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.     

Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and EDTA extractable metal content

This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.     

Evaluation of the state-of-the-art of butyl- and phenyltin compound determinations in freshwater sediment prior to certification of a reference material

In order to control the quality of butyl- and phenyltin compound determinations in sediment, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a freshwater sediment for its contents of a range of organotin compounds (mono-, di- and tributyltin, and mono-, di- and triphenyltin). The first part of this project involved an interlaboratory study which aimed to test the feasibility of preparation of candidate freshwater sediment reference material and to detect and remove most of the pitfalls observed in organotin determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The agreement obtained among laboratories for the six compounds determined was considered to reflect the state-of-the-art and was encouraging enough to decide upon the organisation of a certification campaign, which will be concluded in June 1999.     

Collaborative evaluation of the analytical state-of-the-art of platinum, palladium and rhodium determinations in road dust

In order to control the quality of platinum, palladium and rhodium determinations in road dust, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a road dust reference material for its contents of platinum group elements. The first part of this project consisted of an interlaboratory study, which aimed to test the feasibility of the preparation of a candidate road dust reference material and to detect and remove most of the pitfalls observed in platinum, palladium and rhodium determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The concordance of the data obtained by the participating laboratories for the three elements was considered to reflect the state-of-the-art and was encouraging enough to decide on the organization of a certification campaign to be conducted during the year 2000. The progress made with respect to the analytical state-of-the-art for these elements will be of great benefit to the quality of measurements carried out in environmental monitoring in this particular field.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Interlaboratory trial to determine the analytical state-of-the-art of bromate determination in drinking water

The new European Directive for water intended for human consumption has established a regulatory level for bromate at 10 microg L(-1). This Maximum Admissible Concentration requires analytical methods with detection limits of a least 2.5 microg L(-1). A project funded by the Standards, Measurements and Testing Programme of the European Commission has enabled the improvement and/or development of methods for the determination of bromate at such concentration levels. This collaborative work was concluded by the organisation of an interlaboratory trial involving 26 European laboratories, which enabled the testing of both a draft ISO Standard method and alternative methods. This paper presents the results of this interlaboratory trial, along with results of a bromate stability study. The progress made with respect to the analytical state-of-the-art for bromate will greatly benefit the quality of measurements carried out in water quality monitoring.     

Interlaboratory evaluation of an extraction and fluorescence method for the determination of trace beryllium in soils

Analytical methods for the determination of trace beryllium in soils are needed so that anthropogenic sources of this element can be distinguished from native (background) levels of beryllium. In this work, a collaborative interlaboratory evaluation of a new extraction and fluorescence-based procedure for determining beryllium in soil samples was carried out to fulfil method validation requirements for ASTM International voluntary consensus standard test methods. A Canadian reference material, CCRMP Till-1 soil, with a background beryllium concentration of 2.4 microg g(-1), was selected for study. This certified reference material (CRM) was spiked and homogenized with varying levels of beryllium oxide in order to give batches of material with beryllium concentrations of 4.36 +/- 0.69, 11.5 +/- 0.7, 124 +/- 7 and 246 +/- 16 microg g(-1) (+/- values are standard deviations). In the interlaboratory study (ILS), which was carried out in accordance with an applicable ASTM International standard practice (ASTM E691), samples of these spiked soils were subjected to extraction in dilute ammonium bifluoride at approximately 90 degrees C for 40 h. Fluorescence measurement of the extracted beryllium was carried out via detection using the high quantum yield fluorophore, hydroxybenzoquinoline sulfonate (HBQS). Interlaboratory precision estimates from six participating laboratories ranged from 0.048 to 0.103 (relative standard deviations) for the five different beryllium concentrations. Pooled bias estimates resulting from this ILS were between -0.049 and 0.177 for the various beryllium levels. These figures of merit support promulgation of the analytical procedure as an ASTM International standard test method.     

