BCR Sequential Extraction Scheme Research Articles

Chemical association of copper and selenium in coals of Sindh by time saving single step strategy and their impact on groundwater.

The aim of the present study is to estimate the different chemical fractionations of copper (Cu) and selenium (Se) in coal samples of different coal mining areas. The Cu and Se bound to various chemical fractions of coal collected from two mining fields of Sindh, Pakistan, have been determined by BCR sequential extraction scheme (BCR-SES). The long duration of the BCR sequential scheme (51h) was reduced by a time-saving shaking device (ultrasonic bath) termed as ultrasonic-assisted extraction (USE) depending on the same operating conditions and extracting solutions used for BCR sequential extraction scheme. The both trace elements were determined in aquifer water, sampled from different depth of both coal mining fields. In addition, the groundwater of dug well in the vicinity of coal mining areas were also analyzed for Cu and Se using reported extraction methodologies. The partitioning of Cu and Se bound with different chemical fractions of coal was successfully made by proposed USE, within 2h as compared to long duration of BCR-SES (51h). The Cu and Se concentrations in acid-soluble fractions of coal samples were > 10%, enhanced by USE extraction procedure than those values gained via BCR-SES (p < 0.01). About 67 to 69% of Cu were found in the first three fractions, whereas their remaining amount corresponding to 31 to 33%, respectively bound with crystalline/residual fraction, while up to 66.1 to 71.1% of total Se contents extracted in three extractable phases, followed up to 28.9 to 33.8% of it was bound with residual phase. The concentrations of Cu and Se in groundwater of different aquifers were found in decreasing order as AQ1 > AQII > AQIII; the same trend was observed for two aquifers of Lakhra coal mining, whereas the groundwater samples have two to three folds higher levels of Se than WHO limit. The Cu levels in water samples were significantly lower than the recommended limit of WHO for drinking water (p < 0.01).

A Comprehensive Exploration on Pollution Characteristics and Ecological Risks of Heavy Metals in Surface Paddy Soils around a Large Copper Smelter, Southeast China

To assess heavy metal pollution and ecological risk, a total of 28 surface paddy soil samples were collected and analyzed around a famous copper smelter in Guixi, China. The results showed that all sites were heavily contaminated by both Cu and Cd, compared with soil background values, whose average concentrations exceeded the standard by 5.7 and 12.3 times, respectively, posing a slight ecological risk related to Cu (potential ecological risk index &lt;40) and an extremely serious ecological risk related to Cd (potential ecological risk index &gt;320). The risks were also demonstrated through the speciation analyses of Cu (CaCl2-Cu 2.63%, acid-soluble Cu 8.67%, and residual Cu 74.17%, on average) and Cd (CaCl2-Cd 47.30%, acid-soluble Cd 45.02%, and residual Cd 28.87%, on average) in the surface paddy soil, including the use of a CaCl2 extraction procedure and the BCR (Community Bureau of Reference) sequential extraction scheme. Several soil properties (residual carbon, cation exchange capacity, and soil texture) were significantly correlated with soil Cd but made a small contribution to their variability with a poor linear fit because of external Cd input to the soil, while soil total potassium largely influenced the soil Cu species except for residual Cu. Therefore, an effective Cu pollution regulation strategy through soil potassium control is suggested for this smelter soil.

Exposure of heavy metals in coal gangue soil, in and outside the mining area using BCR conventional and vortex assisted and single step extraction methods. Impact on orchard grass

It was investigated that toxic metals (cadmium and lead) enhanced in coal gangue soil used for the reclamation of soil, creates adverse impacts on atmosphere. Presently the chemical fractionation of toxic metals in coal, inner and outer coal gangue soil samples of Lakhra coalfield were studied along with the impact on the orchard grass grown on coal gangue soil in a subside land of the coal mining area. The BCR sequential extraction scheme (BCR-SES) was carried out to determine the different chemical profiles of heavy metals in coal and coal gangue soil samples. For comparative purpose time saving conventional single step extraction (CSE) and vortex assisted single step extraction (VSE) schemes based on same working setting used BCR extraction scheme. The all three procedures were validated by a certified soil sample (BCR 483) and standard addition method in real samples. The total Cd and Pb in coal, soil and grass samples were determined prior to oxidize by acid mixture. The separation of each fraction of Cd, and Pb in all types of environmental samples by VSE could be completed in 30-120s. The extracted Cd and Pb concentrations in reducible fractions by CSE and VSE extraction procedure were 2.5-5% higher than those values gained through BCR-SES. About 71 and 50% of Cd and Pb in coal samples were observed in acid soluble, reducible and oxidizable fraction, respectively, whilst rest of Cd and Pb (29 and 50%) were found in residual phase. The orchard grass (Dactylis glomerata) grown on land reclaimed with OSG was analysed, the bioaccumulate Cd and Pb may create adverse impacts on grazing cattle.

