Allan M. Ure

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.

Speciation of Heavy Metals in Soils and Sediments. An Account of the Improvement and Harmonization of Extraction Techniques Undertaken Under the Auspices of the BCR of the Commission of the European Communities

Abstract An account is presented of a series of investigations and collaborative studies, initiated by BCR, on current methods of metal speciation by extraction of soils and sediments with chemical reagents. It was established by extensive consultation with European experts that the diverse procedures used could be harmonized into agreed methods. These methods, including both single extractant and sequential extraction procedures were subjected to collaborative, interlaboratory trials and the results, presented briefly here, showed that it was both possible and desirable that reference soils and sediments, characterised by certified values for extractable contents, be prepared. As a consequence of these studies two soils have been prepared and will shortly be the subject of interlaboratory analysis with a view to certification of their EDTA and acetic acid extractable contents of some heavy metals. Following this workshop a feasibility study of the agreed sequential extraction procedure will, it is believ...

Use of a certified reference material for extractable trace metals to assess sources of uncertainty in the BCR three-stage sequential extraction procedure

Various potential sources of irreproducibility in the BCR three-stage sequential extraction procedure have been investigated using the lake sediment CRM 601. Of the variables considered, the pH of the hydroxylamine hydrochloride in Step 2 proved most important. Factors such as the type of acid used in pH adjustment, the temperature and duration of extraction, and working under nitrogen did not affect precision, although they did alter the amounts of metals extracted. Improved precision was obtained when the hydroxylamine hydrochloride concentration was increased from 0.1 to 0.5 mol l(-1) and when the speed of the centrifugation was increased from 1500 to 3000 x g. The addition of a MgCl2 wash between the steps of the extraction procedure gave rise to increased uncertainty. Although it did not adversely affect reproducibility, the use of filtration to separate solid and liquid phases was not recommended since it promoted dissolution of non-target phases. Neither ammonium hydrogen oxalate nor oxalic acid proved suitable alternatives in Step 2 owing to precipitation of insoluble lead salts, particularly in the presence of calcium

Certification of trace metal extractable contents in a sediment reference material (CRM 601) following a three-step sequential extraction procedure

Abstract Sequential extraction schemes have been developed in the past 20 years for the determination of binding forms of trace metals in sediment. The lack of uniformity of these schemes, however, did not allow the results so far to be compared worldwide nor the procedures to be validated. Indeed, the results obtained by sequential extraction are operationally defined, i.e. the ‘forms’ of metals are defined by the determination of extractable elements using a given procedure. Therefore the significance of the analytical results is related to the extraction scheme used. Another problem which hampered a good comparability of data was the lack of suitable reference materials which did not enable the quality of measurements to be controlled. Owing to this lack of comparability and quality control, the Community Bureau of Reference (BCR, now Standards, Measurements and Testing Programme) has launched a programme of which one of the aims was to harmonize sequential extraction schemes for the determination of extractable trace metals in sediment. This programme involved the comparison of existing procedures tested in two interlaboratory exercises, and it developed into a certification campaign of extractable trace element contents in a sediment reference material, following a three-step sequential extraction procedure duly tested and adopted by a group of 18 EU laboratories. This paper briefly describes the results of the interlaboratory studies and gives all details on the preparation of the sediment reference material, CRM 601, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a standardized sequential (three-step) extraction procedure.

A CRITICAL EVALUATION OF THE THREE-STAGE BCR SEQUENTIAL EXTRACTION PROCEDURE TO ASSESS THE POTENTIAL MOBILITY AND TOXICITY OF HEAVY METALS IN INDUSTRIALLY-CONTAMINATED LAND

Cadmium, chromium, copper, lead, manganese, nickel, vanadium and zinc have been determined in samples of made-up ground from layers of a trial pit excavated on a recently derelict, industrially contaminated site. The pseudototal metal content of the layers was determined following a microwave-assisted digestion with aqua regia. Operational speciation was performed using the BCR three-step sequential extraction procedure. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). A suppressive interference (30%) was observed in the determination of cadmium in aqua regia digests by ETAAS, but not in 0.11 mol l ˇ1 acetic acid, 0.1 mol l ˇ1 hydroxylammonium chloride or 1.0 mol l ˇ1 ammonium acetate extracts. Agreement between duplicate samples was acceptable (i.e. within 10%) for most elements in most layers, but some large discrepancies were apparent, especially for lead. The amount of metal extracted in the sequential procedure (i.e. Step 1aStep 2aStep 3aresidual) did not generally agree well with pseudototal digestion. Various layers of the trail pit contained significant levels of contaminant metals, but these were not always in easily mobilized forms. For example, less than 0.2% of the lead (4000 m gg ˇ 1 ) at 65‐85 cm depth was present as exchangeable or acid-soluble species. The study illustrates the importance of considering metal speciation when assessing the mobility of potentially toxic elements in industrially-contaminated land. # 1998 Elsevier Science B.V.

