Comparison of metal analysis in sediments using EDXRF and ICP-OES with the HCl and Tessie extraction methods

The work presents an investigation on metal availability in sediments during 13 months using the dispersive-energy X-ray fluorescence (EDXRF) and atomic emission spectrometry with induced argon plasma (ICP-OES) techniques and single extraction (0.1 mol l⁻¹ HCl) and Tessie’s sequential speciation methods. The EDXRF technique could yield essentially the same profile as ICP-OES for the seasonal variation of metals in sediments, but in a more practical way. The sequential extraction procedure (SEP) was more efficient in metal dissolution than single extraction. The Pb, Ni, Al, Cr, and Fe elements were less efficiently extracted with single extraction in relation to sequential extraction. For Co both methodologies were equivalent, but for Cu and Mn the extraction was higher with single extraction. Single extraction does not mobilize Pb, Ni, Al, Cr, and Fe adsorbed on oxides and bound to organic matter. However for Cu and Mn, not only extracted these metals from the four fractions, but it also dissolved part of the fifth fraction (residual). Principal Component Analysis discriminated seasonal variations in the content of several metals, mainly Fe, Co, Ni, and Zn. The mobility of metallic ions in the sediments is conditioned to the seasonal flow of organic and inorganic material coming from the river or by the erosion of adjacent soils.     

A critical evaluation of the 0.05 M EDTA extraction of Pb from forest soils

Among many single-step extraction procedures proposed, 0.05 M EDTA (ethylenediaminetetraacetic acid) extraction is widely used. Although it has been often criticised, this protocol remains an effective and simple approach for a fast determination of the potential availability of several metals (e.g., Pb, Cd, Cu, Zn, etc.). However, other metallic elements present in soils at high concentrations such as Ca and Fe can possibly influence the extraction of the target metal due to competition for the EDTA ligand. The aim of this study was to evaluate the role of these metals during the 0.05 M EDTA extraction procedure. Furthermore, sequential extraction and Pb isotope analyses (^206/207Pb) were used in order to obtain more detailed information. The results of this study showed that especially the concentration and crystallinity of Fe play a very important role during the extraction of the target metals from low to moderately contaminated soils and this fact should be taken into account during result interpretation.     

Investigation of heavy-metal uptake by vegetables growing in contaminated soils using the modified BCR sequential extraction method

The heavy metal (Cu, Fe, Co, Ni, Cd, Cr, Pb, Zn, and Mn) concentrations in soils and in vegetable samples, i.e. lettuce (Lactuca sativa L.), parsley (Petroselinum crispum), dill (Anethum graveolens), and onion (Allium cepa L.), taken from three urban vegetable gardens in Kayseri, Turkey, were determined by FAAS. The modified three-step sequential extraction procedure proposed by the European Bureau of References (BCR), now the Standards, Measurements and Testing Programme, was used in order to evaluate trace elements mobility in soil samples, and heavy-metal uptake by vegetables. Three operationally defined fractions were isolated using the BCR procedure: acid extractable (i.e. bound to carbonates), reducible (bound to Fe/Mn oxides), and oxidizable (bound to organic matter and sulphides). The vegetable samples were prepared to analysis using the wet-ashing procedure. To estimate the accuracy of the method used in analysis of the vegetable samples, the standard reference material (NIST SRM 1573a, Tomato leaves) was used. The results of recovery for all the elements were relatively satisfactory (87.7–108%). For the soil samples, the recovery values were calculated by proportioning the sum of the steps of the BCR procedure to those of the pseudototal digestion (i.e. aqua regia). In soils, the mobility of heavy metals followed the order Mn>Cd>Cu>Pb>Zn>Cr>Ni>Co>Fe. The relationship between the vegetable–metal and soil–extractable metal concentrations was examined in order to evaluate the bioavailability of metals, and the positive correlation, especially for the first (i.e. water, acid-soluble and exchangeable fraction) and for the third (i.e. oxidizable fraction) extraction steps, was obtained.     

