A study on the association of two iodine isotopes,of natural127I and of the fission product129I,with soil components using a sequential extraction procedure

Sequential extraction techniques have been utilized in order to investigate the degree of binding or association of natural iodine¹²⁷I and the radioactive iodine isotope¹²⁹I with soil components. The results indicate that only a small fraction of natural iodine (2.5–4%) but a large fraction of the recently added radioactive¹²⁹I (38–49%) is water-soluble. The other forms of iodine which were determined for both iodine isotopes were exchangeable iodine, iodine bound to metal-oxides and iodine bound to organic matter.     

Resolution of uncertainty of a four-stage sequential extraction procedure using analysis of variance

Sequential extraction procedures are mostly applied to soils and sediments. Investigations were made for testing the applicability of a selected extraction scheme on spoil pile material. Therefore, different spoil pile samples from uranium mining were extracted into four steps (exchangeable, reducible, oxidizable, and aqua regia soluble phase) and the contents of the elements Cr, Cu, Fe, K, Ni, and Zn were analyzed. To substitute the sequential extraction by a sequence of single extractions and thus keep uncertainties of extraction on a low level, both procedures were compared regarding conformity of their results. The effects of sample handling as well as those of analysis on the measured metal contents were determined by means of analysis of variance and sources of uncertainties were discussed.     

Study of partitioning and dynamics of metals in contaminated soil using modified four-step BCR sequential extraction procedure

The modified four-step BCR sequential extraction procedure (exchangeable and weak acid available species, reducible, oxidisable and residual fractions) was used to examine the distribution of As, Cd, Cr, Cu, Pb, and Zn with soil depth in an area (Baia Mare — Bozanta, Romania) with both high natural level of elements considered as toxic and historical pollution resulting from nonferrous metallurgy. The BCR approach proved a high metal input of anthropogenic origin down to 40 cm, while at lower depths the naturally elevated metal content must be considered. Results of the partitioning study and XRD analysis of solid matrix showed the greatest potential for chemical remobilisation of Cd, Zn, and Cu in weak acidic medium as well as their affinity for the oxidisable fraction (organic matter/sulphide). The tendency of Cr, Pb, and As to be immobilised as residual or reducible species on Fe-Mn oxides was evident. Although the partitioning of As in chemically inactive forms such as scorodite (FeAsO₄ · 2H₂O) soluble under reducible conditions and beudantite (PbFe₃(AsO₄)(SO₄)(OH)₂)), a residual species soluble in acid media, chemical mobilisation from soil in groundwater was confirmed. Dynamic processes of metal retention in soil under different conditions, namely acidic, reducing or oxidisable, were predicted from the Pearsonșs correlation analysis of element species with soil characteristics and components such as Fe, Mn, organic matter content, pH, and total element content, respectively. At the moment of the study, soil and groundwater in the area were found to be polluted with As, Cd, Cu, Pb and Zn. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases

This study considers the selectivity of the extractants used in a sequential extraction scheme for metals mobility assessment by analyzing individual mineral phases previously coprecipitated or sorbed with trace metals. The scheme evaluated was a modification of the Tessier et al. [A. Tessier, P.G.C. Campbell, M. Bisson, Anal. Chem. 51 (1979) 844] sequential procedure proposed by the authors. The phases studied were calcite, amorphous iron oxide, hausmannite, humic acid, kaolinite and illite. Selective extractions were obtained for As, Cr, Cu, Ni, Pb and Zn in metal-coprecipitated phases whereas NH(2)OH-HCl was not selective for the extraction of Hg and Cd coprecipitated in hausmannite and amorphous iron oxide, respectively. Otherwise, Cd, Hg, Ni and Zn sorbed on the different phases were released with MgCl(2) and NaOAc/HOAc, but stronger reagents were needed to release As, Cr, Cu and Pb.     

Dynamic fractionation of trace metals in soil and sediment samples using rotating coiled column extraction and sequential injection microcolumn extraction: A comparative study

Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps.A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min⁻¹ prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry.Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilisable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.     

A sequential extraction procedure for an insight into selenium speciation in garlic

A sequential extraction procedure was developed for the fractionation of different classes of selenium species present in garlic. The consecutive steps included leaching with water, extraction of cell-wall bound species after lysis with a mixture of cellulase, chitinase and β-glucanase completed by a proteolytic attack, extraction with HCl to liberate the residual organic bound species and finally, extractions with sulfite solution and CS₂ to complete the mass balance by the recovery of Se⁰ and Se²⁻, respectively. Selenium speciation in the aqueous fractions was probed by anion-exchange and ion-pairing reversed-phase HPLC-ICP MS after purification by preparative size-exclusion LC. It was found to be strongly affected by the sample redox conditions. The peak identity was matched with a mixture of 9 compounds expected to be present in allium plants; electrospray QTOF MS turned out to be unsuccessful. Selenite, selenate and selenomethionine were the dominating species present.     