Evaluation of the BCR sequential extraction scheme for trace metal fractionation of alkaline municipal solid waste incineration fly ash

The BCR sequential extraction scheme (SES), initially developed for soils and sediments, is frequently adopted to evaluate the environmental risks of municipal solid waste incineration (MSWI) fly ash. Within the procedure, metals are liberated from the matrix hosting them relying on the selectivity of the chosen chemical reagents or operation conditions. However, the effect of the high content of alkaline substances in MSWI fly ash on the selectivity of acetic acid to acid-soluble fraction metals was ignored. In this study, the feasibility of the BCR SES for evaluating MSWI fly ash was assessed by adjusting the acetic acid washing times in the acid-soluble extraction step. The metal fractionation, as well as mineralogy, morphology, and surface chemistry of the residues after three successive acid washing processes, were analyzed. The results reveal that only easily soluble salts, but not hydroxides, are entirely extracted after the first acid washing (pH∼12.0). Importantly, carbonates (generally reported as an indicator of the complete release of acid-soluble metals) are mostly decomposed only after the third acid washing (pH∼3.8). The incomplete dissolution of calcium carbonates in a single-step acid washing may convey misleading results of metal fractionation and underestimates the environmental risk of potentially toxic elements. Therefore, complete removal of carbonates should be employed as the endpoint of the acid-soluble fraction extraction step in the evaluation of MSWI fly ash. This work can help in selecting proper strategies for fly ash management and developing proper sequential extraction schemes for similar high-alkalinity hazardous waste risk assessment.

Understanding the solid phase chemical fractionation of uranium in soil profile near a hydrometallurgical factory

Uranium (U) contamination of soil has become a major concern with respect to its toxicity, accumulation in the food chain, and persistence in the environment. Anthropogenic activities like mining and processing of U ores has become pressing issues throughout the world. The aim of the work is to understand the chemical fractionation of U in polluted soil and the mechanism involved. U-free soils samples of eluvial (E), illuvial (B), and parent-material (C) horizons from a hydrometallurgical factory area were used. The experimental results showed that the U adsorption capacity decreased with depth, and its mobility in the upper soil is better than the lower. It was closely related to distribution coefficient (Kd), pH, organic-matter (OM), and carbonate content of soil horizons. The chemical fractionation of U was studied using the BCR sequential extraction scheme for soils after saturated adsorption. It was noted that the U reducible and oxidizable fraction in the E and B horizons can vertically transfer to the C horizon and occurs a significant rearrangement of U in different horizons. BET, SEM, XRD, and FT-IR analyses showed that different U distribution and migration in soil profile is mainly affected by specific surface area, soil particle size, mineral composition, and active groups. The XPS data further indicated that U (VI) is gradually converted to U (IV) with decreased depth and fixed in deeper soil becoming insoluble and immobile. It is the first step to investigate potential migration and plan U mining and milling area long-term management.

An alternative sequential extraction scheme for the determination of trace elements in ferrihydrite rich sediments

Sequential extraction schemes (SES) were evaluated to investigate the fractionation of Al, As, Cd, Cs, Cr, Co, Cu, Fe, Mn, Mo, Pb, Sr, U and Zn between the different mineral phases in iron oxide rich deposits of a former uranium mining site. Ineffective dissolution of iron oxide was observed when applying the BCR sequential extraction scheme. The hydroxylamine hydrochloride reagent in nitric acid could not effectively dissolve the iron oxide phase, even after several consecutive extractions. The use of sodium pyrophosphate to remove organic matter prior to the dissolution of the iron oxides and the use of oxalic acid buffer and dithionite citrate buffer to dissolve the amorphous and crystalline iron oxides was evaluated. An alternative six step SES for iron oxide rich sediments is proposed consisting of F1) Exchangeable-Carbonate fraction using acetic acid/ sodium acetate buffer (pH 5) F2) Labile organic fraction using sodium pyrophosphate, F3) Easily reducible amorphous oxides using an oxalic acid buffer, F4) Organic and Sulfide fraction using hydrogen peroxide, followed by ammonium acetate extraction, F5) Poorly reducible crystalline oxides using sodium dithionite and F6) residual fraction using a microwave digestion step with hydrofluoric acid, nitric acid and hydrochloride acid mixture. A good correspondence between the sum of the sequential extraction steps and total metal concentrations was found. Both the BCR method and new method were also applied to the CRM BCR 701 providing indicative values for non-certified elements with the BCR method and indicative values for the method presented.

