Fractionation of heavy metals in sediment by using microwave assisted sequential extraction procedure and determination by inductively coupled plasma mass spectrometry

In this work, a fast microwave assisted extraction procedure was developed and optimized for the heavy metals (Cu, Ni, Cr, Pb and Cd) partitioning in the three-stage sequential extraction procedure proposed by the European Standards, Measurements and Testing (SM&;T) Program, formerly the Community Bureau of Reference (BCR). The microwave oven procedure was optimized to obtain extraction efficiencies similar to the conventional BCR procedure, in less time, while using smaller volumes of reagents. In the optimization process, three variables (extraction time, ramping time and microwave power) were considered as factors and as a response the concentration of different metal ions in each individual BCR fraction. Interactions between analytical factors and their optimized levels were investigated using a central composite design. Extractable metals obtained by both comparable methodologies were measured by inductively coupled plasma mass spectrometry. With the use of optimal microwave conditions, steps 1–3 of the sequential extraction (including the hydrogen peroxide digestion in step 3) could be completed between 21 and 22 min. Detection limits were between 1 and 18 ng l^{− 1}. The accuracy of the proposed method was checked with a certified reference material (CRM) of Lake Sediment BCR 701. Values obtained were in accordance with those reported for the certified material with only a few exceptions. Different origin sediments (river and marine) were analyzed by both BCR and MW procedures, and the results obtained were comparable according to the t-paired-test for a 95% confidence level.     

Evaluating the mobility of toxic metals in untreated industrial wastewater sludge using a BCR sequential extraction procedure and a leaching test

The distribution and speciation of toxic metals in industrial wastewater sludge (IWS) was investigated. In this work, the modified BCR three-stage sequential extraction procedure was applied to the fractionation of Cr Pb Ni, and Cd in untreated industrial wastewater sludge from industrial sites in Hyderabad (Pakistan). The extracts were analyzed using electrothermal atomic absorption spectrometry. The procedure was evaluated using a certified reference material for soil mixed with sewage sludge BCR 483. The results from the partitioning study indicate that more easily mobilized forms (acid exchangeable) of Cd were dominant. The oxidizable fraction was dominant for all four toxic metals. Metal recovery was good, with <4% difference between the total metal recovered through the extractant steps and the total metal determined after microwave digestion. Lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of toxic species from IWS, and it was observed that levels of leachable toxic metals were low compared to the amount of metal extracted in the exchangeable fraction of the BCR protocol.     

A rapid fractionation method for heavy metals in soil by continuous-flow sequential extraction assisted by focused microwaves

A microwave-assisted continuous-flow sequential extraction system was developed for rapid fractionation analysis of heavy metals in soil. Insertion of pressure-adjusted air between the extractants provided stable flows of the extractants without mutual mixing and back-pressure influence of a column packed with soil, thereby facilitating reliable continuous-flow extractions. In addition, use of pure water as a pumping solvent removed metal contamination because of direct contact between corrosive extractants and the pump containing metallic materials. Focused microwave irradiation to the soil accelerated the selective extractions of the acid-soluble and reducible fractions of heavy metals in soil in the first and second steps of the sequential extraction conditions, as defined by the Commission of the European Bureau of Reference (BCR). The microwave-assisted continuous-flow extraction provided high correlations in amounts of six heavy metals except Zn in the first step and Cu in the second step extracted from a reference sludge soil, BCR CRM 483, with a conventional batchwise extraction proposed by BCR; continuous-flow extraction assisted by conductive heating provided lower correlations for all the six metals. The proposed method drastically reduced the time required for the sequence extraction to ca. 65 min without losing accuracy and precision of the fractionation analysis of heavy metals in soil, whereas the BCR batchwise method requires ca. 33 h. An erratum to this article can be found at     

Microanalytical flow-through method for assessment of the bioavailability of toxic metals in environmental samples

The application of a recently proposed microanalytical flow-through system for on-line sequential extraction of heavy metals from solid samples of environmental interest is described. Using various extraction schemes (a nitric acid scheme, a two-stage extraction scheme using two reagents applied in the BCR procedure) and comparison with the common batch sequential BCR procedure, the suitability of the system for fast screening of solid environmental samples is demonstrated. By pumping leaching agents sequentially through the sample held in a micro cartridge, the different metal fractions present can be assessed in less than an hour. Method evaluation was performed using SRM 1648 urban particulate matter and BCR 701 lake sediment reference material certified for extractable metals. The need for and design of laboratory internal reference material suitable for simulating the natural (dynamic) processes of metal release into the environment is also discussed. For the first time correlation is sought between fractionation techniques and physiologically based methods for assessment of the bioaccessibility of metals in biomatrices.     