A modified acid digestion procedure for extraction of tungsten from soil

Interest in tungsten occurrence and geochemistry is increasing due to increased use of tungsten compounds and its unknown biochemical effects. Tungsten has a complex geochemistry, existing in most environmental matrices as the soluble and mobile tungstate anion, as well as poly- and heteropolytungstates. Because the geochemistry of tungsten is substantially different than most trace metals, including the formation of insoluble species under acidic conditions, it is not extracted from soil matrices using standard acid digestion procedures. Therefore, the current work describes a modification to a commonly used acid digestion procedure to facilitate quantification of tungsten in soil matrices. Traditional soil digestion procedures, using nitric and hydrochloric acids with hydrogen peroxide yield <1 up to 50% recovery on soil matrix spike samples, whereas the modified method reported here, which includes the addition of phosphoric acid, yields spike recoveries in the 76-98% range. Comparison of the standard and modified digestion procedures on National Institute of Standards and Technology Standard Reference Materials yielded significantly improved tungsten recoveries for the phosphoric acid modified method. The modified method also produces comparable results for other acid extractable metals as the standard methods, and therefore can be used simultaneously for tungsten and other metals of interest.     

Some sources of variability in application of the three-stage sequential extraction procedure recommended by BCR to industrially-contaminated soil

Copper, lead, manganese and zinc have been determined in extracts of industrially-contaminated soil to investigate possible sources of variability in the three-stage sequential extraction procedure recommended by BCR. Analysis was performed by flame or electrothermal atomic absorption spectrometry, using reagent matched, multi-element standard solutions. Interferences were assessed by use of a single-point standard addition. Although the distribution of contaminants in the soil was expected to be heterogeneous, little difference in precision was found when replicate samples ranging in mass from 1–5 g were extracted, provided the extractant:soil ratio was kept constant. Significant differences in operational speciation were, however, obtained when the procedure was carried out independently by three different analysts. This may be due to the critical effect of pH in Step 2. Reproducibility was higher for air-dried than for field-moist soils, but larger amount of metals were extracted, suggesting alterations in speciation occurred during drying.     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

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.     

Application of a sequential extraction procedure to study the release of elements from municipal solid waste incineration bottom ash

The release of five elements (Cr, Cu, Mn, Pb and Zn) from a municipal solid waste incineration bottom ash (BA) under different extraction conditions has been investigated by performing the three-step sequential extraction procedure proposed by the Standards, Measurements and Testing Program of the European Union. A fourth step (strong acid attack) has been added in order to calculate the mass balance. The results of this study provide information on the potential mobility of the studied elements. Almost all of the Cr and part of the Mn are extracted with strong acid which indicates low potential mobility in the environment. Most of the Cu is extracted under oxidizing conditions. Pb and Zn are released under acidic condition, indicating the possibility of their mobilization by changes in pH. The reproducibility of the sequential extraction procedure is also discussed.     

A sequential extraction scheme to ascertain the role of organic matter in radionuclide retention in Mediterranean soils

A sequential extraction scheme which indicates the role of organic matter in radionuclide retention was applied to two types of Mediterranean soil (sandy-loam and sandy), with low percentages of organic matter and with different contents of clay mineral, which had been previously contaminated with a radioactive aerosol, containing⁸⁵Sr,¹³⁴Cs and^110mAg. Different distributions were obtained for the three radionuclides, depending on the type of soil.⁸⁵Sr was the most available radionuclide for both types of soil, showing significant binding to organic matter in sandy-loam soil.¹³⁴Cs was the most retained radionuclide: for low-organic-matter soils, its availability seemed to depend on clay mineral content.^110mAg associated with available organic sites showed a positive correlation with organic matter content.     

A rapid sequential separation of actinides using Eichrom's extraction chromatographic material

For the past 10 years, Eichrom has provided a variety of innovative products for faster separation of radionuclides to radioanalytical laboratories. However, recently, environmental testing laboratories have been challenged to generate reliable data more quickly. To assist our customers with rapid separations, Eichrom has developed a new configuration for its existing extraction chromatographic material that operates with vacuum assisted flow. After pre-concentration of actinides from a given sample, the actinides are dissolved in a suitable solution. Appropriate Eichrom Resin Cartridges are placed on a vacuum box system. Sample solutions are then passed through the cartridges under optimal vacuum pressure. In this paper, a scheme for separation of actinides in different matrices are discussed using Eichrom Resin Cartridges. Time required for separations, test results and ease of use are the primary discussions of this paper.     

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.     

