Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants.     

Microwave extraction of organochlorine pesticides from soils

The purpose of this work was to develop a rapid, reliable and sensitive method for the extraction of organochlorine pesticides from soils using microwave energy with closed vessel technology. Three oven programs were assayed with two different solvent mixtures in order to achieve adequate experimental conditions for the complete extraction of organochlorine pesticides from the matrix. The method was validated using a certified reference soil material (CRM804-050).     

Substoichiometric extraction of metals and its application to the determination of heavy metals in environmental samples by neutron activation analysis

Solvent extraction as a technique for the separation of ionic solutes and the advantages and application of substoichiometric extraction in neutron activation analysis have been discussed. The application of this technique has been elucidated with reference to the determination of Zn, Cd and Hg in environmental samples. The decontamination factor, accuracy, precision, sensitivity and radiochemical purity of the separated fraction have been discussed.     

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%.     

Speciation of heavy metals in polluted soils by sequential extraction and ICP spectrometry

Heavy metals were leached from various polluted soils by selective extraction reagents (water, BaCl2, acetate buffer + EDTA, HNO3) in order to establish the distribution of the chemical species of Cd, Zn, Cu and Pb. The leachates were directly injected into a plasma spectrometer in order to analyse immediately the extraction solution. This continuous on-line analysis gives qualitative information about the chemical behaviour of each element in function of the type of soil. It permits also to modify the extraction procedure for each sample studied by adjusting the volume of the extraction solution, the time of extraction, or by choosing another extraction reagent more adapted to the sample. The sum of the respective fraction is in rather good agreement with the total analysis of the soil.     

Microwave assisted extraction of organochlorine pesticides from sediments and its application to contaminated sediment samples

A method was established and optimized for rapid and reproducible analyses of 17 organochlorine pesticides in sediments employing microwave assisted extraction followed by gas chromatographic separation with mass spectrometric detection using a computer optimized temperature program. For optimization, 5 g portions of sediment were spiked with a standard solution of the 17 analytes in isooctane at ∼50 ng/g for each pesticide and extracted in a microwave oven for 30 min at 100 °C using three different solvents. The best recoveries between 74% and 99% (RSD = 1.0–10.2%) were obtained with tetrahydro furan. The time consuming and laborious clean-up using liquid/liquid-extraction and two column-chromatographic steps was replaced by a one step liquid/solid-extraction, showing the same or even better performance in terms of recovery and reproducibility. Calibration plots were linear for all analytes and MDLs were in the range from 2–9 ng/g. To show the environmental applicability, the method was employed for the analysis of naturally contaminated sediments from the Netherlands (SETOC 701). The results were compared with the results obtained in our lab with ultrasonic extraction and supercritical fluid extraction and corresponded well with the median of results obtained from different interlaboratory comparison studies. Received: 18 January 1998 / Revised: 30 March 1998 / Accepted: 2 April 1998     

Microwave assisted extraction of organochlorine pesticides from sediments and its application to contaminated sediment samples

A method was established and optimized for rapid and reproducible analyses of 17 organochlorine pesticides in sediments employing microwave assisted extraction followed by gas chromatographic separation with mass spectrometric detection using a computer optimized temperature program. For optimization, 5 g portions of sediment were spiked with a standard solution of the 17 analytes in isooctane at ∼50 ng/g for each pesticide and extracted in a microwave oven for 30 min at 100 °C using three different solvents. The best recoveries between 74% and 99% (RSD = 1.0–10.2%) were obtained with tetrahydro furan. The time consuming and laborious clean-up using liquid/liquid-extraction and two column-chromatographic steps was replaced by a one step liquid/solid-extraction, showing the same or even better performance in terms of recovery and reproducibility. Calibration plots were linear for all analytes and MDLs were in the range from 2–9 ng/g. To show the environmental applicability, the method was employed for the analysis of naturally contaminated sediments from the Netherlands (SETOC 701). The results were compared with the results obtained in our lab with ultrasonic extraction and supercritical fluid extraction and corresponded well with the median of results obtained from different interlaboratory comparison studies. Received: 18 January 1998 / Revised: 30 March 1998 / Accepted: 2 April 1998     