Multivariate Analyses and Evaluation of Heavy Metals by Chemometric BCR Sequential Extraction Method in Surface Sediments from Lingdingyang Bay, South China

Sediments in estuary areas are recognized as the ultimate reservoirs for numerous contaminants, e.g., toxic metals. Multivariate analyses by chemometric evaluation were performed to classify metal ions (Cu, Zn, As, Cr, Pb, Ni and Cd) in superficial sediments from Lingdingyang Bay and to determine whether or not there were potential contamination risks based on the BCR sequential extraction scheme. The results revealed that Cd was mainly in acid-soluble form with an average of 75.99% of its total contents and thus of high potential availability, indicating significant anthropogenic sources, while Cr, As, Ni were enriched in the residual fraction which could be considered as the safest ingredients to the environment. According to the proportion of secondary to primary phases (KRSP), Cd had the highest bioavailable fraction and represented high or very high risk, followed by Pb and Cu with medium risks in most of samples. The combined evaluation of the Pollution Load Index (PLI) and the mean Effect Range Median Quotient (mERM-Q) highlighted that the greatest potential environmental risk area was in the northwest of Lingdingyang Bay. Almost all of the sediments had a 21% probability of toxicity. Additionally, Principal Component Analysis (PCA) revealed that the survey region was significantly affected by two main sources of anthropogenic contributions: PC1 showed increased loadings of variables in acid-soluble and reducible fractions that were consistent with the input from industrial wastes (such as manufacturing, metallurgy, chemical industry) and domestic sewages; PC2 was characterized by increased loadings of variables in residual fraction that could be attributed to leaching and weathering of parent rocks. The results obtained demonstrated the need for appropriate remediation measures to alleviate soil pollution problem due to the more aggregation of potentially risky metals. Therefore, it is of crucial significance to implement the targeted strategies to tackle the contaminated sediments in Lingdingyang Bay.

Leachability of cadmium, lead, and zinc in a long-term spontaneously revegetated slag heap: implications for phytostabilization

Purpose: For abandoned slag heaps, the spontaneous establishment of a vegetation cover is usually considered beneficial as it represents a means of phytostabilization. However, for slag containing heavy metals, such a vegetation cover has a potential long-term effect on the fate of the metals. The objective of this study was to investigate how the long-term spontaneous revegetation of a slag heap can affect the fractionation and the leachability of Cd, Zn, and Pb. Materials and methods: Soils from two plots covered by either Armeria maritima or Agrostis tenuis and a bare plot soil were sampled from a slag heap from a zinc smelting plant and characterized. The BCR sequential extraction scheme was adopted to determine the metal pools. The leachability of Cd, Pb and Zn was assessed by means of a leaching column experiment. Results and discussion: Long-term presence of a plant cover increased the proportion of Zn in the most mobile fraction and Pb in the fraction bound to organic matter. Cd distribution was relatively unaffected. Overall, the metal leachability was enhanced in the revegetated soils, notably due to higher organic anion release. However, responses of metal behavior to revegetation depended on the established plant species. The highest leachability of Cd was found in the soil covered by A. tenuis while the highest leachability of both Zn and Pb was observed in the soil below A. maritima. Conclusions: Any remediation strategy for metal-rich waste dumps by phytostabilization should take into careful consideration the potential long-term mobilization effect of plant establishment on heavy metals. We conclude that when using pioneer plants for phytostabilization purposes, preference should be given to pseudo-metallophyte over hyperaccumulator species.