Continuous-flow extraction system for elemental association study: a case of synthetic metal-doped iron hydroxide

A continuous-flow extraction system originally developed for sequential extraction was applied to study elemental association of a synthetic metal-doped amorphous iron hydroxide phase. The homogeneity and metal association of the precipitates were evaluated by gradual leaching using the system. Leachate was collected in fractions for determination of elemental concentrations. The result obtained as extractograms indicated that the doped metals were adsorbed more on the outermost surface rather than homogeneously distributed in the precipitates. The continuous-flow extraction method was also used for effective removal of surface adsorbed metals to obtain a homogeneous metal-doped synthetic iron hydroxide by a sequential extraction using acetic acid and small volume of hydroxylamine hydrochloride solution. The system not only ensures complete washing, but the extent of metal immobilization in the synthetic iron hydroxide could be determined with high accuracy from the extractograms. The initial metal/iron mole ratio (M/Fe) in solution affected the M/Fe mole ratio in homogeneous doped iron hydroxide phase. The M/Fe mole ratio of metal incorporation was approximately 0.01–0.02 and 0.03–0.06, for initial solution M/Fe mole ratio of 0.025 and 0.100, respectively.     

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.     

Fractionation of Sb and As in soil and sludge samples using different continuous-flow extraction techniques

The fractionation of Sb and As in soil and sludge samples had been comparably studied using two continuous-flow systems: a microcolumn (MC) and a rotating coiled column (RCC). The leachants were applied in correspondence with a five-step sequential extraction scheme addressing water-soluble, non-specifically sorbed, specifically sorbed, and bound to amorphous and crystalline Fe/Al oxide fractions of Sb and As. Inductively coupled plasma atomic emission spectroscopy was applied to determine antimony, arsenic, and major elements in the effluent and in the residual fractions after their digestion. Resemblances and discrepancies of the two methods were evaluated by the fractionation of Sb and As in forest soil, river sludge, and dumped waste (soil) samples. For the forest soil sample, which is very poor in organic matter, RCC and MC extractions yielded similar quantitative values of As and Sb contents in individual leachable fractions. However, for the river sludge sample with a moderate concentration of C _org (3.3 %), the results obtained by both continuous-flow methods are in satisfactory agreement. RCC extraction enabled water-soluble and non-specifically sorbed As fractions to be recovered, whereas after MC leaching, these environmentally relevant forms of As were not detected. For the soil rich in organic matter (C _org = 11.5 %), the discrepancy between the data of RCC and MC fractionations is significant. RCC extraction provides about six times higher recoveries of As and Sb bound to amorphous Fe/Al oxides. More efficient leaching of As and Sb in RCC may be attributed to the migration of organic-rich particles with low density inside the column that might enhance the mixing of the solid and liquid phases.     

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.     

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martínez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thorium and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (F2) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (F3) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure. According to correlativity analysis of various fractions, it might be predicted that how the non-residual fractions of thorium were directionally transformed into interrelated fractions under the changes of conditions.     

Environmental mobility of trace metals in sediments collected in the Lake Balaton

In environmental pollution studies on solid materials sequential extraction techniques are used for the identification of the main binding sites of trace metals. A four-step sequential extraction procedure was applied to the determination of the distribution of elements like Cd, Cu, As, Pb, Cr, Ni, Zn, Al, Fe, and Mn in sediment samples collected in the Lake Balaton. The fractions were (1) exchangeable and bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter and sulfides, and (4) acid-soluble. Elements were mainly accumulated in the stable, acid-soluble fractions. Arsenic and Cd-ions were found in low concentration (1.2–13 mg/kg and < 1 mg/kg, respectively) in the samples. Based on the results determined at 15 sampling points it can be stated that the Lake Balaton has not yet been polluted by the elements investigated.     