Comparison of three sequential extraction procedures (original and modified 3 steps BCR procedure) applied to sediments of different origin

The 3 steps sequential extraction procedure proposed by the Standards Measurements and Testing program (SM&T--formerly BCR) of the European Union has been applied for the speciation of metals in sediments. Results obtained by the application of the BCR standardized procedure were compared to those of two four step sequential extraction procedures, which are different from the BCR procedure only for the introduction of an additional step with NaOCl, as 2nd and 3rd step respectively. Five different metals have been taken into consideration: Cd, Cu, Ni, Pb and Zn. The analytical performances of the laboratory have been evaluated using three certified reference materials: the BCR 601 lake sediment for the BCR sequential extraction procedure, PACS-1 and MESS-1 for total metal concentration. Results showed that the efficiency of NaOCl treatment is higher or at least equal to that of H2O2 treatment and that its selectivity is quite satisfying. Moreover the NaOCl treatment doesn't significantly influence the extraction of the easily reducible fraction.     

Metal fractionation in olive oil and urban sewage sludges using the three-stage BCR sequential extraction method and microwave single extractions

The conventional three-stage BCR sequential extraction method was employed for the fractionation of heavy metals in sewage sludge samples from an urban wastewater treatment plant and from an olive oil factory. The results obtained for Cu, Cr, Ni, Pb and Zn in these samples were compared with those attained by a simplified extraction procedure based on microwave single extractions and using the same reagents as employed in each individual BCR fraction. The microwave operating conditions in the single extractions (heating time and power) were optimized for all the metals studied in order to achieve an extraction efficiency similar to that of the conventional BCR procedure. The measurement of metals in the extracts was carried out by flame atomic absorption spectrometry. The results obtained in the first and third fractions by the proposed procedure were, for all metals, in good agreement with those obtained using the BCR sequential method. Although in the reducible fraction the extraction efficiency of the accelerated procedure was inferior to that of the conventional method, the overall metals leached by both microwave single and sequential extractions were basically the same (recoveries between 90.09 and 103.7%), except for Zn in urban sewage sludges where an extraction efficiency of 87% was achieved. Chemometric analysis showed a good correlation between the results given by the two extraction methodologies compared. The application of the proposed approach to a certified reference material (CRM-601) also provided satisfactory results in the first and third fractions, as it was observed for the sludge samples analysed.     

Application of sequential extraction and the ICP-AES method for study of the partitioning of metals in fly ashes

In this work, the original BCR extraction scheme was modified and applied to study the partitioning of metals in fly ashes. In the first step, the water-soluble fraction was investigated here. The next metal fractions were acid-soluble, reducible, and oxidisable. Two kinds of coal fly ash certified reference materials were analysed. Metal concentrations in the extracts were measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). The efficiency of the extraction process for each step was examined. The partitioning of metals between the individual fractions was investigated and is discussed.     

The utilization of modified BCR three-step sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in soil reference materials of different origins

A modified three-step sequential extraction procedure for the fractionation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) has been applied to the Slovak reference materials of soils (soil orthic luvisols, soil rendzina and soil eutric cambisol), which represent pedologically different types of soils in Slovakia. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). The fractions extracted were: exchangeable (extraction step 1), reducible-iron/manganese oxides (extraction step 2), oxidizable-organic matter and sulfides (extraction step 3). The sum of the element contents in the three fractions plus aqua-regia extractable content of the residue was compared to the aqua-regia extractable content of the elements in the origin soils. The accuracy obtained by comparing the determined contents of the elements with certified values, using BCR CRM 701, certified for the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in sediment following a modified BCR-three step sequential extraction procedure, was found to be satisfactory.     

Fast ultrasound-assisted extraction of copper,iron, manganese and zinc from human hair samples prior to flow injection flame atomic absorption spectrometric detection

A dynamic ultrasound-assisted extraction procedure utilizing diluted nitric acid was developed for the determination of copper, iron, manganese and zinc in human hair taken from workers in permanent contact with a polluted environment. The extraction unit of the dynamic ultrasound-assisted extraction system contains a minicolumn into which a specified amount of hair (5–50 mg) is placed. Once inserted into the continuous manifold, trace metals were extracted at 3 mL min⁻¹ with 3 mol L⁻¹ nitric acid under the action of ultrasound for 2 min for zinc and 3 min for copper, iron and manganese determination, and using an ultrasonic water-bath temperature of 70 °C for zinc and 80 °C for copper, iron and manganese determination. The system permits the direct analysis of hair and yields concentrations with relative standard deviations of <3% (n = 11). The applicability of the procedure was verified by analysing human hair samples from workers exposed to welding fumes, and its accuracy was assessed through comparison with a conventional sample dissolution procedure and the use of a certified reference material (BCR 397, human hair).     