Adsorption and redox reactions of heavy metals on Fe-Mn nodules from Chinese soils

Adsorption of heavy metals and redox reactions of Cr(W) ions on Fe-Mn nodules from five soils of China were investigated by chemical analysis, equilibrium adsorption/redox, and X-ray photoelectron spectroscopy (XPS). Results show that Mn is mainly present as Mn(3+) and Mn(4+) forms in Fe-Mn nodules. The maximum adsorption amounts for different heavy metal ions follow the order Pb(2+) approximately Cu(2+)>Zn(2+)>Co(2+)>Ni(2+)>Cd(2+). The adsorption capacity for heavy metals by Fe-Mn nodules from calciaquert in Shandong province (N5-1) is the highest, while that from hapludalf in Shandong province (N6-1) is the lowest. About 44-100% of the heavy metals adsorbed on Fe-Mn nodules were dissolved in 0.1 mol/L hydroxylamine hydrochloride (HAHC). The maximum amounts of Cr(VI) production by Fe-Mn nodules follow the order of N1-1 (69 mmol/kg)>N4-1 (57 mmol/kg)>N2-1 (52 mmol/kg)>N5-1 (44 mmol/kg). Based on the content of MnO(2) in Fe-Mn nodules dissolved in HAHC, the amount of Cr(VI) production by Mn oxides in N1-1, N2-1, N4-1, and N5-1 is 326, 624, 726, and 482 mmol/kg (MnO(2)), respectively. We propose that the amounts of Cr(VI) production through oxidation Cr(III) by Mn oxides are related to the types of Mn oxides in Fe-Mn nodules.     

Separation and recovery of heavy metals from hydrometallurgical effluents by solvent extraction

Summary The possibility of separating and recovering heavy metals from hydrometallurgical effluents by successive solvent extractions has been investigated by two different procedures with liquid waste from the Espindesa Zinc process. The waste (pH value near to 1.5) includes significant amounts of Zn (1.35), Cu (0.12), Co (0.32) and Mn (0.6 g/l) in the presence of big concentrations of macro-constituents (sulphate, chloride, Na) and Fe [8.8 g/l, mostly as Fe(II) salts]. As extractants, Amberlite La-2 (a secondary ammine, as chlorohydrate) and DEHPA (di-2-ethylhexyl-phosphoric acid) at 25% volume in kerosene were selected. The first method includes two extraction stages with LA-2 for Zn and Cu separation (the last one with 60 g/l of chloride ions) and three stages with DEHPA at pH values near to 1.5, 2.0 and 3.5 for isolating Fe, Mn and Co. The second method separates firstly Fe (as ferric salts) with DEHPA. Afterwards, one stage with LA-2 isolates Zn and three stages with DEHPA at pH values near to 2.0, 3.0 and 3.5 lead to fractions rich in Mn, Cu and Co. Reextractions from organic layers with water or HCl at different concentrations lead to purer solutions of the isolated metals. With both methods, the liquid waste can be converted into a saline solution with lesser problems for disposal.     

Separation of rhenium from molybdenum and other heavy metals by solvent extraction

Summary Two methods are presented for the extractive separation of rhenium from molybdenum and other heavy metals in hydrochloric acid solution. In the first method, Mo(VI) and Re(VII) are reduced by hydrazine in strong hydrochloric acid solution to Mo(V) and Re(IV). The former is then extracted intoiso-amyl acetate. The Re(IV) remaining in the aqueous phase is oxidised to Re(VII) and determined by known procedures. In the second method, Re(VII) and other ions in 1–1.3N HCl are boiled with hydrazine sulphate for 5 minutes. After adding EDTA to complex Mo(V) and adjusting the solution to 0.33N HCl, rhenium is extracted into chloroform containing 1% tribenzylamine, and is recovered by shaking with water having sufficient ammonia to neutralise the acid and a little hydrogen peroxide.