Comparative study of optimised BCR sequential extraction scheme and acid leaching of elements in the certified reference material NIST 2711

The optimised BCR sequential extraction procedure and a 4 h 1 mol L⁻¹ HCl partial extraction have been performed on the NIST 2711 reference material for a suite of 12 elements (Cd, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using magnetic sector ICP-MS. A pseudo-total aqua regia digest of NIST 2711 has also been undertaken for quality assurance purposes, and comparison of the sum of the four BCR fractions, which included an aqua regia digest on the residue, with the pseudo-total aqua regia digest has been used to assess the accuracy of the BCR partitioning approach. As a result of this work, discrepancies between previous studies about BCR partitioning of elements in NIST 2711 have been discussed and an increase in confidence about the use of BCR partitioning scheme on seven elements (Cd, Pb, Al, Mn, Fe, Cu, Zn) in this standard material has been obtained. On the other hand, BCR partitioning for Sb, Cr, Co, Ni and As has been provided for the first time. Partial extraction results are also reported for the same 12 elements analysed by the optimised BCR procedure, with the partial extraction results exhibiting a strong correlation with the sum of the three labile steps of the BCR procedure.     

Evaluation of Ammonium Oxalate for Fractionating Metallic Trace Elements in Soils by Sequential Extraction

Abstract

Ammonium oxalate is largely used to extract the trace elements bound to Mn-oxides, amorphous compounds and crystalline Fe-oxides. The objective of this work was to evaluate the selectivity and the efficiency of ammonium oxalate for extracting Cd, Cu, Ni, Pb and Zn by sequential extraction of soils. For this purpose, three schemes were selected and applied to three different soil samples of the Swiss Jura. Each extraction scheme consisted of six steps, where different reagents were used to extract Cd, Cu, Ni, Pb and Zn bound to the Mn and Fe compounds. The results showed that metallic trace elements extraction with ammonium oxalate are very dependant on the metal studied. The reason could be the capability of oxalate to form stable complexes with the metals considered which sometimes are only slightly soluble.     

A comparison of an optimised sequential extraction procedure and dilute acid leaching of elements in anoxic sediments, including the effects of oxidation on sediment metal partitioning

The effect of oxidation of anoxic sediment upon the extraction of 13 elements (Cd, Sn, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using the optimised Community Bureau of Reference of the European Commission (BCR) sequential extraction procedure and a dilute acid partial extraction procedure (4 h, 1 mol L⁻¹ HCl) was investigated. Elements commonly associated with the sulfidic phase, Cd, Cu, Pb, Zn and Fe exhibited the most significant changes under the BCR sequential extraction procedure. Cd, Cu, Zn, and to a lesser extent Pb, were redistributed into the weak acid extractable fraction upon oxidation of the anoxic sediment and Fe was redistributed into the reducible fraction as expected, but an increase was also observed in the residual Fe. For the HCl partial extraction, sediments with moderate acid volatile sulfide (AVS) levels (1-100 μmol g⁻¹) showed no significant difference in element partitioning following oxidation, whilst sediments containing high AVS levels (>100 μmol g⁻¹) were significantly different with elevated concentrations of Cu and Sn noted in the partial extract following oxidation of the sediment. Comparison of the labile metals released using the BCR sequential extraction procedure (ΣSteps 1-3) to labile metals extracted using the dilute HCl partial extraction showed that no method was consistently more aggressive than the other, with the HCl partial extraction extracting more Sn and Sb from the anoxic sediment than the BCR procedure, whilst the BCR procedure extracted more Cr, Co, Cu and As than the HCl extraction.     

Influence of the physical properties and handling of silica gel modified carbon paste electrodes on the phase transfer of solved Cu(II) ions

EDTA, a powerful chelating agent, is used extensively in soil sciences to determine the bioavailability of trace metals and their possible decontamination from polluted soils. Because of its non-selective nature, the co-dissolution of major elements also occurs, in addition to the extraction of trace metal ions.In this work, the reactivity of trace and major elements (Pb, Cu, Cd, Al, Fe, Ca and Mg) with different concentrations of EDTA was studied in eight soil samples (Burgundy, France). The limit between lack and excess of EDTA with respect to total metal extracted, determined after 24 h of reaction for different types of soil varied from 0.002 to 0.05 M, respectively.For calcareous samples the amount of Pb, Cu and Cd extracted by EDTA was reduced to 50% of that extracted in non-calcareous soils.From the kinetic point of view, the extraction behavior of major elements seemed to depend heavily on excess or lack of EDTA and the soil Ca content. For a lack of EDTA, different competitive behaviors were revealed for the major elements (Al, Ca, Fe and Mg) towards the reagent, depending on the soil matrix.According to these experimental results, the mass balance between the reagent and cations in any EDTA-soil media is strongly controlled by major metal extraction. When choosing the reagent concentration needed to extract the trace metals efficiently, all the extractable metal present in the concerned sample must be taken into account.     

