Atomic spectrometry for trace determinations in the environment with a view to government regulations

Governments and international organizations have a continuous need for information on levels of environmental pollution for two main reasons: 1. Limit values, given in regulations or directives have to be checked regularly. 2. General levels of pollutants have to be known in order to determine systematic changes (trends) and to be able to establish sources of pollution. Of course data from analytical programmes must be accurate and comparable to the results from other programmes. In most regulations and directives, however, analytical methods and - even more important - sampling, are very briefly specified. Analytical quality is therefore essential. The needed comparability and accuracy of the analysis of trace elements by atomic spectrometric methods is discussed, giving attention to interlaboratory comparison programmes, standardization of methods and the use of standard reference samples. Specific examples are presented, dealing with trace element analysis in different parts of the environment : 1. Sampling and analysis of hazardous waste and sewage sludge in relation to national and international regulations. 2. Representativity of sampling for the analysis of surface waters (including suspended matter) and sediments. 3. Sampling and analysis of suspended particulate matter (dust) in air, especially for lead and sulphur.     

Hydrogen Transport in Non‐Ideal Crystalline Materials

Hydrogen‐transport behaviour under (non‐)isothermal conditions is discussed. An extended modelling approach based on the effective diffusion coefficient is outlined for arbitrary temperature programmes, defect properties and hydrogen‐loading pressures. The influence of mathematical terms, such as the trap equilibrium reaction or microstructural changes, is critically discussed and examples of thermal desorption spectra and isothermal diffusion behaviour are given.     

Transfer of radiation technology to developing countries

Transfer of technology is a complex process with many facets, options and constraints. While the concept is an important step in bringing industrialization process to agricultural based countries, it is clear, however, that a country will only benefit from a new technology if it addresses a real need, and if it can be absorbed and adapted to suit the existing cultural and technological base.

International Atomic Energy Agency, as UN body, has a mandate to promote nuclear applicationsand assist Member States in transfer of technology for peaceful applications. This mandate has been pursued by many different mechanisms developed in the past years: technical assistance, coordinated research programmes, scientific and technical meetings, publications, etc. In all these activities the Agency is the organizer and initiator, but main contributions come from expert services from developed countries and, increasingly, from developing countries themselves. The technical cooperation among developing coutries more and more becomes part of different programmes.

In particular, regional cooperation has been demonstrated as an effective instrument for transfer of technology from developed and among developing countries.

Some examples of actual programmes are given.     

Procedes nouveaux de traitement par ordinateur de spectres gamma

The author remarks upon the detailed technique described in an article published in the Nuclear Instruments and Methods. He tries to explain the variety of the gamma-spectrometry programmes. Then the original points of his work is given. These are as follows: criteria of the automatic investigation of the peaks, grouping of the multiplets, the nature of the parameters of the functions to be adjusted, the presentation of the results.      

Statistical model for assessing the quality and cost of inspection procedures in forensic and environmental analysis.

Legal regulations on the composition and safety of food products require inspection programmes to maintain the standards required or to obtain an insight in the real situation. Such programmes consist of a sampling procedure followed by analysis of the samples. When monitoring environmental contamination similar programmes are required. When large numbers of samples have to be analysed in order to monitor contaminants in either environmental or food-chain samples, and the majority fulfil the legal requirements, a two-stage control system is desirable. Firstly, samples are analysed by a simple 'screening method', to sift out the large number of samples that fulfil the requirements (negative results). The minority not fulfilling the requirements (positive results) are investigated further by a more sophisticated confirmatory method, specific for the analyte(s) of interest, for an ultimate judgement. For this type of inspection a simple model is used in this study, in order to calculate the fraction of false negative results in the final decision. It is assumed, that, when the quality criteria for the confirmatory method are appropriate, the fraction of false positive results is negligibly small. The quality of the inspection is expressed in terms of the fraction f of false negative results with respect to the real positive samples and is related to labour and costs. In an example given, the costs of analysing 40,000 samples with f = 6.6% are ecu 7,800,000. Improving f down to 3.2% creates additional costs of ecu 16,000,000. The proposed model might not be sufficiently realistic, but more realistic models can be implemented.(ABSTRACT TRUNCATED AT 250 WORDS)     

