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.     

Oxidative extraction versus total decomposition of soil in the determination of thallium

An aqua regia extraction and a total decomposition of soil were compared in terms of thallium determination. A sequential extraction of soil, according to the BCR protocol, was also performed for additional information on thallium distribution in soil fractions. Certified reference material—soil GBW 07401 of Chinese origin, containing 1 ± 0.2 ppm of thallium was used in these experiments. Thallium was determined by flow injection-differential pulse-anodic stripping voltammetry (FI-DP-ASV). Only 35% of total thallium was extracted in the aqua regia extraction, while the total decomposition led to satisfactory recovery. The sequential extraction showed that only 5% of thallium in GBW 07401 is dissolvable in the four BCR procedure fractions, and that 95% of the element is entrapped in the residual parent matter. These results show that the aqua regia extraction does not ensure complete thallium extraction from soil. Surprisingly, the total decomposition is significantly less time consuming than the aqua regia extraction.     

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.     

Fractionation of potentially toxic elements in urban soils from five European cities by means of a harmonised sequential extraction procedure

The revised (four-step) BCR sequential extraction procedure has been applied to fractionate the chromium, copper, iron, manganese, nickel, lead and zinc contents in urban soil samples from public-access areas in five European cities. A preliminary inter-laboratory comparison was conducted and showed that data obtained by different laboratories participating in the study were sufficiently harmonious for comparisons to be made between cities and land types (e.g. parks, roadside, riverbanks, etc.). Analyte recoveries by sequential extraction, with respect to direct aqua regia digestion, were generally acceptable (100 ± 15%). Iron, nickel and, at most sites, chromium were found mainly in association with the residual phase of the soil matrix. Copper was present in the reducible, oxidisable and residual fractions, whilst zinc was found in all four sequential extracts. Manganese was strongly associated with reducible material as, in some cities, was lead. This is of concern because high lead concentrations were present in some soils (>500 mg kg⁻¹) and the potential exists for remobilisation under reducing conditions. As would be expected, extractable metal contents were generally highest in older, more heavily industrialised cities. Copper, lead and zinc showed marked (and often correlated) variations in concentrations between sites within the same city whereas manganese and, especially, iron, did not. No overall relationships were, however, found between analyte concentrations and land use, nor between analyte partitioning and land use.     

Selective extractions to assess the biogeochemically relevant fractionation of inorganic mercury in sediments and soils

Here we present a new method for sequential selective extractions (SSEs) for Hg in geological solids, validated with extensive quality assurance procedures. Mercury was separated into fractions which “make sense” biogeochemically, rather than being identified by specific compounds. Experiments elucidated the effects of extraction time, solids-to-liquid ratio, and alternate solvents in natural samples, reference materials, and pure compounds. Compounds tested included HgS (red and black), HgCl₂, Hg⁰, Hg₂Cl₂, HgSe, HgO, Hg(II) adsorbed on goethite, Hg-humate, and gold amalgamated Hg. Based on these findings, a five-step sequence of extractions was established to separate the compounds into biogeochemically distinct categories. The fractions and leaching media were as follows: F1 (deionized water), F2 (0.01 M HCl+0.1 M CH₃COOH), F3 (1 M KOH), F4 (12 M HNO₃), and F5 (aqua regia). Method blanks and method detection limits (MDLs) of 0.1-5 ng/g were obtained for the various analytical fractions, depending on the reagent concentrations used. Precision ranged from 2 to 8% for the major fractions in a sample, but increased to 2-40% for fractions making up <5% of the total. Recovery of total Hg by the sum of species in reference materials showed that the accuracy of the method ranges from 90 to 105%. Methylation potential, determined by anoxic incubation sample aliquots with biologically active sediments, showed that inorganic Hg extracted in the F3 fraction is most strongly correlated with methylation potential. In most natural and sediment incubation samples, the majority of Hg present was found either in the F3 or F5 fractions.     