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.     

Field-flow fractionation: An efficient approach for matrix removal of soil extract for inductively coupled plasma optical emission spectrometry

An on-line coupling between a continuous-flow sequential extraction (CFSE) unit and flow field-flow fractionation with cross flow matrix removal (FlFFF/CFM) with ICP-OES detection was developed for determination of metal leachability from soil. The use of high concentration of Mg(NO₃)₂ in exchangeable phase can cause undesirable matrix effects by shifting ionization equilibrium in the plasma, etc., resulting in a clear need for matrix removal. Therefore, the capability of FlFFF/CFM to remove Mg matrix ion from soil extract was evaluated. Poly(ethylene imine) (PEI) having molecular weight of 25,000 Da was added to form complexes with analyte elements (Cu, Mn, Pb, and Zn) but not the matrix element (Mg). The free Mg matrix ions were then removed by filtering off through the ultrafiltration membrane, having a 1000-Da molecular weight cut-off, inside the FlFFF channel. With the use of FlFFF/CFM, matrix removal efficiency was approximately 83.5%, which was equivalent to approximately 6-fold dilution of the matrix ion. The proposed hyphenated system of CFSE and FlFFF/CFM with ICP-OES detection was examined for its reliability by checking with SRM 2710 (a highly contaminated soil from Montana). The metal contents determined by the proposed method were not significantly different (at 95% confidence) from the certified values.     

Study of mineralogical speciation of arsenic in soils using X ray microfluorescence and scanning electronic microscopy

In this paper we studied the As content in natural contaminated soils, classified as Dystric Leptosol, Chromic Luvisol, Eutric Cambisol and Mollic Leptosol. In soil samples, sieved (<2 mm), total As was determined by XRF and chemical speciation by sequential extraction. As-bearing minerals were concentrated from fine sand fraction of soil (200-20 μm) using heavy liquid. In this fraction, mineralogical speciation was studied by X-ray microfluorescence, XRD with Göbbel mirror and SEM-BEI-EDX. Total As contents ranging from 61.00 to 131.00 mg kg⁻¹. The results of the sequential extraction showed that As was, mainly, in the residual fraction (52.51-98.76 mg kg⁻¹) and in the fraction bound to iron oxyhydroxides (0-36.5 mg kg⁻¹). Mapping of As with X-ray microfluorescence show strongly relationship between Fe and As. Iron (III) oxyhydroxides (FeOHs) (lepidocrocite and goethite), scorodite, angelellite, schultenite and dussertite were identified by XRD analysis as most likely mineral phases. The contents of As, Fe, Pb and Ba obtained with EDX-microprobe, confirmed the results of XRD. The results of sequential extraction and X-ray microfluorescence indicate that As is strongly bound to the soils because the identified As-bearing mineral phases are very stable at the pH conditions of studied soils. Consequently, a low mobility of As can be assumed in these soils.     