Radiochemistry in chemistry and chemistry related undergraduate programmes in Argentina

Summary The evolution of education in Argentina at the university level is described. The detailed search of the educational offer shows that less than half of the universities (35 out of 92) include chemistry and chemistry related undergraduate programmes in their curriculum. The revision of the position of radiochemistry in these programmes reveals that only seven courses on radiochemistry are currently offered. Radiochemistry is included only in few programmes in chemistry and biochemistry. With respect to the programmes in chemical engineering the situation is worse. This offer is strongly concentrated in Buenos Aires and its surroundings.     

IAEA analytical quality assurance programmes to meet the present and future needs of developing countries

For many years the International Atomic Energy Agency (IAEA) has been promoting analytical quality assurance and quality control in its Member States with emphasis on measurands that are amenable to analysis by nuclear and related techniques, i.e. radionuclides, trace elements, and stable isotopes. This paper reviews briefly the rationale for some of these activities, particularly in relation to the needs of participants in developing countries arising out of co-ordinated research programmes, technical co-operation projects and global and regional networks. Emphasis is given to biological and environmental reference materials with a matrix of natural origin. Also described are some activities arising out of the requirements of ISO-25 and other relevant international quality standards.     

Requirements for screening and confirmatory methods for the detection and quantification of marine biotoxins in end-product and official control

An overview is given of the biological origin of phycotoxins, as well as their chemical characteristics. Major poisoning types are described and examples of poisoning events are given to illustrate the importance of the phenomenon to both shellfish consumers and the shellfish producing industry. The characteristics of phycotoxins as natural products, the lack of predictability of their occurrence, economic drivers and the freshness of shellfish consumed in many countries result in a number of requirements for methods to be used in the efficient detection of these compounds. Subsequently, the performance of mouse bioassays and mass spectrometry as detection tools are compared for examples from Irish and French monitoring programmes to assess the usefulness of qualitative and quantitative tools in official control, and their fitness for purpose compared with the requirements. The final part of the paper critically reviews methods available for the end-product and official control of shellfish toxins and their use in screening and confirmatory approaches in monitoring. Recent expert consultations on the methodology for phycotoxins at European and global level are summarised and recommendations are made for future progress in this area.     

Computer programmes for representing mass spectra on a computer plotter

The Fortran IV programmes have been written for plotting mass spectra on a Calcomp 565 plotter. The spectra can be displayed sequentially or one on top of the other. One of the programmes also calculates relative abundance and percent sigma for each peak, and possible origins for metastable peaks.     

Trace-level determination of pesticides in water by means of liquid and gas chromatography

The trace-level determination of pesticides and their transformation products (TPs) in water by means of liquid and gas chromatography (LC and GC) is reviewed. Special attention is given to the use of (tandem) mass spectrometry for identification and confirmation purposes. The complementarity of LC- and GC-based techniques and the potential of comprehensive GC×GC are discussed, and also the impressive performance of time-of-flight mass spectrometry. It is also indicated that, in the near future, the TPs rather than the parent compounds should receive most attention—with a better understanding of matrix effects and eluent composition on the ionization efficiency of analytes being urgently required. Finally, the merits of using much shorter LC columns, or even no column at all (flow-injection analysis) in target analysis are shown, and a more cost-efficient and sophisticated strategy for monitoring programmes is briefly introduced.     

