Effective monitoring of pollution by toxic trace elements in waters,sediment and biota of the Derwent River Estuary,Tasmania, through long-term retention of analytical facilities

This study considers the effectiveness of the monitoring of toxic trace elements in various media from a polluted river estuary over a period of 15 years, using the same analytical techniques, facilities and, in some cases, the same operators. It shows that reliable comparisons can be made for monitoring waters, sediment and biota from the Derwent River Estuary between 1975 data and that from 1990. Rigorous studies were undertaken before and during 1975 to ensure that reliable data was achieved at that time. Such studies are reviewed and included the evaluation of digestion techniques for a range of heavy metals, specific attention to the reliability of mercury determination in sediments between laboratories, a comparison of direct calibration and standard addition techniques for metals in seawater, recoveries of an organomercury compound from fish, and sources of error arising from sample preparation of biota for subsequent metal analysis. Comparative results for standard reference materials in both 1975 and 1990 show good agreement and are considered reliable except for lead at low concentrations. The long-term retention of the analytical facilities permits a direct comparison of data from 2 monitoring programmes over the space of 15 years.     

Two fish bile reference materials certified for PAH metabolites

Environmental pollution with polycyclic aromatic hydrocarbons (PAHs) from pyrogenic or petrochemical sources is a matter of concern in many aquatic ecosystems. For field monitoring purposes, PAH metabolite levels in fish bile samples can be used as biomarkers of exposure, but previously there were no reference materials for analytical method validation or quality control. In this paper we describe the preparation and certification of two fish bile materials. BCR 720 is a pure bile material from sediment-exposed flounder (Platichthys flesus) and BCR 721 is a pure bile material from oil-exposed plaice (Pleuronectes platessa). Homogeneity and stability tests were carried out and a group of 12 expert laboratories was assembled for the certification measurements. The methods applied were liquid chromatography with fluorescence detection or gas chromatography with mass spectrometric detection. In BCR 720 three PAH metabolites were certified: 1-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo[a]pyrene. In BCR 721 1-hydroxypyrene was certified. The fourth target compound, 2-hydroxynaphthalene, could not be certified, but the results obtained are listed. The major findings from earlier feasibility studies and recommendations for the optimal use of the reference materials are also included.     

A new organic-rich soil reference material certified for its EDTA- and acetic acid- extractable contents of Cd, Cr, Cu, Ni, Pb and Zn, following collaboratively tested and harmonised procedures

There is an increasing requirement for assessment of the bioavailable metal fraction and the mobility of trace elements in soils upon disposal. One of the approaches is the use of leaching procedures, but the results obtained are operationally defined; therefore, their significance is highly dependent on the extraction protocol performed. So, for this type of study, there is a need for reference materials that allow the quality of measurements to be controlled. This paper describes the steps involved in the certification of an organic-rich soil reference material, BCR-700, for the EDTA- and acetic acid-extractable contents of some trace elements, following collaboratively tested and harmonised extraction procedures. Details are given for the preparation of the soil, homogeneity and stability testing, analytical procedures and the statistical selection of data to be included in the certification.     

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.     

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.     

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.     

Trace-level beryllium analysis in the laboratory and in the field: state of the art, challenges and opportunities

Control of workplace exposure to beryllium is a growing issue in the United States and other nations. As the health risks associated with low-level exposure to beryllium are better understood, the need increases for improved analytical techniques both in the laboratory and in the field. These techniques also require a greater degree of standardization to permit reliable comparison of data obtained from different locations and at different times. Analysis of low-level beryllium samples, in the form of air filters or surface wipes, is frequently required for workplace monitoring or to provide data to support decision-making on implementation of exposure controls. In the United States and the United Kingdom, the current permissible exposure level is 2 microg m(-3) (air) and the United States Department of Energy has implemented an action level of 0.2 microg m(-3) (air) and 0.2 microg/100 cm(2) (surface). These low-level samples present a number of analytical challenges, including (1) a lack of suitable standard reference materials, (2) unknown robustness of sample preparation techniques, (3) interferences during analysis, (4) sensitivity (sufficiently low detection limits), (5) specificity (beryllium speciation) and (6) data comparability among laboratories. Additionally, there is a need for portable, real-time (or near real-time) equipment for beryllium air monitoring and surface wipe analysis that is both laboratory-validated and field-validated in a manner that would be accepted by national and/or international standards organizations. This paper provides a review of the current analytical requirements for trace-level beryllium analysis for worker protection and also addresses issues that may change those requirements. The current analytical state of the art and relevant challenges facing the analytical community will be presented, followed by suggested criteria for real-time monitoring equipment. Recognizing and addressing these challenges will present opportunities for laboratories, research and development organizations, instrument manufacturers and others.     

Interpretation of standard leaching test BS EN 12457-2: is your sample hazardous or inert?

A slag sample from a lead refiner has been obtained and given to two analytical laboratories to determine the release of trace elements from the sample according to BS EN 12457-2. Samples analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert material; samples of the same material analysed by the other laboratory failed waste acceptance criteria and were classified as hazardous. It was found that the sample preparation procedure is the critical step in the leaching analysis and that the effects of particle size on leachability should be taken into account when using this standard. The purpose of this paper is to open a debate on designing a better defined standard leaching test and making current waste acceptance criteria more flexible.     