Simultaneous determination of arsenic, cadmium, copper, chromium, nickel, lead and thallium in total digested sediment samples and available fractions by electrothermal atomization atomic absorption spectroscopy (ET AAS)

This study describes the optimization and validation of a quick and simple method for the simultaneous determination of total content and available fractions of As, Cr, Cu, Ni, Pb and Tl in sediments by ET AAS, which has been proved to be useful for environmental research. The optimization was carried out using a 33 Box–Behnken factorial design which was applied to matrices of total digestion and to stages 1 and 2 of the modified BCR sequential extraction scheme for sediments in order to determine the appropriate atomization temperatures and masses for the chemical modifiers: Pd(NO3)2 and Mg(NO3)2. The simultaneous determination of the elements in all matrices considered was performed, without the use of chemical modifiers at atomization temperatures of 1700°C for Cd and Tl, and 2100°C for As, Cu, Cr, Ni and Pb, using a standard calibration curve for calibration purposes. The characteristic masses and limits of detection obtained were 36.5, 1.8, 6.5, 28, 34, 46.5 and 48ρg and 0.11, 0.001, 0.022, 0.04, 0.2, 0.03 and 0.003μgg−1 for As, Cd, Cr, Cu, Ni, Pb and Tl, respectively. The analytical procedure was validated by analyzing three sediment certified reference materials (CRM NCS DC 73315 and LKSD-4 for total content and BCR 701 for available fractions). Good accuracy was obtained (tested statistically, P=0.05, and shown by the high recovery for each element in each matrix), except for total As in the matrix of total digestion, where losses of the analyte could be attributed to sample treatment with HNO3. The precision of the procedure was between 0.6% and 6%.

Comparison of unmodified and modified BCR sequential extraction schemes for the fractionation of heavy metals in shrimp aquaculture sludge from Selangor, Malaysia

A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.

Assessment of the BCR sequential extraction procedure for thallium fractionation using synthetic mineral mixtures

This work focused on the specific behavior of Tl-bearing phases in the BCR (Community Bureau of Reference) sequential extraction (SE) scheme, namely Tl-bearing ferrihydrite, goethite, birnessite, calcite, illite, sphalerite and feldspar in their simple model mixtures with quartz. Several significant discrepancies between the obtained and expected behaviors of these phases in the BCR SE were observed. The amount of Tl released as the exchangeable/acid-extractable fraction (55–82% of the total Tl content) showed a substantial H +-promoted dissolution of all Fe(III) and Mn(III, IV) oxides (corresponding to up to 61% of solid Fe dissolved) and incongruent (increased) extraction of Tl from ferrihydrite and goethite. Reductive conditions of the second SE step were insufficient to complete goethite dissolution with corresponding Tl amount retained in the solid phase. Similarly, insufficient oxidation of sphalerite and lower Tl recovery of the oxidisable fraction was identified. In contrast, the BCR SE seems to produce well predictable results of Tl leaching from Tl-bearing calcite and feldspar. Only 70% of total Tl content was extracted from Tl-modified illite in the exchangeable/acid-extractable step, while 30% was associated with the reducible and residual fractions, i.e., Tl was strongly fixed to the illite matrix.

Accumulation and fractionation of trace metals in a Tunisian calcareous soil amended with farmyard manure and municipal solid waste compost

A field plots experiment was carried out to assess the effects of repeated application of municipal solid waste compost in comparison to farmyard manure on the accumulation and distribution of trace metals, as well as organic carbon and nitrogen in Tunisian calcareous soil. Compared with untreated soil, the application of the two organic amendments significantly increased the organic carbon and nitrogen contents of the soil. Particle-size fractionations showed that carbon and nitrogen were mainly found to occur in the macro-organic matter fraction (80%). The two organic amendments significantly increased organic carbon in the macro-organic and mineral >150 μm fraction and the 150–50 μm fraction, as well as the organic nitrogen in 150–50 μm and macro-organic fraction. Compared with farmyard manure, municipal solid waste compost significantly increased total Cd, Cu, Pb and Zn contents in the topsoil. These trace metals were mainly present in the macro-organic matter fraction. Significant increases of Cu, Zn and Pb were detected in the 150–50 μm, <50 μm and macro-organic fractions after application of municipal solid waste compost. A significant increase of Cd content was only observed in the 150–50 μm fraction. The trace metals also showed different fractionation patterns when the BCR sequential extraction scheme was applied on untreated and compost-treated soil. The residual fraction was found to be the major fraction, especially for Cu, Cr, Ni and Zn. In contrast, Cd was mainly present in the acid-extractable and reducible fraction, whereas Pb was mainly associated with the reducible fraction.

