Projects for the improvement of the quality of chemical speciation analyses in environmental matrices

Summary The release of organometallic compounds and other chemical forms of elements in the environment has caused great concern because of their possible high toxicity. To validate the analytical techniques, the Community Bureau of Reference (BCR) has undertaken a series of projects for the improvement of the quality of determinations of chemical species in environmental matrices. The implementation of these projects follows a stepwise approach involving intercomparisons to detect and remove sources of errors in different phases of the analytical methods and the certification of the compounds in various matrices. The current projects deal with the determination of the extractable content of trace metals in soils (single extraction) and sediment (sequential extraction), forms of aluminium in water, elements with different oxidation states (e.g. As, Cr and Se) and organic forms (e.g. methylated forms of As in solution, methyl-mercury in fish, arseno-betaine and -choline in solutions, triethyl- and trimethyl-Pb compounds in solution, and butyltin compounds in sediment).Abbreviations AAS atomic absorption spectrometry - CVAAS cold vapour AAS - DPP differential pulse polarography - ECD electron capture detector - ETAAS electrothermal AAS - FIA flow injection analysis - FID flame ionisation detector - FLUOR spectrofluorimetry - FPD flame photometric detector - GC gas chromatography - HG hydride generation - HPLC high performance liquid chromatography - HPLC-AES HPLC atomic emission spectrometry - INAA instrumental neutron activation analysis - ICPAES Inductively coupled plasma AES - MS mass spectrometry - QFAAS quartz furnace AAS - RNAA neutron activation analysis with radiochemical separation     

Conclusions of the workshop

The development of analytical techniques for the determination of chemical species has been one of the fastest growing features of the 90's in analytical chemistry. The need for good quality control of these determinations has led the Measurements and Testing Programme (BCR) to organize several series of interlaboratory studies in the field of speciation analysis over the last five years. The state of the art of speciation analysis was discussed at a first workshop in 1990 (Arcachon, F) and, at this stage, it was deemed necessary to discuss the progress achieved and the trends which should be developed in the near future. A workshop on Trends in Speciation Analysis was therefore held in Rome in February 1994, which allowed recommendations to be made based on round-table discussions. This paper gives a summary of these recommendations in the field of inorganic speciation. Projects currently undertaken in the field of inorganic speciation within the Measurements and Testing Programme are also described. An outline of the programme along with the panel of experts participating in this workshop is given in the appendix.     

Conclusions of the workshop

The development of analytical techniques for the determination of chemical species has been one of the fastest growing features of the 90's in analytical chemistry. The need for good quality control of these determinations has led the Measurements and Testing Programme (BCR) to organize several series of interlaboratory studies in the field of speciation analysis over the last five years. The state of the art of speciation analysis was discussed at a first workshop in 1990 (Arcachon, F) and, at this stage, it was deemed necessary to discuss the progress achieved and the trends which should be developed in the near future. A workshop on Trends in Speciation Analysis was therefore held in Rome in February 1994, which allowed recommendations to be made based on round-table discussions. This paper gives a summary of these recommendations in the field of inorganic speciation. Projects currently undertaken in the field of inorganic speciation within the Measurements and Testing Programme are also described. An outline of the programme along with the panel of experts participating in this workshop is given in the appendix.     

Recent developments in speciation and determination of organometallic compounds in environmental samples

Summary Recent developments in the techniques of speciation and determination of organometallic compounds in the environment are reviewed. There is an increasing trend in the use of high performance liquid chromatography as separation tool, and in the use of plasma-excited atomic emission spectrometry as detector. New techniques have been reported to overcome the historically difficult interface of HPLC to furnace AAS. There are also new techniques in the derivatization of ionic organometallic species for gas chromatography. Tandem analytical systems are getting more and more sophisticated, so are the sensitivity and specificity.     

Trends in trace element determinations in environmental and food matrices: Conclusions of the workshop

The improvement and development of analytical techniques for the determination of trace elements in environmental and food matrices are one of the main challenges of analytical chemists nowadays. The need for a good quality control of these determinations has led the Measurements and Testing Programme (BCR) to organize series of intercomparisons and to produce certified reference materials (CRM's) for improving the quality of environmental and food matrices. At this stage, it was deemed necessary to discuss the research which should be undertaken to further improve the state of the art of trace element determinations and to develop new methodologies. A workshop on Trends in Trace Element Determinations in Environmental and Food Matrices has therefore been held in Thessaloniki in October 1994 which allowed to identify the research needs and make some recommendations based on round-table discussions. This paper gives a summary of the conclusions of the discussions. An outline of the programme along with the panel of experts participating in this workshop is given in the appendix.     