A microwave-assisted sequential extraction of water and dilute acid soluble arsenic species from marine plant and animal tissues

This paper describes the use of dilute nitric acid for the extraction and quantification of arsenic species. A number of extractants (e.g. water, 1.5 M orthophosphoric acid, methanol-water and dilute nitric acid) were tested for the extraction of arsenic from marine biological samples, such as plants that have proved difficult to quantitatively extract. Dilute 2% (v/v) nitric acid was found to give the highest recoveries of arsenic overall and was chosen for further optimisation. The optimal extraction conditions for arsenic were 2% (v/v) HNO₃, 6 min⁻¹, 90 °C. Arsenic species were found to be stable under the optimised conditions with the exception of the arsenoriboses which degraded to a product eluting at the same retention time as glycerol arsenoribose. Good agreement was found between the 2% (v/v) HNO₃ extraction and the methanol-water extraction for the certified reference material DORM-2 (AB 17.1 and 16.2 μg g⁻¹, respectively, and TETRA 0.27 and 0.25 μg g⁻¹, respectively), which were in close agreement with the certified concentrations of AB 16.4 ± 1.1 μg g⁻¹ and TETRA 0.248 ± 0.054 μg g⁻¹.To preserve the integrity of arsenic species, a sequential extraction technique was developed where the previously methanol-water extracted pellet was further extracted with 2% (v/v) HNO₃ under the optimised conditions. Increases in arsenic recoveries between 13% and 36% were found and speciation of this faction revealed that only inorganic and simple methylated species were extracted.     

Should acid ammonium oxalate replace hydroxylammonium chloride in step 2 of the revised BCR sequential extraction protocol for soil and sediment?

The revised, four-step BCR sequential extraction for soil or sediment has been compared with an alternative procedure in which 0.2 mol l⁻¹ ammonium oxalate (pH 3) replaced 0.5 mol l⁻¹ hydroxylammonium chloride (pH 1.5) in step 2, the reducible step. A variety of substrates were studied: BCR CRM601, a sewage sludge amended soil, two industrial soils, and a steel manufacturing by-product (basic oxygen furnace filter cake). Greater amounts of iron were recovered in step 2 when acid ammonium oxalate was used, for all substrates. Similar trends were observed for copper. Manganese and zinc were not strongly affected by the procedural modification, except for zinc in the two industrial soils, where oxalate extraction proved more efficient than use of hydroxylammonium chloride. A large proportion of the calcium and lead isolated in step 2 of the BCR procedure was not released until step 3 when the alternative procedure with oxalate in step 2 was used. This is probably due to rapid precipitation of analyte oxalates from solution. Thus, whilst oxalate offers superior dissolution of iron-containing matrix components, it should not be used if calcium or lead concentrations are to be measured. Selection of the most appropriated sequential extraction protocol for use in a particular study must always be carried out on the basis of “fitness for purpose” criteria. However, the revised BCR protocol, involving use of 0.5 mol l⁻¹ NH₂OH·HCl in the reducible step, appears to be more generally applicable than procedures involving acid ammonium oxalate.     

Selectivity assessment of an arsenic sequential extraction procedure for evaluating mobility in mine wastes

An optimized sequential extraction (SE) scheme for mine waste materials has been developed and tested for As partitioning over a range of pure As-bearing mineral phases, their model mixtures, and natural mine waste materials. This optimized SE procedure employs five extraction steps: (1) nitrogen-purged deionized water, 10 h; (2) 0.01 M NH₄H₂PO₄, 16 h; (3) 0.2 M NH₄-oxalate in the dark, pH3, 2 h; (4) 0.2 M NH₄-oxalate, pH3/80 °C, 4 h; (5) KClO₃/HCl/HNO₃ digestion. Selectivity and specificity tests on natural mine wastes and major pure As-bearing mineral phases showed that these As fractions appear to be primarily associated with: (1) readily soluble; (2) adsorbed; (3) amorphous and poorly-crystalline arsenates, oxides and hydroxosulfates of Fe; (4) well-crystalline arsenates, oxides, and hydroxosulfates of Fe; as well as (5) sulfides and arsenides. The specificity and selectivity of extractants, and the reproducibility of the optimized SE procedure were further verified by artificial model mineral mixtures and different natural mine waste materials. Partitioning data for extraction steps 3, 4, and 5 showed good agreement with those calculated in the model mineral mixtures (<15% difference), as well as that expected in different natural mine waste materials. The sum of the As recovered in the different extractant pools was not significantly different (89–112%) than the results for acid digestion. This suggests that the optimized SE scheme can reliably be employed for As partitioning in mine waste materials.     

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.     

Determination of bioavailable fractions of Zn, Cu, Ni, Pb and Cd in soils and sludges by atomic absorption spectrometry

The single extraction procedures validated by the standards, measurement and testing programme (formerly BCR), extraction with 0.05 mol l⁻¹ EDTA and 0.43 mol l⁻¹ acetic acid, have been applied to reference materials of soils and sludges with certified total values of elements, in order to determine bioavailable contents of Cd, Cu, Ni, Pb and Zn. These soils, which represent uncontaminated pedologically different types of soils from Slovakia and sludges from city water treatment are characterized for the bioavailable fraction of the metals using the procedures followed by SM&T Programme. Concentrations of the elements under the study in the extracts were determined by flame (FAAS) using calibration curves in appropriate extractants and by electrothermal (ETAAS) atomic absorption spectrometry, using technique of standard additions for the evaluation of the results. The accuracy of the extraction procedures and determinations of the elements in the extracts was controlled using CRM 483 certified for EDTA- and acetic acid-extractable contents of Cd, Cu, Ni, Pb and Zn in sewage sludge amended soil.     