Determination of cadmium and lead in biological samples by three ultrasonic-based samples treatment procedures followed by electrothermal atomic absorption spectrometry

The development of 3 different ultrasonic-based sample treatment methods, ultrasonic probe-assisted acid extraction, ultrasonic-assisted acid slurry, and ultrasonic-assisted acid pseudodigestion is presented. These methods were compared for the determination of Cd and Pb by electrothermal atomic absorption spectrometry in biological samples (blood and scalp hair) and validated by using certified materials BCR 397 human hair and BCR 185R bovine liver. The sample amounts chosen to perform the analysis were 100 mg and 0.5 mL for solids (human hair and bovine liver) and blood samples, respectively. An acid digestion induced by microwave energy was used to obtain the total metal concentrations and for comparative purposes. The best results were obtained with the ultrasonic-assisted acid pseudodigestion, with which it was possible to perform accurate and precise determination of the Cd and Pb contents in 2 certified reference materials and biological samples of 50 normal males of ages 25-40 years. The precision of the methods, together with their efficiency, rapidity, low cost, and environmental acceptability, make them good alternatives for the determination of trace metals from biological samples. The precision of the methods for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level, and the relative standard deviations were lower than 10% (n=10) for all determinations.     

Utilization of optimized BCR three-step sequential and dilute HCl single extraction procedures for soil-plant metal transfer predictions in contaminated lands

The prediction of soil metal phytoavailability using the chemical extractions is a conventional approach routinely used in soil testing. The adequacy of such soil tests for this purpose is commonly assessed through a comparison of extraction results with metal contents in relevant plants. In this work, the fractions of selected risk metals (Al, As, Cd, Cu, Fe, Mn, Ni, Pb, Zn) that can be taken up by various plants were obtained by optimized BCR (Community Bureau of Reference) three-step sequential extraction procedure (SEP) and by single 0.5 mol L(-1) HCl extraction. These procedures were validated using five soil and sediment reference materials (SRM 2710, SRM 2711, CRM 483, CRM 701, SRM RTH 912) and applied to significantly different acidified soils for the fractionation of studied metals. The new indicative values of Al, Cd, Cu, Fe, Mn, P, Pb and Zn fractional concentrations for these reference materials were obtained by the dilute HCl single extraction. The influence of various soil genesis, content of essential elements (Ca, Mg, K, P) and different anthropogenic sources of acidification on extraction yields of individual risk metal fractions was investigated. The concentrations of studied elements were determined by atomic spectrometry methods (flame, graphite furnace and hydride generation atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry). It can be concluded that the data of extraction yields from first BCR SEP acid extractable step and soil-plant transfer coefficients can be applied to the prediction of qualitative mobility of selected risk metals in different soil systems.     

A study on the extraction and quantitation of total arsenic and arsenic species in seafood by HPLC-ICP-MS

Various internal standards and analytical methods were investigated using certified reference materials to evaluate the accuracy of the quantitation of the total As in seafood. Inductively coupled plasma mass spectrometry (ICP-MS) was used to measure the total arsenic. Enhancement of the total arsenic in its concentration caused by the methanol matrix was clearly observed. Selenium (mass 77) was the best internal standard, and the standard addition method combined with the use of Se as an internal standard was the best analytical method. The total arsenic was determined in bluefin tuna, yellowfin tuna, bigeye tuna, and swordfish by ICP-MS. The concentrations of total arsenic in the seafoods ranged from 0.74 to 6.87 mg/kg.Various extraction procedures were also investigated using reference materials to evaluate the extraction efficiency of the different arsenic species in seafood. Inductively coupled plasma mass spectrometry (ICP-MS) was used in conjunction with high performance liquid chromatography (HPLC) to quantitate the arsenic species in seafood. The arsenic species were extracted from tuna fish (BCR 627) with water/methanol mixtures using sonication, a microwave-assisted system, and ultrasonic processor. The major species was arsenobetaine. The total arsenic extraction efficiency ranged from 81 to 87% for water and various methanol concentrations. Chromatograms of the arsenic species extracted from the Korea Research Institute of Standards and Science (KRISS) tuna, bluefin tuna, yellowfin tuna, bigeye tuna, and swordfish were obtained by the optimum extraction methods and the species were quantified.     