A modification of the BCR sequential extraction procedure to investigate the potential mobility of copper and zinc in shrimp aquaculture sludge

The mobility, bioavailability and persistence of copper and zinc were investigated by comparing the effect of concentration and pH changes in step 2 BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction procedure in shrimp aquaculture farm sludge from Selangor, Malaysia. The pseudototal metal contents of shrimp aquaculture sludge samples were determined following an aqua regia digestion. The metal content in the extracts was measured by flame atomic absorption spectrometry (AAS). The concentration of Zn was increased with the increase in the concentration of hydroxylammonium chloride from 0.1 M to 0.5 M, However, further increase in the concentration of reductant caused a significant reduction in released Zn. Zinc showed the highest release percentage for hydroxylammonium chloride 0.5 M with pH 1.5 (modified BCR sequential extraction scheme). In contrast, Cu showed the highest speciation percentage in step 2 when the unmodified sequential extraction procedure was used. Copper and zinc concentrations in this sludge, however, were not higher than the typical concentrations in soil, hence the use of this sludge as a fertilizer is suitable.

Assessment of chromium biostabilization in contaminated soils using standard leaching and sequential extraction techniques

The iron reducing microorganism Desulfuromonas palmitatis was evaluated as potential biostabilization agent for the remediation of chromate contaminated soils. D. palmitatis were used for the treatment of soil samples artificially contaminated with Cr(VI) at two levels, i.e. 200 and 500 mg kg − 1 . The efficiency of the treatment was evaluated by applying several standard extraction techniques on the soil samples before and after treatment, such as the EN12457 standard leaching test, the US EPA 3060A alkaline digestion method and the BCR sequential extraction procedure. The water soluble chromium as evaluated with the EN leaching test, was found to decrease after the biostabilization treatment from 13 to less than 0.5 mg kg − 1 and from 120 to 5.6 mg kg − 1 for the soil samples contaminated with 200 and 500 mg Cr(VI) per kg soil respectively. The BCR sequential extraction scheme, although not providing accurate estimates about the initial chromium speciation in contaminated soils, proved to be a useful tool for monitoring the relative changes in element partitioning, as a consequence of the stabilization treatment. After bioreduction, the percentage of chromium retained in the two least soluble BCR fractions, i.e. the “oxidizable” and “residual” fractions, increased from 54 and 73% to more than 96% in both soils.

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges – Investigations combining the BCR extraction scheme and isotopic analysis

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30–100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.

Evaluation of the BCR sequential extraction for trace elements in European reference volcanic soils

SummaryTrace metal behaviour in volcanic ash soils displays distinctive features related to the soils’ large contents of metal‐binding phases and to the rapid release of trace metals from glasses and weatherable minerals. In this work, the BCR (Community Bureau of Reference) sequential extraction scheme (exchangeable + weak acid soluble, reducible, oxidizable, and non‐extractable metal fractions) was applied to selected COST‐622 European reference volcanic soils to determine partitioning of zinc and copper between various solid‐phase constituents, along with the major elements Al, Fe and Mn. The total extracted Al (ΣAl) was strongly correlated with acid ammonium oxalate extractable Al (Alo) (ΣAl = 0.985Alo+ 0.11, R2= 0.98), while the total extracted Fe clearly underestimated the amorphous fraction. Large values for the non‐extractable Al fraction were associated with the presence of gibbsite and phyllosilicates. Although the Zn and Cu contents of the soils were generally large, total amounts extracted (the potentially mobilizable fraction) were small, especially for Zn and for soils with crystalline secondary minerals. The fraction of the total Cu which was potentially mobilizable generally exceeded that of Zn. In the potentially mobilizable Cu the oxidizable fraction was generally dominant. Biocycling appears to play an important role in the surface enrichment of potentially mobilizable Zn and Mn. Although further methodological research seems necessary, the BCR sequential extraction appears to be a valuable tool for studies on metal dynamics in soils with andic properties.