Evaluation of analytical strategies for the determination of metal concentrations to assess landfill leachate contamination

Due to the complex nature of landfill leachates, metal and metalloid analyses prove to be tricky and suffer from a lack of standard protocols. A complete approach has been adopted to investigate the influence of the different steps during the sample processing of French landfill leachates. The validation of the entire protocol has been achieved using a laboratory reference material. This material, which is a real landfill leachate, is representative of real samples. Its evaluation has allowed a quality control for metal and metalloid analyses in landfill leachates. Precautions concerning storage temperature, aeration and filtration are proposed to perform accurate metal analyses in these complex matrices. The sample processing has been applied to the seasonal monitoring of a French landfill. The assessment of major leachate metallic contaminants such as As, Cr, Sb, Sn, has been performed by evaluating the relative enrichment of metals and metalloids in comparison with rain water and groundwater. In addition, hydrological data are useful and complementary information for pointing out the main factors affecting metal concentrations and thus their potential remobilisation pathways.     

固定污染源废气监测用挥发性卤代烃标准气体制备不确定度研究

针对固定污染源挥发性卤代烃污染物的排放监测需求,采用称量法制备固定污染源废气监测用挥发性卤代烃标准气体(各组分具有浓度差异),并开展制备不确定度评定研究。通过分析原料试剂纯度、液态/气态组分称量、混合液配比、摩尔质量、气体残留等因素和环节引入的不确定度,确立标准气体制备不确定度评定流程。最终,确定固定污染源废气监测用挥发性卤代烃标准气体制备过程引入的相对扩展不确定度(k=2)小于1%。液态/气态组分称量和上一级中间气浓度引入的不确定度对特性量值不确定度的贡献较大,原料试剂纯度对不确定度的影响较小,摩尔质量和气体残留对不确定度的影响可忽略。     

Characterisation of trace elements and methylmercury in an estuarine sediment reference material, IAEA-405

An estuarine sediment sample, IAEA-405, was recently characterised for trace elements and methylmercury (MeHg) for ultimate use as a marine reference material. The reference values were calculated using data sets from 120 laboratories that participated in a world-wide intercomparison exercise. The data evaluation is highlighted, and includes comparisons of different analytical methods, as well as the distribution of data. Overall laboratory performance for this exercise was encouraging: 86 laboratories (72%) reported data with <25% outliers. There was sufficient acceptable data to establish recommended values for 17 elements and information values for a further 15 elements. In addition, a recommended value was established for methylmercury. The estuarine sediment sample, IAEA-405, can be used as a reference material for quality control in the determination of trace elements and methylmercury in moderately polluted sediments.     

Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

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.     

The efficiency of Amberlite XAD-4 resin loaded with 1-(2-pyridylazo)-2-naphthol in preconcentration and separation of some toxic metal ions by flame atomic absorption spectrometry

A selective method has been developed for the determination of trace amount of metal ions after preconcentration on 1-(2-pyridylazo)-2-naphthol loaded Amberlite XAD-4 resin. The chelating resin was characterized on the basis of infra red spectra, thermal and chemical stability, and hydrogen ion capacity. High preconcentration factor of 160?C400 up to a low preconcentration limit of 10 ??g L^???1 has been achieved for almost all the metals. The chelating resin was highly selective even in the presence of large concentrations of alkali and alkaline earth metals and various matrix components. Chromatographic separation of metal ions in binary mixtures has been accomplished. The analytical utility of the resin for metal ions was explored by analyzing natural water and standard reference materials.     

Two thousand years of atmospheric rare earth element (REE) deposition as revealed by an ombrotrophic peat bog profile,Jura Mountains,Switzerland

A peat core from a Swiss bog represents 2110 14C years of peat accumulation and provides a continuous record of atmospheric rare earth element (REE) deposition. This is the first study providing a time-series of all REE originating from the atmosphere. Concentrations of the 14 REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) were determined using inductively coupled plasma-mass spectrometry (ICP-MS) after dissolution of 200 mg aliquots of age-dated peat samples with 3 ml HNO3 and 0.1 ml HBF4 at 240 degrees C in a microwave autoclave. Strict quality control schemes were applied to ensure the accuracy of the applied analytical methodology. Previous analyses of selected REE by instrumental neutron activation analysis (INAA) in the same set of peat samples revealed that INAA frequently under- or overestimated REE concentrations in a systematic manner. Concentration profiles obtained for all REE were almost identical, except for Ce and Eu. Calculation of enrichment factors (EF) revealed a distinct depletion of heavy REE relative to light REE in peat samples since the beginning of the 19th century which marks the onset of the Industrial Revolution in Europe, suggesting a pronounced influence by anthropogenic activities. Enrichments of REE calculated using Sc as a reference element exceeded unity, relative to the Upper Continental Crust. Overall, EF in all peat samples ranged from 1.96 for Sm to 2.34 for Gd, with considerably lower EF for Ce (1.82) and Eu (1.44), respectively. A significant enrichment of all REE which may have been caused by military activities, was observed in the peat sample dating from World War II (1944); this exceptional sample, however, is not enriched in Ce. The concentration profiles of REE were similar but not identical to those of other lithogenic, conservative reference elements such as Sc, Y, Al, Zr and Ti. While it has been suggested that individual REE concentrations or the sum of REE can be used as a reference parameter to calculate crustal EF in environmental samples the data presented here indicates that anthropogenic emissions of REE cannot simply be ignored.     

Determination of organochlorinated compounds and petroleum hydrocarbons in sediment sample IAEA-408. Results from a world-wide intercalibration exercise

A sediment sample from the intertidal mudflats of the Tagus estuary was prepared, homogenised and distributed globally to laboratories as the IAEA-408 intercomparison material for the analyses of organochlorinated pesticides, PCBs and petroleum hydrocarbons (PHs). A total of 48 laboratories from 36 countries reported their results. The data from participants show that there still remain some difficulties with the accurate determination of organic contaminants such as pesticides and polycyclic aromatic hydrocarbons (PAHs). More consistent interlaboratory results were obtained for PCBs congeners. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-408 can now be used as a reference material for quality control in the determination of some persistant organic pollutants (POPs) in marine sediment samples.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

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.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).