollar zone shows that arsenate is the main species in all the soils analysed and that in some samples arsenite and methylated species could also be detected. The determination of the "pseudototal" arsenic in these soils, obtained by applying extraction with aqua regia (ISO Standard 11466), is also carried out. Both the speciation method and the aqua regia method are applied to several certified reference materials (CRMs) in which total arsenic content is certified. Finally, the same LC-UV-HG coupling with atomic fluorescence spectrometry (AFS) detection reveals to be a valid coupling system to perform arsenic speciation in the soils according to its fair quality parameters and easy utilisation.