Trends in selenium determination/speciation by hyphenated techniques based on AAS or AFS

The field of selenium speciation has been studied for decades and the growing interest in this field seems never to reach a plateau. Although powerful techniques based on mass spectrometry are nowadays used for selenium determination/speciation, few laboratories can support the high cost of such techniques. The hyphenation of chromatography to atomic absorption or atomic fluorescence spectrometry (AAS or AFS) is still a reliable and low-cost alternative for routine laboratories. In this work we present the most important parameters dealing with selenium speciation along with the latest trends in this subject, namely in the items related with sample treatment and hyphenation techniques with AAS and AFS detection.     

Certification of total mercury and methylmercury concentrations in mussel homogenate (Mytilus edulis) reference material, IAEA-142

Due to the increased demand for new reference materials certified for total and methylmercury (MeHg) a sample of mussel homogenate (IAEA-142) has been prepared. Thirteen experienced laboratories reported results for total Hg of which 9 laboratories also reported results for MeHg content. Laboratories reporting MeHg results used various isolation techniques (solvent extraction, saponification, acid leaching, ion-exchange separation, and distillation) and detection systems (cold vapour atomic absorption spectrometry (CV AAS), cold vapour atomic fluorescence spectrometry (CV AFS), gas chromatography with electron capture detector (GC/ECD) and HPLC with CV AAS detector). In the case of total Hg, most of the laboratories used acid digestion, only two used alkaline dissolution, followed either by CV AAS or CV AFS. One laboratory used neutron activation analyses with radiochemical separation. The data received were in good agreement. The value for total Hg was certified to be 126 ng/g, with a 95% confidence interval from 119 to 132 ng/g. For MeHg the certified value of 47 ng/g expressed as Hg was assigned, with a 95% confidence interval from 43 to 51 ng/g. Stability testing has shown that both total and MeHg are stable if samples are stored in a dry and dark place at room temperature. The sample is now available as a certified reference material and is, in particular, useful for quality control measurements of Hg and MeHg in mussel samples at low concentration levels. Received: 24 September 1996 / Revised: 20 November 1996 / Accepted: 8 December 1996     

Certification of total mercury and methylmercury concentrations in mussel homogenate (Mytilus edulis) reference material, IAEA-142

Due to the increased demand for new reference materials certified for total and methylmercury (MeHg) a sample of mussel homogenate (IAEA-142) has been prepared. Thirteen experienced laboratories reported results for total Hg of which 9 laboratories also reported results for MeHg content. Laboratories reporting MeHg results used various isolation techniques (solvent extraction, saponification, acid leaching, ion-exchange separation, and distillation) and detection systems (cold vapour atomic absorption spectrometry (CV AAS), cold vapour atomic fluorescence spectrometry (CV AFS), gas chromatography with electron capture detector (GC/ECD) and HPLC with CV AAS detector). In the case of total Hg, most of the laboratories used acid digestion, only two used alkaline dissolution, followed either by CV AAS or CV AFS. One laboratory used neutron activation analyses with radiochemical separation. The data received were in good agreement. The value for total Hg was certified to be 126 ng/g, with a 95% confidence interval from 119 to 132 ng/g. For MeHg the certified value of 47 ng/g expressed as Hg was assigned, with a 95% confidence interval from 43 to 51 ng/g. Stability testing has shown that both total and MeHg are stable if samples are stored in a dry and dark place at room temperature. The sample is now available as a certified reference material and is, in particular, useful for quality control measurements of Hg and MeHg in mussel samples at low concentration levels.     

Improvement of quality control of speciation analysis using hyphenated techniques A decade of progress within the European Community

The awareness of a need for an improved control of environmental contamination levels has led to the development of new hyphenated techniques for the determination of a wide variety of chemical species (e.g., organotins, methyl-mercury, alkyl-lead compounds etc.). These techniques generally involve many analytical steps such as extraction, derivatisation, separation and detection which have to be carried out in such a way that the speciation is not changed during the abalytical process. The need for evaluating the method's performance has led the BCR programme of the European Commission (now Standards, Measurements and Testing programme) to conduct series of interlaboratory studies during the last decade. These projects followed a step-by-step approach for the evaluation of different steps of the analytical methods used, e.g., simple solutions to test the detection, cleaned extract to evaluate the separation, spiked samples to test the extraction and natural samples to evaluate the whole analytical procedures. These collaborative projects allowed most of the sources of errors related to either a technique or a laboratory to be detected and removed. This paper gives an account of discussions of possible errors occurring in speciation analysis and presents examples of technical scrutiny of hyphenated techniques using chromatography as applied to the determination of tributyltin, methyl-mercury and trimethyllead.     