---

Zusammenfassung Zwei Arbeitsweisen für die extraktive Trennung des Rheniums von Molybdän und anderen Schwermetallen in salzsaurer Lösung wurden angegeben. Bei dem ersten Verfahren werden Mo(VI) und Re(VII) mit Hydrazin in stark salzsaurer Lösung zu Mo(V) und Re(IV) reduziert. Ersteres wird dann mit Isoamylacetat extrahiert. Re(IV) verbleibt in der wäßrigen Phase, wird zu Re(VII) oxydiert und auf bekannte Art bestimmt. Beim zweiten Verfahren werden Re(VII) und die anderen Ionen in 1- bis 1,3-n Salzsäure 5 Minuten mit Hydrazinsulfat gekocht. Nachdem man ÄDTA zur Komplexierung des Mo(V) zugesetzt und die Lösung auf 0,33-n an Salzsäure eingestellt hat, wird Rhenium mit einer 1%igen Lösung von Tribenzylamin in Chloroform extrahiert. Die Rückextraktion erfolgt mit Wasser, worin Ammoniak (zur Neutralisation der Säure) und etwas Wasserstoffperoxid gelöst sind.

     

Investigations on the supercritical fluid extraction of spiked organic pollutants from wet soils

The possibility of a fractionation (sequential extraction) of certain groups of compounds has been investigated during supercritical fluid extraction (SFE) from wet and dry wetland-soils. The classes of compounds considered are chlorinated hydrocarbons on the one hand and nitrogen- or phosphorus-containing pesticides (N/P-pesticides) on the other hand. The results show the great influence of water on the efficiency of the extraction and the limited possibility of attaining a fractionation during the extraction.     

Distribution of heavy metals of agricultural soils of central Greece using the modified BCR sequential extraction method

The state of heavy metal (Cd, Cu, Ni, Zn, Pb, and Cr) pollution was studied, in 440 texturally different soil profiles in Thessaly, an intensely cultivated region in Central Greece. The study was carried out in 2004 and 2005 on 220 soil samples for each year. Soil samples were classified in three soil orders: Endisols, Alfisols, and Vertisols according to the Soil Taxonomy System. The pseudo-total concentrations of heavy metals were determined by the aqua regia procedure. Heavy metals were also determined after division into four fractions by sequential extraction with (a) acetic acid (exchangeable and specifically adsorbed metals), (b) a reducing agent (bound to Fe/Mn hydroxides), (c) an oxidizing agent (bound to soil organic matter), and (d) aqua regia (bound to mineral structures, residual). The concentrations of all the metals studied were higher in the topsoil (0–30?cm) and lower in the second soil layer (30–60?cm). Concentrations of 70–82% of Cd, 39–64% of Cu, 41–69% of Ni, 29–51% of Zn, 75–89% of Pb, and 52–87% of Cr were found in the first two fractions. Cd appeared to be the most mobile of the metals studied, while Cu and Zn were found in forms associated with soil organic matter. The chemical partitioning patterns of Pb and Cr indicated that these metals are largely associated with the Fe–Mn hydroxides, while Cr was also found in the residual fractions. Significant correlations between heavy metals fractions and soil physicochemical parameters were obtained and discussed.     

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

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

Carbon nanotube-based extraction and electrochemical detection of heavy metals

In this mini review, recent trends and challenges in developing carbon nanotube-based extraction and electrochemical detection of heavy metals in water are reviewed. Carbon nanotubes (CNT) have electrical, mechanical, chemical, and structural properties superior to those of conventional materials, for example graphite and activated carbon. CNT-based procedures are also more efficient than traditional techniques and methods, for example liquid?Cliquid extraction, atomic-absorption spectroscopy, flame photometry, and inductively coupled plasma, because they can enable rapid, sensitive, simple, and low-cost on-site detection. Different forms of CNT, including as-grown, oxidised, and functionalised CNT, can be well suited to metal adsorption. The measurement procedure relies on adsorbing the metal on the CNT surface after reasonable contact time, either by applying an electrical potential or under open-circuit conditions, and subsequent quantification. Different types of CNT-based electrode, including composite, paste, and binder-free, can be fabricated and used for metal detection. Application of CNT and their novel properties to the adsorption and detection of heavy metals is discussed in detail.     