Harmonisation Of Ec Air Quality Directives

Abstract

The Environment Institute of the Joint Research Centre in Ispra devotes an important part of its activities to support the Commission of the European Communities in scientific and technical matters. As an example of these activities, a general overview is given of the harmonisation work lead by its Central Laboratory of Air Pollution for the implementation of EC air quality directives in the European Member States. The different stages of a directive's development are reviewed and illustrated with typical examples of harmonisation work recently undertaken.

Preparatory actions for future regulations are illustrated by the recent intercomparison exercise for VOC measurements, realized in view of the coming directive on photo-oxidants.

Quality assurance programmes are developed that are mainly focused on the evaluation of sampling, calibration and measurement techniques in the Member States. Special attention is also paid to the harmonisation of network design. The results of a recent network design campaign realised in Madrid, using passive sampling techniques in combination with mobile measurements, are presented.

An example of the development of scientific and technical progress is given by the intercomparison of primary NO₂ calibration standards, where the reference method of the directive was checked and compared to new standard methods.     

Current status of nuclear science education and training in India

Nuclear science and education and training programmes conducted by the Department of Atomic Energy of India are described. The programmes have helped not only the basic research in nuclear science but also in the application of sophisticated technology in a wide variety of areas.     

Monitoring performance of nucleic acid-based diagnostic measurement system users by EQA

External quality assurance (EQA) programmes allow a laboratory to monitor independently its performance and provide feedback to identify and investigate potential areas of concern. However, both the definition of appropriate ‘performance indicators’ and their statistical analysis vary across EQA providers. Typically, performance scores have an unknown statistical distribution and hence arbitrary thresholds are used to measure performance. In this paper, we introduce a scoring system based on well-known statistical principles. The system is simple, flexible and easy to interpret. It can be used to measure performance for single samples or across a panel so providing useful and meaningful information to participants in EQA programmes. The score is illustrated using the 2005 QCMD Hepatitis B Virus Proficiency programme.     

Inorganic chemical fingerprinting of the environment: “reference freshwater” — a useful tool for comparison and harmonization of analytical data in freshwater chemistry

An enormous amount of information about the state of the environment is being created in many programmes worldwide. Optimum use of this data requires, beside a high degree of quality control, a basis for comparability of single analytical values. This requirement is already fulfilled within the programmes, but more or less neglected between international programmes (Keune et al. [9]). The establishment of a synthetic “reference freshwater” can be a useful tool for the harmonization of environmental measurement. After normalization of the data measured in different inland water samples versus “reference freshwater”, a chemical fingerprinting of aquatic samples is now possible. In this paper, a fingerprint of Lake Baikal will be discussed and its comparability demonstrated.     

Computer-assisted transfer of programmed elutions in reversed-phase high-performance liquid chromatography

Computer-assisted procedures were used to simulate modifications in chromatograms caused by the transfer of elution programmes between instruments with significantly different dwell volumes. Moreover, for the first time the same approach was used to modify the elution programmes to match the chromatograms produced in the different instruments. The process may consist of making minor modifications to gradient programmes or transforming the original gradient programme into a stepwise gradient profile and/or the simultaneous programming of flow and solvent composition. The combination of these approaches has been shown to have an enormous potential for producing matched chromatograms in instrumental systems with dwell volumes that differ by several millilitres. The efficiency and robustness of the proposed procedure is demonstrated with a variety of compounds (two different mixtures of 10 and 11 analytes), mobile phases (methanol and acetonitrile gradients), flow rates (0.5-1.5 mL/min range), temperatures (35-45 degrees C interval) and gradient profiles (linear, multilinear, curved and stepwise).     

Analytical Intercomparison Exercises and Harmonization within Environmental Laboratories from Developing Countries

Abstract

Since the early 60's, the IAEA implements a Quality Assurance (QA) programme for the Member States. As part of this programme, the IAEA organized more than 150 analytical intercomparison exercises and produced more than 70 Certified Reference Materials for a wide range of determinands, encompassing radionuclides, trace elements, petroleum hydrocarbons, pesticides and PCBs. From the IAEA — Marine Environment Laboratory in Monaco, analytical Quality Assurance services are provided for non-nuclear contaminants in marine materials.

