Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

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.     

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.     

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).     

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.     

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.     

A risk assessment study of water quality,biota, and legacy sediment prior to small dam removal in a tributary to the Delaware River

The proposed removal of three run-of-river dams (all ≤5-m height) in eastern Pennsylvania along lower Bushkill Creek, a tributary of the Delaware River, has provided a valuable opportunity for multidisciplinary research involving the collection of more than 5 years of pre-removal monitoring data, analysis of heavy metals in legacy sediment cores, and associated toxicity assays to determine the singular and interactive effects of lead, copper, and cadmium on survival and behavior of a common macroinvertebrate found in Bushkill Creek. Monitoring data were collected from sites approximately 35 m upstream and downstream of dams and reference sites located approximately 5 km upstream of all dams. Results indicate that oxygen levels, macroinvertebrate diversity, and proportion of sensitive taxa were significantly lower upstream and downstream of dams in comparison with upstream reference reaches. The strong correlation between water quality and macroinvertebrates in this system implies that removal of the lower three dams would lead to improvements in water quality, biotic integrity, and resilience in lower Bushkill Creek. Sediment analyses and toxicity assays suggest that dam removal and sediment mobilization may route contaminated sediments downstream at concentrations that may harm more sensitive biota. However, macroinvertebrate mortality and behavior were not significantly different from clean water controls for the large majority of toxicity assays. All together, these results suggest that dams 1–3 are good candidates for successful stream restoration but that the removals would best be planned in a way that mitigates potential impacts of contaminated legacy sediment.     

Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

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.     

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.     

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.     

Evaluation of four mathematical models to describe dissipation kinetics of 4-n-nonylphenol and bisphenol-A in groundwater-aquifer material slurry

The performance of four mathematical models (hockey stick, biexponential, first-order double exponential decay, and first-order two-compartment) was evaluated to describe the dissipation kinetics for 4-n-nonylphenol (4-n-NP) and bisphenol-A (BPA) in groundwater-aquifer material slurry under aerobic and anaerobic conditions conducted under controlled laboratory conditions. The fit of each model to the measured values under both conditions was tested using an array of statistical indices to judge the model's ability to fit the measured datasets. Corresponding 50% (DT(50)) and 90% (DT(90)) dissipation values for each compound were numerically obtained and compared against each model. The model derived DT(50) values in groundwater-aquifer material ranged from 1.06 to 1.24 (4-n-NP) and 0.341 to 0.568 days (BPA) under aerobic condition, while they were 2- to 4-fold higher under anoxic condition. DT(90) values for 4-n-NP ranged anywhere between 2.3 and 4.45 days under both conditions, while DT(90) values for BPA ranged from around 1 day to as high as 12 days under both conditions tested. A visual examination of the measured and fitted plots as well as the statistical indices showed that, with the exception of the hockey stick model, the models performed satisfactorily. Despite having only 3 parameters, the biexponential model could describe the dissipation kinetics very well and this was supported by the statistical indices generated for each case.     

Evaluation of the effect of porous check dam location on fine sediment retention (a case study)

This study was carried out to evaluate the influence of porous check dam location on the retention of fine sediments in the Droodzan watershed in Southern Iran. Five long streams with several porous check dams that were more than 27 years old were studied. In each stream three check dams: at the very upstream section, at the middle section and at the far downstream section were selected for analysis. A number of samples from trapped sediments and from the undisturbed soils in the stream banks (adjacent to the check dams) were collected. Laboratory analysis showed that the soil samples taken from undisturbed banks have smaller particle sizes compared to the trapped sediments. The results indicated that the check dams located at the far downstream sections were more efficient at trapping fine sediment than those located at the middle sections. Also the check dams located at the middle sections were more effective than those located at the upstream sections. Comparison of sediment texture also showed that the portion of clay and silt trapped by the check dams decreased from the downstream sections toward the upstream sections. Hence, whenever, the retention of fine sediments is the primary function of the check dams, it appears that they should be located in the far downstream sections of a stream. The experimental analysis indicated that using broken and angular rocks instead of rounded rocks in porous check dam's construction improves the effectiveness of the check dams for the retention of fine sediments. The analysis of the failed check dams also showed that erosion of the bank sides underneath the check dams is the primary cause of dam collapse.     