New methods for acceleration of meat sample preparation prior to determination of the metal content by atomic absorption spectrometry

Focused microwave-assisted digestion and ultrasound leaching have been applied for the extraction of Pb, Cd, Cr, Cu, Fe, Zn, Ca, and Mg from raw meat. Semimembranous muscle (SM) of raw pig ham was used for optimizing both the digestion and extraction steps by multivariate approaches. The detection and quantification limits were 0.5 and 0.9 g kg^–1 for Pb, 0.06 and 0.1 g kg^–1 for Cd, 0.2 and 1.2 g kg^–1 for Cr, 0.4 and 3 g kg^–1 for Cu, 0.04 and 0.1 mg kg^–1 for Fe, 0.012 and 0.017 mg kg^–1 for Zn, 0.3 and 0.4 mg kg^–1 for Ca, and 0.01 and 0.03 mg kg^–1 for Mg. The precision, expressed as relative standard deviation (RSD), ranged between 2.5 and 9.6% for focused microwave-assisted digestion and between 3.5 and 10.6% for ultrasound leaching. The methods were then compared with a reference method and applied to a certified reference material (bovine muscle 184, from the BCR). The t-test, applied to the results obtained from focused microwave-assisted digestion, revealed that they are in agreement (p>0.01) with the certified and estimated values in the case of Pb, Cd, Cr, Cu, Fe, Ca, Mg, and Zn but not in that of Fe. In the case of ultrasound leaching, only the extraction of Pb, Cu, and Ca was quantitative. The method based on microwave digestion provides more accurate and precise results than ultrasound leaching. These new procedures have many advantages with regards to conventional methods, namely, reduction of the extraction time, simplification of the process, avoidance of chemical emissions to the atmosphere, and no losses of metals by volatilization.     

Kinetic speciation of BCR reference materials

The accurate study of heavy metal speciation is important in environmental monitoring. There has been much work developing various operationally defined speciation methods for soil and sediment, but there is a need to compare the different approaches by evaluating them for the same sample. In this article, a kinetic method was applied for the heavy metal speciation of the two BCR reference materials, CRM601 and BCR701, which have been specifically developed as materials to evaluate the validated BCR three-step sequential extraction method. When EDTA was used as an extractant, 81.0% of Cd, 68.0% of Cu, 21.5% of Ni, 80.3% of Pb and 71.9% of Zn was extracted from CRM601. For BCR701, the removal ratios were 92.0, 52.3, 18.7, 50.6 and 67.5% with EDTA and 95.7, 25.2, 20.0, 52.4 and 68.5% with hydroxylamine hydrochloride as an extractant, for Cd, Cu, Ni, Pb and Zn respectively. A two-component kinetic model was applied to the extraction curve and the extractable metals were readily classified into two categories, namely, labile fraction and non-labile fractions. The rate constants obtained from the regression model were found to be useful in quantifying the lability of an element. The rate constants obtained from the labile fractions in BCR701 were higher than that of obtained from CRM601, which indicated the high lability of metals in BCR701. When compared with the sequential extraction data, it seemed that the lability of an element was positively correlated to the first step extraction fraction.     

Efficient extraction of PAHs in aqueous organised media assisted by focused microwaves

Summary A novel method for the extraction into an aqueous medium of PAHs in soil is described, where sodium dodecyl sulphate (SDS) is used as micelle former. After optimisation of this step using a multivariate approach, recoveries of the target analytes from spiked soil ranging between 98.3%–99.7% were obtained when the samples were subjected to extraction with 25 mL of an aqueous SDS solution (2.9 10⁻² mol L⁻¹) while irradiated with focused microwaves at 240 W for 40 min. The overall method involving determination of the extracted compounds consists of three steps: 1) extraction of the analytes into the aqueous micellar medium assisted by focused microwaves; 2) trapping of the analytes on a C₁₈ cartridge for clean up and preconcentration and; 3) HPLC separation with fluorimetric detection. The method was validated using the certified reference material CRM 524 and the results found were in agreement with the certified values.     

Investigation of heavy metals mobility in shrimp aquaculture sludge—Comparison of two sequential extraction procedures