A kinetic study of trace element leachability from abandoned-mine-polluted soil treated with SS-MSW compost and red mud. Comparison with results from sequential extraction

The effect of adding treated red mud, a by-product of alumina production, to soil polluted by an abandoned mine and characterised by high concentrations of heavy metals, relatively low reaction grade, and low organic carbon content, was investigated. Also studied was addition of both red mud and compost (produced from source-separated municipal solid waste)—the synergistic action of red mud and compost could be exploited to achieve both metal trapping and an increase in organic carbon content. Leaching batch tests were performed on four different systems: soil, soil and treated red mud, soil and compost, soil and compost plus treated red mud. Dilute sulfuric acid and EDTA solution (liquid/solid ratio 10:1) were used in the tests—sulfuric acid to mimic acid rain and EDTA in accordance with general methods for estimating plant-available metals. Sequential extraction was also applied to the same samples. The use of relatively non-specific extractant reagents in the leaching tests led to a kinetic approach (already proposed in literature), because measurements of trace elements extracted at equilibrium cannot be related to their speciation. Comparison of information obtainable by the kinetic approach to evaluation of data from leaching tests with results from sequential extraction enabled evaluation whether the kinetic fractionation method, a relatively rapid and simple procedure, furnishes adequate information about the mobility and bioavailability of trace elements. Especially interesting results were obtained for Mn, Zn, and Ni, present in large amounts in the soil studied—their leachability was significantly reduced by addition of red mud and compost, suggesting interesting perspectives in soil-remediation activity.     

Thallium fractionation in polluted environmental samples using a modified BCR three-step sequential extraction procedure and its determination by electrothermal atomic absorption spectrometry

Determination of thallium in polluted environmental samples and their extracts obtained by a modified BCR three-step sequential extraction procedure was used to study thallium distribution and mobility in the monitored polluted area affected by acidification (Šobov, Central Slovakia). The results of fractionation applied to 5 soil certified reference materials and 14 environmental samples show that the vast majority of thallium occurred in the residual fraction. This means that highly toxic thallium is strongly entrapped in the parent rock materials remains immobile and its environmental toxicity is therefore reduced. The limit of detection for thallium in the studied fractions was lower than 0.050 mg kg⁻¹, the precision (RSD) of the ultratrace determination of thallium in the studied fractions was better than 17 % and the accuracy of the used method was verified by analyzing certified reference materials. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Development of a procedure for the sequential extraction of substances binding trace elements in plant biomass

This work investigates how the amounts of some important substances in a plant, and their behaviour inside the plant, depend on the levels of stress placed on the plant. To this end, model plant spinach (Spinacia oleracea L.) was cultivated on soil treated with sewage sludge. The sewage sludge contained various trace elements (As, Cd, Cu, Zn), and the uptake of these trace elements placed the plant under stress. Following this, a sequential extraction procedure was employed to determine the levels and distributions of trace elements within the most important groups of compounds present in the spinach plants. Since the usual five-step sequential extraction procedure provides only general information on the distributions of elements within individual groups of organic compounds, due to the wide range of organic compounds within the individual fractions, this scheme was extended and improved through the addition of two solvent extraction steps—a butanol step (between the ethyl acetate and methanol solvent steps) and an H₂O step (after the methanol+H₂O solvent step). The distributions and levels of the trace elements within the main groups of compounds in spinach biomass was investigated using this new seven step sequential extraction (water free solvents: petroleum ether (A) ethyl acetate (B) butanol (C) methanol (D) water solvents: methanol+H₂O (1+1; v/v) (E) H₂O (F) methanol+H₂O+HCl (49.3+49.3+1.4; v/v/v) (G)). The isolated fractions were characterized using IR spectroscopy and the trace element contents were determined in the individual fractions. Lipophilic compounds with low contents of Cd, Cu and Zn were separated in the first two fractions (A, B). Compounds with higher As contents (11.5–12.8% of total content) were also extracted in the second fraction, B. These two fractions formed the smallest portion of the isolated fractions. Low molecular compounds from secondary metabolism and polar lipids were separated in the third (C) and fourth (D) fractions, and high molecular compounds (mainly polypeptides and proteins) separated in the fifth and sixth fractions (E, F). The addition of the H₂O solvent step was particularly useful for separating compounds that have a significant impact on trace element bounds. The methanol fraction was dominant for all treatments, and a significant decrease in the spinach biomass separated in this fraction was observed when the soil was treated with sewage sludge. Most of the As (35.5–38.8% of total content), Cu (45.0–51.6%) and Zn (39.8–47.2%) was also determined in this fraction. The G fraction (obtained after acid hydrolysis) contained polar compounds. Most of the Cd was also found in this fraction, as was a significant amount of Zn. Non-extractable residues formed the last fraction (polysaccharides, proteins).     

Evaluation of a sequential extraction procedure for the determination of extractable trace metal contents in sediments

The determination of extractable trace metals in sediments using sequential extraction procedures has been performed in many laboratories within the last ten years in order to study environmental pathways (e.g. mobility of metals, bounding states). However, the results obtained by different laboratories could hardly be compared due to lack of harmonized schemes. Owing to the need for standardization and subsequent validation of extraction schemes for sediment analysis, the Measurements and Testing Programme (formerly BCR Programme) of the European Commission has organized a project to adopt a sequential extraction procedure that could be used as a mean of comparison of data of extractable trace metals in sediments. A scheme was designed after a series of investigations on existing schemes and tested in interlaboratory studies. This paper presents the results of two round-robin exercises on extractable trace metals using this sequential extraction protocol and describes the final version of the extraction procedure amended according to the most recent improvements.