Results of recently organized worldwide intercomparison exercises using the sample materials IAEA-142 (mussel tissue homogenate) and IAEA-140 (seaweed homogenate), show that some progress was achieved worldwide in the analyses of the more common environmental contaminants. However, results also show that difficulties in obtaining accurate data for trace elements and especially for organic contaminants are still widespread, particularly in developing countries. Therefore, the success of international cooperative programmes as well as of many regional environmental monitoring programmes, depends on improved quality and comparability of data which has to be achieved still through reinforced Quality Assurance programmes. To this aim, the IAEA/UNEP/IOC-UNESCO inter-agency programme on marine pollution promotes the adoption of Reference Methods for harmonization of techniques used in developing and developed countries, organizes frequent intercomparison exercises, and produces certified marine Reference Materials which are made available to laboratories worldwide.     

Self-assembled monolayers at electrode metal surfaces

Neutral organic compounds, dissolved in an electrolyte in contact with an electrode, adsorb and form different monolayers which may range from dilute to compact films. In some instances, non-electroactive organic molecules are highly associated and form 2D condensed phases which are characterized by the presence of phase transitions. The occurence of these self-assembled monolayers is discussed on the basis of experimental results obtained at equilibrium as well as under dynamic conditions. Self-assembling depends on the relative magnitude of the interactions involving the surfactant, the solvent and the electrode. Adequate potential-step programmes have been successfully used to trigger the formation of the ordered phase. It is found that the kinetics are controlled by a nucleation and growth mechanism. According to the experimental conditions, a deterministic or stochastic behaviour is observed. The amplitude of the supersaturation, given by the surface free energy gap between the final and metastable states, is independently controlled by the potential, temperature and surfactant concentration. The classical nucleation theory allows the determination of key parameters such as the line tension, the radius and free energy of formation of the critical nucleus. Ion and electron transfer processes through condensed monolayers are also briefly described.     

The multivariate coefficient of variation for comparing serum protein electrophoresis techniques in external quality assessment schemes

External quality assessment (EQA) schemes are national or transnational programmes designed to control the analytical performance of clinical laboratories and to maintain inter-laboratory variability within acceptable limits. In such EQA programmes, participants are usually grouped by the type of assay technique/equipment they use. The coefficient of variation (CV) is a simple tool for comparing the inter-laboratory reproducibility of such techniques: the lower the CV, the better the analytical performance. Serum protein electrophoresis, a laboratory test profile consisting of five fractions (albumin, α ₁, α ₂, β and γ globulins) summing up to 100% of total proteins, can also be assayed in different ways depending on the media or the analytical principle. We propose a multivariate CV for comparing the performance of electrophoretic techniques in EQA, thus extending the univariate CV concept. First, the compositional nature of electrophoretic data requires a one-to-one transformation from the five-dimensional to the four-dimensional space. Next, robust estimations of the mean and the covariance matrix are needed to avoid the effect of outliers. The new approach is illustrated on electrophoretic datasets from the French and Belgian national EQA programmes.     

Comparison of different approaches to the statistical evaluation of proficiency tests

The objective of this study was to compare different z-score calculation for the results from proficiency testing programmes. The comparison was carried out on the data from proficiency tests for four different matrices and for all analytes included in the proficiency testing programmes organised by UKZUZ institute from the year 2005 to 2007. It represented 99 samples (three periods per year and eleven samples distributed in each period); the number of determined analytes was 108 in each period. The total number of investigated data sets was 953. Three different approaches to z-score calculation were compared. The results gave reasonably comparable evaluation in most cases but sometimes UKZUZ method proved to be rather strict. The procedure using the robust average and robust standard deviation calculated according to Algorithm A described in ISO 13528 was found to be the most suitable for matrices and level of measurands in UKZUZ proficiency tests.