Element-selective detection in liquid and gas chromatography by diode laser absorption spectrometry

An element-selective detector for chromatography based on atomic absorption spectrometry with semiconductor diode lasers is described. The analytical utility of the technique is demonstrated by speciation examples of HPLC and GC employing analytical flames and plasmas to atomize.     

An evaluation of reversed-phase and ion-exchange chromatography for use with inductively coupled plasma—mass spectrometry for the determination of organotin compounds

An evaluation of reversed-phase high-performance liquid chromatography (HPLC) employing mobile phases compatible with direct coupling to inductively coupled plasma-mass spectrometry (ICP-MS) is described for the selective and sensitive detection of organotin species. The findings of this study are compared with established methods, employing ion-exchange chromatography. In order to achieve optimum performance, both the HPLC and ICP-MS were optimized for speciation work. The results from studies using various mobile phases for the separation of a range of tin compounds (inorganic tin, tributyltin, dibutyltin and monobutyltin) are discussed both in terms of resolution and compatibility with ICP-MS instrumentation. Tropolone, a commonly used complexing agent for organotin species, is also discussed with reference to the chromatographic separation of tin species. Finally, the role of isotope dilution analysis in conjunction with HPLC-ICP-MS for organotin speciation is described with respect to the European Community Standards, Measurements and Testing (BCR) certified material programme.     

Arsenic and its speciation analysis using high-performance liquid chromatography and inductively coupled plasma mass spectrometry

It is known that arsenic has different toxicological properties dependent upon both its oxidation state for inorganic compounds, as well as the different toxicity levels exhibited for organic arsenic compounds. The field of arsenic speciation analysis has grown rapidly in recent years, especially with the utilization of high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS), a highly sensitive and robust detector system. Complete characterization of arsenic compounds is necessary to understand intake, accumulation, transport, storage, detoxification and activation of this element in the natural environment and living systems. This review describes the essential background and toxicity of arsenic in the environment, and more importantly, some currently used chromatographic applications and sample handling procedures necessary to accurately detect and quantify arsenic in its various chemical forms. Applications and work using only HPLC-ICP-MS for arsenic speciation of environmental and biological samples are presented in this review.     

CRMs for quality control of determinations of chemical forms of elements in support to EU legislation

The concern for the control of toxic chemical forms of elements in the environment is reflected by an increasing number of analyses performed by research and routine laboratories. The European Commission has recognised the need to include some of these species in the list of dangerous substances to be monitored, e.g. in the marine environment or in groundwater. However, in most cases, the specifications are far from being sufficient in respect to the chemical forms of the element to be determined. Furthermore, these determinations are in most cases based on multi-step analytical techniques which are often prone to errors (e.g. at the extraction, derivatization or separation steps). Certified reference materials (CRMs) certified for their content in chemical forms of elements are, therefore, necessary to ensure the accuracy of these measurements and hence the respect of the regulations. However, the lack of CRMs for speciation analysis hampers the quality control of determinations which in turn leads to an incomparability of data produced; so far the number of CRMs produced by international organisations, e.g. NIST (USA), NIES (Japan), NRCC (Canada) and BCR (Belgium), is very limited and concerns mainly compounds such as e.g. methyl-mercury and butyltin compounds in biological matrices or sediments. The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a series of projects for the improvement of speciation analysis in environmental matrices, the final aim of which being the production of a variety of environmental CRMs. The existing EU legislation involving chemical forms of elements is presented, the requirements for the preparation of CRMs for speciation analysis are discussed and an update of the most recent CRMs produced within the Standards, Measurements and Testing Programme (SM&T) is given.     