Evaluation of chromium contamination in water, sediment and vegetation caused by the tannery of Jijel (Algeria): a case study

In order to evaluate the chromium (Cr) contamination due to the discharge of waste waters from the tannery of Jijel in the Mouttas river (Algeria), samples of water, sediment and vegetation (Agropyrum repens) were collected during a 6 month period in four stations located upstream (control) and downstream of the tannery. The total chromium was measured by atomic absorption spectrophotometry. Metal inputs were clearly related to effluent discharges from the tannery into the river. Although only traces of chromium were found in water samples upstream of the tannery, very high concentrations (up to 860 times higher) were detected downstream. The contamination was not limited to water of Mouttas River because a same difference in chromium concentrations was also found in sediments and plants Agropyrum repens that were sampled upstream and downstream of the tannery. This work showed that the treatment process used in the wastewater treatment plant of the tannery of Jijel is not able to remove the chromium detected in their influents. The occurrence and chromium levels detected in the aquatic environment represent a major problem concerning drinking water resources and environmental protection of water bodies.     

Plankton diversity and water quality assessment of three freshwater lakes of Mandi (Himachal Pradesh, India) with special reference to planktonic indicators

The present study deals with the limnobiotic status of three selected lakes of Himachal Pradesh using physicochemical and biological parameters (especially phytoplankton and zooplankton) over a period of 2 years. One hundred forty-eight species belonging to nine groups of phytoplankton and 79 species belonging to five groups of zooplankton were identified from the lakes. Trophic level and the pollution status of the lakes were assessed upon the basis of Shannon diversity index (H′), species richness index (S), and physicochemical parameters. Plankton population size was correlated with biotic and abiotic parameters (pH, alkalinity, temperature, dissolved oxygen, transparency, phosphate, chloride, and nitrate). The present investigation revealed that the distribution of plankton species depended upon the physicochemical parameters of the environment. Based on water quality standards given by the Central Pollution Control Board, the water quality was between “A–B” at Prashar wetland, “C–D” at Kuntbhyog Lake, and “D–E” at Rewalsar Lake. The results from the present study indicated that the potential of planktons as bioindicators of trophic status is very high.     

水中微量偏二甲基肼检测方法的研究和应用

偏二甲基肌是川作火箭推进剂燃料,有较大的毒性,也是环境污染物。它的水中最大允许浓度为０．０６ｍｇ／Ｌ。本研究建立了一种水中微量偏二甲基肼的检测方法,采用钼酸铵作为试剂的比色测定法,方法简便、准确、灵敏度高,可川于现场检测。本文还报道了应用本法测定了水中微量肼和甲基肼的稳定性的结果。     

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.     

Application of an environmental impact assessment methodology to a site discharging low levels of radioactivity to a freshwater environment in Norway

Significant shifts in opinion regarding environmental protection from ionising radiation have resulted in the development and availability of bespoke approaches for the assessment of impacts on wildlife from radioactive contaminants. The application of such assessment methodologies to actual situations, however, remains relatively limited. This paper describes the implementation of the ERICA Integrated Approach and associated tools within the context of routine discharges of radioactive materials to a freshwater environment. The article follows the implementation through its relevant stages and discusses strengths and weaknesses of the approach in relation to the case study. For current discharge levels, ¹³⁷Cs and ⁶⁰Co constitute the main dose contributors to the majority of reference organisms studied, although ²⁴¹Am and ³H are the main contributors for the phyto- and zooplankton categories. Patterns are observed depending on whether the reference organism is sediment-associated or not. At current discharge levels, none of the reference organisms exceeded or approached the selected screening level, and impacts on biota could be regarded as negligible.     

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.