Ion pair-based dispersive liquid-liquid microextraction for gold determination at ppb level in solid samples after ultrasound-assisted extraction and in waters by electrothermal-atomic absorption spectrometry

A new methodology was developed for the determination of ultratrace levels of gold in water samples, soils and river sediments. Dispersive liquid-liquid microextraction was used to preconcentrate the ion pair formed between AuCl₄⁻ and [CH₃(CH₂)₃]₄N⁺ in a microliter-range volume of chlorobenzene using acetone as disperser solvent. When solid samples were analyzed, the method consisted of a combination of ultrasound-assisted extraction and dispersive liquid-liquid microextraction with final detection by electrothermal-atomic absorption spectrometry. Since an HCl medium was required for the formation of the AuCl₄⁻ complex, HCl together with HNO₃ was used as extractants for ultrasound-assisted extraction. After optimization, the enrichment factor obtained was 220 for water samples. Moreover, the extraction efficiency was around 96%. The repeatability, expressed as relative standard deviation ranged from 3.6% to 9.7%. The instrumental detection limit was 8.4 ng L⁻¹, whereas the procedural detection limits were 42 ng L⁻¹ for water samples and 1.5 ng g⁻¹ for environmental solid samples.     

A multisyringe flow-through sequential extraction system for on-line monitoring of orthophosphate in soils and sediments

A fully automated flow-through microcolumn fractionation system with on-line post-extraction derivatization is proposed for monitoring of orthophosphate in solid samples of environmental relevance. The system integrates dynamic sequential extraction using 1.0 mol l⁻¹ NH₄Cl, 0.1 mol l⁻¹ NaOH and 0.5 mol l⁻¹ HCl as extractants according to the Hieltjes-Lijklema (HL) scheme for fractionation of phosphorus associated with different geological phases, and on-line processing of the extracts via the Molybdenum Blue (MB) reaction by exploiting multisyringe flow injection as the interface between the solid containing microcolumn and the flow-through detector. The proposed flow assembly, capitalizing on the features of the multicommutation concept, implies several advantages as compared to fractionation analysis in the batch mode in terms of saving of extractants and MB reagents, shortening of the operational times from days to hours, highly temporal resolution of the leaching process and the capability for immediate decision for stopping or proceeding with the ongoing extraction. Very importantly, accurate determination of the various orthophosphate pools is ensured by minimization of the hydrolysis of extracted organic phosphorus and condensed inorganic phosphates within the time frame of the assay. The potential of the novel system for accommodation of the harmonized protocol from the Standards, Measurement and Testing (SMT) Program of the Commission of the European Communities for inorganic phosphorus fractionation was also addressed. Under the optimized conditions, the lowest detectable concentration at the 3σ level was ≤0.02 mg P l⁻¹ for both the HL and SMT schemes regardless of the extracting media. The repeatability of the MB assay was better than 2.5% and the dynamic linear range extended up to 7.0 mg P l⁻¹ in NH₄Cl and NaOH media and 15 mg P l⁻¹ whenever HCl is utilized as extractant for both the HL and SMT protocols.     

Solvent extractions of zirconium and niobium from HCl solutions by Aliquat 336/Alamine 336 and DOSO mixtures

Liquid-liquid extractions of zirconium(IV) from aqueous HCl solutions by mixtures of Aliquat 336 or Alamine 336 and diocytl sulfoxide (DOSO) in the diluent benzene has been found to be always higher than that by any single extractant. While the cationic extractants extract Zr(IV) above 6M HCl, DOSO extracts from 4M onwards. Synergism has been observed in all cases. With any of these extractants extraction becomes almost quantitative at and above 10M HCl, but with mixtures of the cationic and neutral extractants, extraction is quantitative in the range 8–9M HCl. Although the extracted species with DOSO alone seems to be ZrCl₄·DOSO, with the mixture of extractants, however, the extracted species appear to be Q₂ZrCl₆·DOSO where Q is R₃ ⁺NH (for Alamine 336) and R₃ ⁺N(CH₃) (for Aliquat 336). Studies on separation of⁹⁵Zr–⁹⁵Nb pair from aqueous HCl media by Alamine 336 or DOSO and their mixtures in benzene exhibit preferential extraction of⁹⁵Nb leaving behind⁹⁵Zr in the aqueous phase, and extractions have been found to depend both upon the extractant and HCl concentrations.     