Single extraction schemes for soil analysis and related applications

Abstract The different kinds of elemental soil analysis, for the determination of ‘total’, ‘pseudo-total’ and ‘extractable’ soil contents and their different purposes are reviewed. In particular, methods for assessing the trace element and heavy metal status of soils by selective chemical extraction procedures is considered in detail. Sampling, and sample preparation for extraction are discussed and the use of air-dried soils is justified. The range of extractants whose extractable soil contents correlate with plant growth, health or uptake is outlined and the nature of the soil phases and components extracted by different chemical extractants is discussed. Extraction is considered as a means of metal speciation, where species are defined functionally. The vital role of The Community Bureau of Reference (BCR) in coordinating and sponsoring the development and validation of agreed soil extraction schemes is revealed. The harmonisation of methodology achieved under the auspices of BCR will hopefully make available this year, 1995, two reference soils with certified extractable contents of a group of heavy metals as a major new contribution to quality control in this field.

Evaluation of a sequential extraction procedure for the speciation of heavy metals in sediments

The three-stage sequential extraction procedure for speciation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR), has been applied to a freshwater sediment collected from the River Clyde, Lanarkshire, UK. Initial studies were carried out using flame atomic absorption spectrometry (FAAS). Iron, manganese and zinc could be determined in the sediment extracts by FAAS, but the technique proved insufficiently sensitive for the determination of chromium, copper, nickel and lead. Detection methods based on electrothermal AAS were therefore developed and applied. Furnace conditions were optimised for the determination of the four analytes mentioned, plus molybdenum and vanadium, in acetic acid, hydroxylammonium chloride and ammonium acetate matrices. Interferences by components in the sediment extracts necessitated analysis by the method of standard additions in most cases. The sequential extraction procedure was found to be both repeatable and reproducible. The amounts of analytes released by the sequential extraction procedure plus aqua regia digestion of the residue remaining after extraction were similar to those released by pseudo-total digestion of the sediment (using aqua regia).

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

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

Improvement of Analytical Measurements within the BCR-Programme: Single and Sequential Extraction Procedures Applied to Soil and Sediment Analysis

Abstract The determination of extractable trace metal contents in soil and sediment, using respectively single and sequential extraction procedures, is currently performed in many laboratories to assess the bioavailable metal fraction (and related phyto-toxic effects) and the accessability to the environment (e.g. contamination of ground waters). Owing to the need for validation of the extraction schemes used and of the analytical techniques, the Community Bureau of Reference (BCR) decided to organize a project for the improvement of the quality of determinations of extractable trace metal contents in soil and sediment. The implementation of this project follows a stepwise approach involving feasibility studies, intercomparisons to detect and remove sources of errors in the application of the analytical methods, and the certification of the extractable compounds. This paper describes the organization of the work completed so far (feasibility studies and first intercomparison) and discusses its further dev...

Certified reference materials for the quality control of EDTA- and acetic acid-extractable contents of trace elements in sewage sludge amended soils (CRMs 483 and 484)

Abstract The ecotoxicity and mobility of trace elements in soils are often evaluated through analytical results resulting from operationally-defined determinations (single and sequential extractions), e.g. based on EDTA, acetic acid etc. extractions. The significance and comparability of these results is highly dependent on the procedures used (standardized protocols or standards adopted by international bodies) and their quality control relies on the availability of reference materials certified following these strictly applied procedures. Recognizing the need to harmonize some of the extraction schemes currently used for soil analysis, the Measurements and Testing Programme (formerly BCR) has organized a series of interlaboratory studies, the first aim of which was to evaluate EDTA- and acetic acid-extraction procedures and the second objective was to certify reference materials for their extractable trace element contents. Two sewage amended soils have been prepared for this purpose, originating respectively from Scotland and Catalonia. This paper describes the preparation, homogeneity and stability studies, and gives an overview of the certification campaign.