Sequential heavy metals extraction from polluted solids: influence of sulfate overconcentration

The effect of sulfate on the chemical partitioning of Cu, Cd, and Pb in solid phases was assessed in this study. Modified BCR sequential extraction, speeded up by focused ultrasound, was systematically applied to various mixtures of typical geochemical solid phases (an artificial goethite spiked with Cu, Cd, and Pb and natural clays), with or without the addition of calcium sulfate. Sulfate was added so that three different concentrations were found in sequential extracts: 0.5, 1, and 1.5 g/L of sulfate. First, the results suggested that the goethite-surface adsorption sites for sulfate are limited. Then, significant changes in Cd and Pb fractionation were observed in the presence of sulfate, whereas Cu remained strongly adsorbed on the solid phases. The main modifications observed in all the studied samples were a decrease in metal amounts in the first three fractions to the profit of an increase in the residual fraction. These results suggested that the adsorption of metals onto the studied solids was enhanced by the presence of sulfate. From these considerations, some hypotheses are advanced to describe the behavior of Cu, Cd, and Pb and their adsorption mechanisms on solid phases in sulfate-rich systems.     

The preparation of n-octylaniline and its application in the extraction of noble metals

n-Octylaniline was prepared by nitration of n-octylbenzene followed by reduction with tin and hydrochloric acid and also by the high-temperature reaction of aniline with 1-octanol in the presence of zinc chloride. Little difference was found in the efficiency of extraction of noble metals with the products prepared by the two methods. The first method gives better yields of n-octylaniline and the formation of emulsions in the extraction is not a serious problem provided that the reagent is distilled before use. The para-isomer of n-octylaniline shows a slightly greater tendency than the ortho-isomer to form emulsions in noble metal extractions.     

二苯卡巴腙键合硅胶固定相的制备及对重金属离子的选择性分离富集研究

制备了二苯卡巴腙键合硅胶,研究了此键合硅胶的性质及对常见重金属离子的分离富集行为,发现对水中痕量Hg(Ⅱ)有好的选择性富集效果,通过实验对富集条件进行了选择。研究结果表明:对Hg(Ⅱ)的最大富集率可达100%,最大吸附量为1.84×10-3mmol g。该键合硅胶对于水中痕量Hg(Ⅱ)的富集分离与测定具有较高的灵敏度和较好的富集作用,富集倍率为540。可在Cd(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)等多种金属离子存在下对Hg(Ⅱ)进行选择性富集。     

A green approach for sequential extraction of heavy metals from Li irradiated Au target

An aqueous biphasic extraction system was designed using different molecular weights of polyethylene glycol and concentrated salt solutions of sodium sulphate to separate the heavy metals, Hg, Tl and Pb from Li irradiated Au matrix. All the four elements could be separated from one another by this extraction process by simply optimizing the salt rich phase, the pH of the salt rich phase and the molecular weight of the polymer rich phase.     

Assessment of heavy metals leachability from metallo-organic sorbent-iron humate-with the aid of sequential extraction test

The sequential extraction test, known as a BCR procedure, was used to assess a leachability of heavy metals (Zn, Cd, Pb, Cu) from the metallo-organic sorbent—iron humate—loaded with these metals. The sequential test allowed to discriminate between various fractions of heavy metals, namely the acid-extractable fraction, the fraction bound to Fe oxides, and the fraction bound to organic matter. It was proven that the heavy metals are bound mainly to Fe oxides and organic matter, and thus they may be relatively hardly liberated into the environment. The BCR sequential extraction test exhibited a very good repeatability, when it was applied to the loaded sorbent—relative standard deviations were typically lower than 10%.