An evaluation of the modified BCR sequential extraction procedure to assess the potential mobility of copper and zinc in MSW

Copper and zinc were determined in municipal solid waste (MSW) samples with different deposit ages from Tianziling landfill site. The pseudototal metal contents of the MSW samples were determined following an aqua regia digestion. Operational speciation was performed using the modified BCR sequential extraction procedure. Analyses were carried out by AAS. Agreement between most of triplicate samples was acceptable. The amount of copper and zinc extracted in the sequential procedure (i.e. Step 1, Step 2, Step 3, residual) did not generally agree well with pseudototal digestion. Various MSW samples contained significant different levels of copper and zinc, but these were with different potential migrations. For example, 49.88%-76.34% of copper existed in five MSW samples was present as oxidable fraction while ~ 40% of zinc was present as acid soluble fraction. The study illustrates the feasibility and importance of modified BCR sequential extraction procedure used as evaluation method when assessing the potential mobility of heavy metal in MSW landfill.     

Determination of mercury species by the diffusive gradient in thin film technique and liquid chromatography – atomic fluorescence spectrometry after microwave extraction

A diffusive gradient in thin films technique (DGT) was combined with liquid chromatography (LC) and cold vapor atomic fluorescence spectrometry (CV-AFS) for the simultaneous quantification of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, and C₆H₅Hg⁺). After diffusion through an agarose diffusive layer, the mercury species were accumulated in resin gels containing thiol-functionalized ion-exchange resins (Duolite GT73, and Ambersep GT74). A microwave-assisted extraction (MAE) in the presence of 6 M HCl and 5 M HCl (55 °C, 15 min) was used for isolation of mercury species from Ambersep and Duolite resin gels, respectively. The extraction efficiency was higher than 95.0% (RSD 3.5%). The mercury species were separated with a mobile phase containing 6.2% methanol + 0.05% 2-mercaptoethanol + 0.02 M ammonium acetate with a stepwise increase of methanol content up to 80% in the 16th min on a Zorbax C18 reverse phase column. The LODs of DGT–MAE–LC–CV-AFS method were 38 ng L⁻¹ for CH₃Hg⁺, 13 ng L⁻¹ for Hg²⁺, 34 ng L⁻¹ for C₂H₅Hg⁺ and 30 ng L⁻¹ for C₆H₅Hg⁺ for 24 h DGT accumulation at 25 °C.     

Uranyl ion complexes with long chain aminoalcoholbis(phenolate) [O,N,O,O′] donor ligands

The reaction between uranyl nitrate hexahydrate and phenolic ligand precursor [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-4-amino-1-butanol) · HCl], H₃L1 · HCl, leads to a uranyl complex [UO₂(H₂L1)₂] (1a) and [UO₂(H₂L1)₂] · 2CH₃CN (1b). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-4-amino-1-butanol)H₃L2 · HCl], H₃L2 · HCl, yields a uranyl complex with a formula [UO₂(H₂L2)₂] · CH₃CN (2). The ligand [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-5-amino-1-pentanol) · HCl], H₃L3 · HCl, produces a uranyl complex with a formula [UO₂(H₂L3)₂] · 2CH₃CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-5-amino-1-pentanol) · HCl], H₃L4 · HCl, leads to a uranyl complex with a formula [UO₂(H₂L4)₂] · 2CH₃CN (4). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-6-amino-1-hexanol) · HCl], H₃L5 · HCl, leads to a uranyl complex with a formula [UO₂(H₂L5)₂] · 4toluene (5). The complexes 1–5 are obtained using a molar ratio of 1:2 (U to L) in the presence of a base (triethylamine). The molecular structures of 1a, 1b, 3, 4 and 5 were verified by X-ray crystallography. All complexes are neutral zwitterions and have similar centrosymmetric, mononuclear, distorted octahedral uranyl structures with the four coordinating phenoxo ligands in an equatorial plane. In uranyl ion extraction studies from water to dichloromethane with ligands H₃L1 · HCl–H₃L5 · HCl, ligands H₃L1 · HCl, H₃L4 · HCl and H₃L5 · HCl are the most effective ones.     

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.     