A study of metal and metalloid contaminant availability in Antarctic marine sediments

Previous studies of impacted sites near Casey Station, Antarctica, have revealed elevated concentrations of metals and metalloids, particularly Cd, Cu, Fe, Pb, Sn and Zn in marine sediments. However, attempts to understand the availability and mobility of contaminant elements have not provided a true understanding of speciation. The current work shows, for the first time, that sediments in Brown Bay, an embayment adjacent to the Thala Valley waste disposal site, have elevated concentrations of sulfide, well in excess of that required to bind contaminant metals such as Cd, Cu, Pb and Zn. Furthermore, sediment characterisation using the BCR sequential extraction scheme has shown metal partitioning consistent with sulfides being the controlling factor in metal availability, thus explaining the low porewater concentrations of these metals. The speciation of Sn in Brown Bay, however, is still unclear with the BCR sequential extraction scheme partitioning Sn predominantly into the residual fraction despite Sn being readily extracted by dilute HCl.

Application of the BCR sequential extraction scheme to dredged pond sediments contaminated by Pb–Zn mining: A combined geochemical and mineralogical approach

The modified BCR sequential extraction procedure [Rauret, G., López-Sanchez, J., Sauquillo, A., Rubio, R., Davidson, C., Ure, A., Quevauviller, Ph., 1999. Improvement of the BCR three step sequential extraction procedure prior to certification of new soil and sediment reference materials. J. Environ. Monit. 1, 57–60.] was applied to 4 sediments from a mine tailing pond in La Calamine (East-Belgium). The results showed a very different behaviour of different samples towards the same extraction scheme. In samples with an elevated acid neutralizing capacity, a significant increase in the pH of the extracts was measured after the first two extraction steps. Other artefacts, such as readsorption of metals and precipitation could be deduced by comparing X-ray diffraction patterns after different extraction steps. For example, anglesite was effectively dissolved during the acid extraction step (step 1) but relatively low Pb concentrations were measured in the CH 3COOH extract because of the readsorption of Pb. Mineralogical analysis of the sediments after each extraction step also indicated the incomplete oxidation of sulphides by H 2O 2. Besides a mineralogical analysis, the monitoring of the pH of the extracts and the analysis of major elements (Fe, Ca, Al, Mn) can be helpful for the interpretation of the results of the sequential extraction. The combination of sequential extractions with mineralogical sample investigation provided information on the reactivity and solubility of minerals in the samples. This improved the interpretation, at least within the detection limits of the mineralogical analysis applied. Besides the improved interpretation of the results of the sequential extractions for sediments in which minerals are identified, the information concerning the reactivity of minerals is an important tool to evaluate the risk associated with contaminated sediments.

Development of a simple extraction cell with bi-directional continuous flow coupled on-line to ICP-MS for assessment of elemental associations in solid samples

A continuous-flow system comprising a novel, custom-built extraction module and hyphenated with inductively coupled plasma-mass spectrometric (ICP-MS) detection is proposed for assessing metal mobilities and geochemical associations in soil compartments as based on using the three step BCR (now the Measurements and Testing Programme of the European Commission) sequential extraction scheme. Employing a peristaltic pump as liquid driver, alternate directional flows of the extractants are used to overcome compression of the solid particles within the extraction unit to ensure a steady partitioning flow rate and thus to maintain constant operationally defined extraction conditions. The proposed flow set-up is proven to allow for trouble-free handling of soil samples up to 1 g and flow rates < or =10 mL min(-1). The miniaturized extraction system was coupled to ICP-MS through a flow injection interface in order to discretely introduce appropriate extract volumes to the detector at a given time and with a given dilution factor. The proposed hyphenated method demonstrates excellent performance for on-line monitoring of major and trace elements (Ca, Mn, Fe, Ni, Pb, Zn and Cd) released when applying the various extracting reagents as addressed in the BCR scheme, that is, 0.11 M CH(3)COOH, 0.1 NH(2)OH.HCl and 30% H(2)O(2), even when a well recognized matrix-sensitive detector, such as ICP-MS, is used. As a result of the enhanced temporal resolution of the ongoing extraction, insights into the breaking down of phases and into the kinetics of the metal release are obtained. With the simultaneous multielement detection capability of ICP-MS, the dynamic fractionation system presents itself as an efficient front-end for evaluation of actual elemental association by interelement comparison of metals leached concurrently during the extraction time. Thus, the intimate elemental association between Cd and Zn in contaminated soils could be assessed.

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.