Interaction between electrical double layers of soil colloids and Fe/Al oxides in suspensions

Phyllosilicates with net negative surface charge and Fe/Al oxides with net positive surface charge coexist in variable-charge soils, and the interaction between these oppositely charged particles affects the stability of mixed colloids, aggregation, and even the surface chemical properties of variable-charge soils. The interaction of the diffuse layers of electrical double layers between the negatively charged soil colloidal particles and the positively charged particles of goethite or gamma-Al(2)O(3) was investigated in this article through the comparison of zeta potentials between single-soil colloidal systems and binary systems containing soil colloids and Fe/Al oxides. The results showed that the presence of goethite and gamma-Al(2)O(3) increased the zeta potential of the binary system containing soil colloids and Fe/Al oxides, which clearly suggests the overlapping of the diffuse layers in soil colloids and Fe/Al oxides. The overlapping of the diffuse layers leads to a decrease in the effective negative charge density on soil colloid and thus causes a shift of pH-zeta potential curves toward the more positive-value side. The interaction of the electrical double layers is also related to the charge characteristics on the Fe/Al oxides: the higher the positive charge density on Fe/Al oxides, the stronger the interaction of the electrical double layers between the soil colloid particles and the Fe/Al oxides.     

Assessment of a geochemical extraction procedure to determine the solid phase fractionation and bioaccessibility of potentially harmful elements in soils: A case study using the NIST 2710 reference soil

Three mineral acid sequential extraction regimes (HNO₃ only, HNO₃ followed by HCl and aqua regia) were applied to the NIST 2710 contaminated reference soil. The major and trace element chemical analysis data from the extractions were subjected to a chemometric self-modelling mixture resolution procedure which identified that 12 distinct physico-chemical components were extracted. The fractionation of As, Cd, Ni and Pb between these components were determined. Tentative assignments of the mineralogical sources of the components were made. The human ingestion bioaccessible fraction of As, Cd and Pb were determined using the in vitro BARGE UBM bioaccessibility test and were found to be 51.6%, 68.0% and 68.4% respectively. The relationship between the lability of the physico-chemical components and the bioaccessible fraction of the soils was investigated and the bioaccessible fractions were assigned to specific components. The extraction scheme using aqua regia was found to be the most suitable as it was the only one which extracted the iron sulphide phase in the soil.     

Validation of the Tessier scheme for speciation of metals in soil using the Bland and Altman test

The Tessier extraction method was used for speciation of Cu, Pb, Zn, As, Fe and Mn in a large concentration range in contaminated soil with various mineralogical compositions. The results were compared by X-ray fluorescence spectrometry (XRF) as a reference method using the Bland and Altman test. A sum of five fractions (exchangeable, bound to carbonates, Fe-Mn oxides, organic matter and residual forms) was compared with the total content determined on solid matrix by the reference method. A good agreement between the methods in the whole concentration range was found for Cu, Zn, As, and Fe. For Mn and Pb, XRF was found suitable to verify the sequential extraction only for concentrations above 250 mg kg⁻¹. This was a consequence of a poorer reproducibility of Pb extraction using the Tessier scheme due to a great difference in the mineralogical composition and the diversity of the Pb species identified in soil. The poorer result of Mn was attributed to the spectral interference of Fe in XRF. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Determination of Al, Cu, Fe, Mn, Pb and Zn in certified reference materials using the optimized BCR sequential extraction procedure

Sequential extraction procedures are widely used to characterize the fractionation of metal species in solid media. With the variety of different sequential procedures used in environmental and geochemical exploration studies, it is difficult to compare results between studies. Thus, harmonization and standardization are required to provide greater inter-study comparability for fraction-specific metals. In this study, the optimized BCR three-step sequential extraction procedure is applied to five certified reference materials (SRM 2710, SRM 2711, CRM 483, CRM 601 and CW 7). Four fractions are reported, acid extractable, reducible, oxidizable, and residual for Al, Cu, Fe, Mn, Pb and Zn. The objectives of this study were to characterize experimental precision and/or accuracy and to establish baseline data of fraction-specific element concentrations for future studies applying the optimized BCR three-step extraction procedure. The optimized procedure was found to be precise (typically <5%) for all metals in all fractions. Accuracy was acceptable (typically ±15% relative to published indicative values for Cu, Pb and Zn for CRM 483 and CRM 601) for all individual fractions. Detailed fraction-specific concentration data are presented, based on five replicates, for the first time using the optimized procedure for Al, Fe and Mn in CRM 483 and CRM 601, and for Al, Cu, Fe, Mn, Pb and Zn in SRM 2710, SRM 2711 and CW 7.