Dispersive solid-phase extraction followed by dispersive liquid–liquid microextraction for the determination of some sulfonylurea herbicides in soil by high-performance liquid chromatography

Dispersive solid-phase extraction (DSPE) combined with dispersive liquid–liquid microextraction (DLLME) has been developed as a new approach for the extraction of four sulfonylurea herbicides (metsulfuron-methyl, chlorsulfuron, bensulfuron-methyl and chlorimuron-ethyl) in soil prior to high-performance liquid chromatography with diode array detection (HPLC-DAD). In the DSPE-DLLME, sulfonylurea herbicides were first extracted from soil sample into acetone–0.15 mol L⁻¹ NaHCO₃ (2:8, v/v). The clean-up of the extract by DSPE was carried out by directly adding C₁₈ sorbent into the extract solution, followed by shaking and filtration. After the pH of the filtrate was adjusted to 2.0 with 2 mol L⁻¹ HCl, 60.0 μL chlorobenzene (as extraction solvent) was added into 5.0 mL of it for DLLME procedure (the acetone contained in the solution also acted as dispersive solvent). Under the optimum conditions, the enrichment factors for the compounds were in the range between 102 and 216. The linearity of the method was in the range from 5.0 to 200 ng g⁻¹ with the correlation coefficients (r) ranging from 0.9967 to 0.9987. The method detection limits were 0.5–1.2 ng g⁻¹. The relative standard deviations varied from 5.2% to 7.2% (n = 5). The relative recoveries of the four sulfonylurea herbicides from soil samples at spiking levels of 6.0, 20.0 and 60.0 ng g⁻¹ were in the range between 76.3% and 92.5%. The proposed method has been successfully applied to the analysis of the four target sulfonylurea herbicides in soil samples, and a satisfactory result was obtained.     

Assessment of CaCl2, NaNO3 and NH4NO3 extraction procedures for the study of Cd, Cu, Pb and Zn extractability in contaminated soils

The variety of extraction procedures used in environmental studies makes it very difficult to compare the results obtained; therefore, harmonisation and standardisation is required. The extraction of heavy metals from soil by un-buffered salt solutions is a method used to estimate soil contamination and trace metal availability to plants. The present study assesses three of these methods. All the three methods are standardised or is undergoing standardisation in Europe: 0.01 mol l⁻¹ CaCl₂ (The Netherlands), 0.1 mol l⁻¹ NaNO₃ (Switzerland) and 1 mol l⁻¹ NH₄NO₃ (Germany). The soil-reference material BCR CRM 483, with indicative values for CaCl₂, NaNO₃, NH₄NO₃ extractable metals, was analysed for quality control purposes. The three methods were also applied to 10 contaminated soils and the extracted metals (Cd, Cu, Pb, and Zn) were determined. The procedures were found to be precise (typically <10%) for all metals, taking into account the low metal concentrations extracted. The metal extraction efficiency obtained with each procedure was slightly different, and the three methods provided equivalent information while predicting the relative trace-metal mobility (Cd>Zn>Cu>Pb) in the soils studied. From the experience obtained, the 0.01 mol l⁻¹ CaCl₂ extraction procedure seems to be the most suitable method for performing a harmonisation process, since this procedure combines an appropriate extraction capacity for this type of studies with the lowest salt concentration in the extracts and, consequently, with a more simple matrix for metal determination.     

Comparison of original and modified BCR sequential extraction procedures for the fractionation of copper, iron, lead, manganese and zinc in soils and sediments

This article describes a detailed comparison between the original BCR sequential extraction procedure, step 2 of which involves treatment with 0.1 mol l⁻¹ hydroxylammonium chloride at pH 2, and the revised BCR procedure (step 2: 0.5 mol l⁻¹ hydroxylammonium chloride at pH 1.5). An intermediate protocol was also evaluated in which 0.5 mol l⁻¹ hydroxylammonium chloride at pH 2 was used. The procedures were applied to five soil and sediment substrates: a sewage sludge-amended soil, two different industrially contaminated soils, a river sediment and an inter-tidal sediment. Extractable iron and manganese concentrations were measured to assess the effects of the procedural modifications on dissolution of the reducible matrix components. Trace elements copper, lead and zinc were also determined. Statistical analysis (two-tailed t-tests at 95% confidence interval) indicated that recovery of iron in step 2 was not markedly enhanced when the intermediate protocol was used. However, significantly greater amounts were isolated with the revised BCR scheme than with the original procedure. Copper behaved similarly to iron. Lead recoveries were increased by use of both modified protocols, with the greatest effect occurring for the revised BCR extraction. In contrast, manganese and zinc extraction did not vary markedly between procedures. The work indicates that the revised BCR sequential extraction provides better attack on the iron-based components of the reducible matrix for a wide range of soils and sediments.