高效液相色谱及其联用技术在汞形态分析中的应用

本文对近二十年来高效液相色谱及其联用技术在汞的形态分析中的应用进行了综述，着重讨论了样品的前处理方法，高效液相色谱用于汞化合物的形态分离以及检测器的选择。     

CRMs for quality control of determinations of chemical forms of elements in support to EU legislation

The concern for the control of toxic chemical forms of elements in the environment is reflected by an increasing number of analyses performed by research and routine laboratories. The European Commission has recognised the need to include some of these species in the list of dangerous substances to be monitored, e.g. in the marine environment or in groundwater. However, in most cases, the specifications are far from being sufficient in respect to the chemical forms of the element to be determined. Furthermore, these determinations are in most cases based on multi-step analytical techniques which are often prone to errors (e.g. at the extraction, derivatization or separation steps). Certified reference materials (CRMs) certified for their content in chemical forms of elements are, therefore, necessary to ensure the accuracy of these measurements and hence the respect of the regulations. However, the lack of CRMs for speciation analysis hampers the quality control of determinations which in turn leads to an incomparability of data produced; so far the number of CRMs produced by international organisations, e.g. NIST (USA), NIES (Japan), NRCC (Canada) and BCR (Belgium), is very limited and concerns mainly compounds such as e.g. methyl-mercury and butyltin compounds in biological matrices or sediments. The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a series of projects for the improvement of speciation analysis in environmental matrices, the final aim of which being the production of a variety of environmental CRMs. The existing EU legislation involving chemical forms of elements is presented, the requirements for the preparation of CRMs for speciation analysis are discussed and an update of the most recent CRMs produced within the Standards, Measurements and Testing Programme (SM&T) is given.     

Electron microprobe analysis of micro amount powder samples: A case study on high purity coal

For the major, minor and trace element analysis of the inorganic compounds of a Ruhr-Saar coal different preparation techniques are investigated with X-ray fluorescence analysis, electron microprobe and classical wet chemical methods minimizing sample weight at standard preparation times and analytical accuracies. Considering accuracy as well as preparation efforts, determinations by electron microprobe on small sample amounts (<50 mg) proved to be superior to the other methods.Abbreviations AAS atomic absorbtion spectrometry - EMA electron microprobe analysis - IC ion chromatography - ISE ion sensitive electrode - PHOT photometry - WCA wet chemical analysis - XRF X-ray fluorescence analysis - LTA low temperature plasma ashing - HTA high temperature ashing - l.o.i. loss on ignition     

Solar blind photocell--a simple element specific detector in Hg, As and Se speciation

An element-specific detection method, based on atomic absorption spectrometry (AAS) using solar blind photocells instead of a dispersion system, is described for the determination of Hg-, As-, and Se-species. Spectrometric investigations of AAS background lamps for As and Se measured with a CsI-cathode photocell shows its quality as narrow band detector. Species determination can be carried out subsequently to prior separation by HPLC or GC. The LODs for alkylated Hg species were below 1 ng/L, and for methylated As species below 1 microg/L. The relative standard deviation was < 10%. With the components described the production of cheap and automated dedicated speciation spectrometers is possible.     

On-line coupling between chromatography and inductively coupled plasma mass spectrometry — a current assessment

The current state of on-line coupling between liquid chromatography and inductively coupled plasma mass spectrometry is reviewed. The applications can be divided into three subgroups by changing the importance of the coupling partners. An overview is given of applications in these subgroups, of its use as preconcentration and matrix elimination techniques, for the elimination of spectral interferences and as a tool for speciation analysis. A discussion of current and future development areas in on-line HPLC-ICP-MS is also included.     

Preparation,homogeneity and stability studies of a candidate LRM for Se speciation

A laboratory reference material (LRM) was prepared from Brazil nuts (Bertholletia excelsa) for quality control (QC) purposes of selenium speciation. The preparation of this LRM led through the usual operation steps applied during routine reference material production from biota samples-preparation of the raw material, homogenisation, storage design, checking of homogeneity, microbiological status and possible irradiation effects, and monitoring the species stability vs time at different storage temperatures. The selenium speciation studies to check species stability were carried out on a HPLC-UV-HG-AFS measurement set-up. Special attention was paid to the correct identification of selenium species by applying independent HPLC separation techniques (ion-pairing and anion-exchange chromatography). The concentration of selenomethionine (SeMet) and total Se content were quantified (79.9 microg g(-1) (calculated as Se) and 82.9 microg g(-1), respectively). The homogeneity and stability of this candidate reference material passed the relevant tests recommended by Bureau Communautaire de Référence (BCR).