An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

Ultrasonic extraction and portable anodic stripping voltammetric measurement of lead in paint, dust wipes, soil, and air: an interlaboratory evaluation

Recent studies have demonstrated the utility of ultrasonic extraction (UE), followed by portable anodic stripping voltammetry (ASV), for the on-site determination of lead in environmental and industrial hygiene samples. The aim of this work was to conduct an interlaboratory evaluation of the UE-ASV procedure, with a goal of establishing estimates of method performance based on results from collaborative interlaboratory analysis. In this investigation, performance evaluation materials (PEMs) with characterized lead concentrations were used for interlaboratory testing of the UE-ASV procedure. The UE-ASV protocol examined has been promulgated in the form of two separate national voluntary consensus standards (one for UE and another for electroanalysis, which includes ASV). The PEMs consisted of characterized and homogenized paints, soils, and dusts (the last of which were spiked onto wipes meeting national voluntary consensus standard specifications), and air filter samples (mixed cellulose ester membrane) generated using characterized paints within an aerosol chamber. The lead concentrations within the PEMs were chosen so as to bracket pertinent action levels for lead in the various sample matrices. The interlaboratory evaluation was conducted so as to comply with an applicable national voluntary consensus standard that can be used to estimate the interlaboratory precision of a given analytical test method. Based on the analytical results reported by the participating laboratories, relative standard deviations (RSDs) for repeatability and reproducibility were computed for three different lead contents of the four PEMs. RSDs for repeatability were 0.019-0.100 for paints; 0.030-0.151 for soils; 0.085-0.134 for dust wipes; and 0.095-0.137 for air filters. RSDs for reproducibility were 0.127-0.213 for paints; 0.062-0.162 for soils; 0.085-0.134 for dust wipes; and 0.114-0.220 for air filters. With the exception of one of the air filter samples and one of the paint samples, the precision estimates were within the +/- 20% precision requirement specified in the US Environmental Protection Agency National Lead Laboratory Accreditation Program (NLLAP). The results of this investigation illustrate that the UE-ASV procedure is an effective method for the quantitative measurement of lead in the matrices evaluated in this study.     

Validation of a European standard for the determination of hexavalent chromium in solid material

A European standard for the determination of Cr(vi) in solid material has been elaborated in the framework of an international co-operation and finally validated in the course of an interlaboratory comparison. The procedure is based on the alkaline digestion prescribed by EPA method 3060A followed by ion chromatography and determines an operationally defined content of Cr(vi), including water-soluble and insoluble chromates. A preliminary robustness study was carried out in order to compare different extraction methodologies and to study the equivalency of different analytical methods for the determination of Cr(vi) in alkaline extracts of soil and waste materials. During an interlaboratory validation trial with 19 European laboratories a set of 4 samples (2 soil and 2 waste samples) was analysed to determine performance characteristics for different combinations of digestion and detection methods. With the procedures prescribed by the new European standard (EN 15192) acceptable results were obtained for both soil samples and one of the waste samples (sludge). However, for the second waste sample (fly ash) a large deviation in analytical results was observed. This indicates that particularly for waste materials a possible occurrence of strong matrix effects has to be considered and supplementary quality control data are needed in order to assess the validity of analytical results. The accuracy of the determination of Cr(vi) in solid matrices remains a challenging field in terms of maximum extraction efficiency and minimum species interconversion.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

Prediction of PAH biodegradation in field contaminated soils using a cyclodextrin extraction technique