Influence of heavy metals was investigated by conducting various tests on the samples collected from aquaculture shrimp in Selangor, Malaysia. The concentration of heavy metals in the sludge and potential of mobility based on its association forms was studied. Two sequential extraction methods (five stages Tessier method and three steps BCR method) were used to determine the binding forms of the metals.From the analysis, Ca, Fe and Mn were found to be highest concentrated metals compared to Zn, Cu, Cr, Cd and Pb in aquaculture shrimp sludge. From the sequential extraction, Cd, Mn and Pb were mostly found in exchangeable/carbonate form, showed its susceptibility to be leached easily. Also Cu and Zn were extracted predominantly in oxidizable form. All metal concentrations (except Cd, Zn and Cu) were extracted to be higher in residual fraction in this method. The results of BCR method are totally similar to the five stages Tessier method. By comparing the percent of recovery, the BCR method was better than Tessier method. Nevertheless for both methods the percent of their recoveries were acceptable. For Pseudototal metal digestion, although the concentration of Cd is less than other heavy metals, it is very harmful as a fertilizer because Cd is one of the heavy metals that might be in the leaf or fruit of plants. Also for investigation of Ca in the sludge, this element was measured and high amounts of that show sludge is useful for growing of plant. The results of direct digestion of heavy metals show that with the control of Cd in this sludge we can use this sludge as fertilizer in soils for agriculture but it is better if it is used for fruitless plants.     

Determination of Pt from coke samples by ICP-MS after microwave assisted digestion and microwave assisted cloud point extraction

Platinum in coke samples was determined by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted sample digestion and temperature controlled microwave assisted cloud point extraction (MW-CPE). Interferences due to hafnium (¹⁷⁹Hf¹⁶O) were successfully eliminated using MW-CPE with 2-MBT prior to the determination of platinum by ICP-MS. The validity of the method was studied by spike recovery tests and by analyzing certified reference material (BCR-723 street dust). The results obtained for platinum in the BCR-723 were generally in good agreement with the certified values. Furthermore, the preliminary platinum results obtained for coke sample by ICP-MS after MW-CPE were compared to those obtained by a reference method (NiS-Fire Assay preconcentration/Te coprecipitation and ICP-MS determination).     

Determination of Pyrethroid and Organophosphorus Insecticides in Indoor Air by Microwave-Assisted Extraction with Gas Chromatography/Mass Spectrometry

The goal of this study was to evaluate the efficiency of microwave-assisted extraction for the recovery of pyrethroid and organophosphorus insecticides adsorbed on quartz fiber filters and C18 disks used for indoor air sampling. The extraction solvent, temperature, and time were optimized by spiking tests. The recoveries for the insecticides obtained by microwave-assisted extraction with acetone at 50°C for 5 min were between 71.9% and 119.2% with relative standard deviations between 0.3% and 9.3% at two spike levels (0.1 µg and 1.0 µg). The results of the microwave-assisted extraction under the validation conditions were comparable to those obtained by Soxhlet extraction, which was used as a reference technique. In a preliminary analysis, resmethrin and tetramethrin were determined in the indoor air of an apartment unit at concentrations of 7.8 ng/m³ and 66.0 ng/m³, respectively, using the microwave-assisted extraction-based method with gas chromatography/mass spectrometry.     

Development of an analytical method based on microwave-assisted extraction and solid phase extraction cleanup for the determination of organochlorine pesticides in animal feed

A method to determine 21 organochlorine pesticides in animal feed samples using microwave assisted extraction and solid phase extraction cleanup was optimised regarding its main parameters. After extraction with hexane-acetone (50:50), three different sorbents (alumina/ENVI-Florisil, ENVI-Carb and ENVI-Carb II/PSA) were assayed for the cleanup step. Analytes were eluted with hexane-ethyl acetate (80:20) and determined by gas chromatography and electron capture detection followed by gas chromatography-mass spectrometry. ENVI-Carb and ENVI-Carb II/PSA provided colourless eluates but fewer interferent compounds were found in ENVI-Carb II/PSA chromatograms, so this system was selected to carry out the purification of the extracts. The analytical recoveries obtained with this method were close to 100% in most cases with relative standard deviations lower than 10%. These percentages were similar to those obtained with the Soxhlet extraction procedure, which shows the method suitable for the determination of organochlorine pesticides in animal feed material. The method was also validated with the analysis of a certified reference material (CRM-115 BCR), and the results obtained were in good accordance with the certified values.     

Optimisation and comparison of microwave-assisted extraction and Soxhlet extraction for the determination of polychlorinated biphenyls in soil samples using an experimental design approach

Optimisation of microwave-assisted extraction (MAE) for the extraction of polychlorinated biphenyls (PCBs) from soil samples has been accomplished using an experimental design approach. Variables studied have been: percentage of acetone (v/v) in an acetone:n-hexane mixture, solvent volume, extraction time, microwave power and pressure inside the extraction vessel. Five samples of a certified soil (CRM 481) have been extracted under the optimum conditions of the developed method and the results have been compared to those obtained by Soxhlet extraction. Good recoveries (>95%) have been obtained for all the PCBs studied. All extracts have been analysed by gas chromatography/mass spectrometry (GC/MS) and an optimum determination method for the electron impact mass spectrometric (EIMS) has also been developed.