Biodegradation has been identified as a major loss process for organic contaminants in soils and, as a result, microbial strategies have been developed for the remediation of contaminated land. Prediction of the biodegradable fraction would be important for determining bioremediation end-points in the clean-up of contaminated land. The aim of this study was to investigate the ability of a cyclodextrin extraction to predict the extent to which polycyclic aromatic hydrocarbons (PAHs) would be degraded microbiologically in field contaminated soils; further testing the robustness and reproducibility of this extraction in chemically complex systems. Dichloromethane and hydroxypropyl-beta-cyclodextrin (HPCD) extractable fractions were measured together with the PAH biodegradable fraction in each of the six field contaminated soils. The amounts of PAHs degraded by the catabolic activity of the indigenous microflora in each of the soils were correlated with HPCD-extractable PAH concentrations. The regressions showed that the amounts of lower molecular weight PAHs extracted by the HPCD were not significantly (P > 0.05) different to the amounts that were degraded. However, higher molecular weight PAHs that were extracted by HPCD did differ significantly (P < 0.05) from the amounts degraded. Although the HPCD extraction did overestimate the microbially degradable fraction of the higher molecular weight PAHs, overall the correlations between the HPCD extractable fraction and the microbially degradable fraction were very close, with mean values of the slope of line for the six soils equalling 1. This study further describes the robust and reproducible nature of the aqueous-based soil extraction technique reliably measuring the extent to which PAHs will be microbially degraded in soil.     

A new mussel certified reference material (CRM 477) for the quality control of butyltin determination in the marine environment

The analytical techniques used for the determination of butyltin compounds in biological tissues are generally based on a succession of steps (e.g., extraction, derivatization, separation, detection) which are all prone to systematic errors. An interlaboratory programme performed at the EU level and based on a stepwise approach has enabled one to identify and remove most of these errors and to improve considerably the state of the art so that certification of a mussel reference material has been made possible. This paper describes the preparation of this mussel reference material containing monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT), the homogeneity and stability studies and the analytical work performed for the certification of the contents of MBT [Sn(C4H9)3+], DBT [Sn(C4H9)2(2+)] and TBT [Sn(C4H9)3+]. The results obtained by a group of expert EU laboratories are discussed along with the methods used to certify the mass fractions (based on dry mass) of monobutyltin (1.50 +/- 0.28 mg kg-1 as MBT cations), dibutyltin (1.54 +/- 0.12 mg kg-1 as DBT cations) and tributyltin (2.20 +/- 0.19 mg kg-1 as TBT cations). The paper also describes an attempt to certify the content of triphenyltin in this material which, although reasonable agreement was found among the participants' results, failed owing to the instability of this compound. This new material will be of great support to ensure the quality control of butyltin determination in shellfish, as carried out in environmental monitoring programmes.     

生态地球化学调查评价形态分析实验室间比对试验结果分析

通过对生态地球化学调查评价形态分析实验室间比对试验结果的统计分析和技术分析,进一步验证和统一生态地球化学评价样品形态分析方法,提高实验室间形态分析数据的可比性,了解参加实验室形态分析的技术能力,为制定生态地球化学评价样品形态分析相关规范提供基础数据依据。     

Feasibility study prior to the certification of trace elements in urban and industrial wastewater reference materials

Reliable results for the determination of trace elements in urban and industrial wastewaters are of paramount importance for both checking the performance of sewage treatment and for detecting possible urban or industrial contamination sources. The quality control of measurements should in principle rely on external tools such as certified reference materials (CRM), which should represent, as closely as possible, the matrix of samples currently analysed, e.g., in the frame of environmental monitoring. To date, however, no CRM representatives of wastewater composition are available, which limits the possibility for control laboratories to check their QC externally. To fill this gap, the European Commission's Standards, Measurements and Testing Programme (formerly BCR) has started a European collaborative project of which the aim is to test the feasibility of preparation of wastewater reference materials and the analytical state-of-the-art to enable the certification of trace elements in such matrices. This paper presents the results of the first phase of this project, namely the feasibility study and the results of an interlaboratory trial.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

水中异味物质分析方法研究进展

介绍了水体异味现象及异味物质组分,综述了闭环捕集、吹扫捕集、液液萃取、固相萃取、固相微萃取、搅拌棒吸附萃取等样品前处理技术。指出气相色谱/质谱联用具有很强的分离和定性定量能力,与上述前处理技术联用是目前水体异味物质分析应用最广泛的方法。     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

An interlaboratory comparison of sediment elutriate preparation and toxicity test methods

Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.