100 years of radionuclide metrology.

The discipline of radionuclide metrology at national standards institutes started in 1913 with the certification by Curie, Rutherford and Meyer of the first primary standards of radium. In early years, radium was a valuable commodity and the aim of the standards was largely to facilitate trade. The focus later changed to providing standards for the new wide range of radionuclides, so that radioactivity could be used for healthcare and industrial applications while minimising the risk to patients, workers and the environment. National measurement institutes responded to the changing demands by developing new techniques for realising primary standards of radioactivity. Looking ahead, there are likely to be demands for standards for new radionuclides used in nuclear medicine, an expansion of the scope of the field into quantitative imaging to facilitate accurate patient dosimetry for nuclear medicine, and an increasing need for accurate standards for radioactive waste management and nuclear forensics.

Results of an EC laboratory comparison on 4°K, 9°Sr and ¹³7Cs in dried bilberry powder.

The evaluation is presented of a laboratory comparison (LC) on (90)Sr, (40)K and (137)Cs in dried bilberries organised in 2011 by the IRMM. The activity concentrations reported by 88 participant laboratories are compared to the reference values of the new reference material IRMM-426 Wild Berries. Nine per cent and 17% of activity concentration results for (137)Cs and (40)K, respectively, deviate more than 20% from the reference values, a result worse than that obtained in previous LCs. For (90)Sr, about 88% of results lie within 30% of the reference value, better than observed in previous LCs. But only 58% of (90)Sr results are satisfactory in terms of the En criterion, indicating difficulties with a complete uncertainty estimation.

Certification of the reference material IRMM-426 for radionuclides in dried bilberries.

A new reference material for the activity concentration of (137)Cs, (40)K and (90)Sr in a dried berry matrix was certified from a batch of bilberries collected in the vicinity of the Chernobyl nuclear power plant. Radionuclides in this material were metabolised by the plants, therefore no spiking had to be performed. The material was processed at IRMM and homogeneity and stability of the certified parameters were demonstrated. The certified property values for (137)Cs, (40)K and (90)Sr were determined in the course of a supplementary comparison, CCRI(II)-S8.

Critical remarks on gross alpha/beta activity analysis in drinking waters: conclusions from a European interlaboratory comparison.

The most common gross alpha/beta standard methods used for drinking water analysis are discussed, and sources of interferences are reviewed from a metrological point of view. Our study reveals serious drawbacks of gross methods on the basis of an interlaboratory comparison analyzing commercial mineral water samples with the participation of 71 laboratories. A proposal is made to obtain comparable measurement results using true standardized methods.

"Realisation of the becquerel"--reducing the impact of equipment failure.

The goal of the CCRI(II) "Realisation of the becquerel" project is to design a reproducible radioactivity standard which will increase the robustness of the current international reference system for radioactivity measurements. Tests performed with a first prototype ionisation chamber of this project, built in 2005, are presented. Based on experience with the first prototype, a new design was proposed in 2010 aiming at achieving the very ambitious project goals. The article discusses the status of the project and the advantages of the new design.

Results of an international comparison for the determination of radionuclide activity in bilberry material.

Radioactivity found in wild food products has assumed greater importance when assessing the total exposure of the population. For this reason, IRMM has been developing a reference material for the activity concentration of three radionuclides in bilberry samples. In order to characterise this new material, a CCRI(II) supplementary comparison was organised. The difficulties encountered in this comparison are discussed, in particular the efficiency calibration for volume sources of gamma-ray emitters, and comparison reference values for (137)Cs and (40)K are calculated.

Determination of natural and anthropogenic radionuclides in soil--results of an European Union comparison.

A comparison was organised by the Institute for Reference Materials and Measurements (IRMM) among 73 environmental radioactivity monitoring laboratories for the determination of 15 radionuclides in soil. The reference material IAEA-375 soil was reprocessed to provide the comparison material and reference values traceable to SI units and SIR were established at IRMM. The analytical procedures used by participants laboratories are discussed and performances evaluted using relative deviations and E(n) numbers. This paper focuses on the results for (40)K, (90)Sr, (137)Cs, (226)Ra, (234)U, (235)U and (238)U. Worst performance was found for (90)Sr and (235)U, where 65% and 78% of the results, respectively, deviate more than 20% from the reference values. The use of the E(n) criterion revealed that the uncertainty estimation of many participants is poor.

226Ra and 228Ra determination in mineral waters--comparison of methods.

A comparison of different radiochemical separation procedures and measurement techniques used to determine the activity concentration of (226)Ra and (228)Ra in water is made with respect to accuracy, detection limits and turn-around time. Radium-226 activity concentration was determined by the radon emanation technique, alpha-particle and gamma-ray spectrometry. To determine the (228)Ra activity concentration, four different techniques were used: low-level liquid scintillation counting, low-level proportional counting, alpha-particle and low-level gamma-ray spectrometry.

EC comparison on the determination of 226Ra, 228Ra, 234U and 238U in water among European monitoring laboratories.

In anticipation of new European requirements for monitoring radioactivity concentration in drinking water, IRMM organized an interlaboratory comparison on the determination of low levels of activity concentrations (about 10-100 mBq L(-1)) of the naturally occurring radionuclides (226)Ra, (228)Ra, (234)U and (238)U in three commercially available mineral waters. Using two or three different methods with traceability to the International System of Reference (SIR), the reference values of the water samples were determined prior to the proficiency test within combined standard uncertainties of the order of 3%-10%. An overview of radiochemical separation and measurement methods used by the 45 participating laboratories are given. The results of the participants are evaluated versus the reference values. Several of the participants' results deviate by more than a factor of two from the reference values, in particular for the radium isotopes. Such erroneous analysis results may lead to a crucial omission of remedial actions on drinking water supplies or to economic loss by an unjustified action.

Sequential determination of 210Po and uranium radioisotopes in drinking water by alpha-particle spectrometry.

Procedures for the sequential determination of low level (210)Po and uranium radioisotopes in drinking water by alpha-particle spectrometry are presented. After addition of (208)Po and (232)U tracers, the radionuclides were preconcentrated from water samples by co-precipitation on Fe(OH)(3) or MnO(2) at pH 9 using ammonia solution. The (210)Po source was prepared by spontaneous deposition onto a copper disc either before or after uranium separation. The uranium source for alpha-particle counting was prepared by micro co-precipitation with CeF(3). The procedures were tested on mineral water and the results obtained are compared.

Measurement comparisons of radioactivity among European monitoring laboratories for the environment and food stuff.

For more than 15 years, European Union (EU) laboratories monitoring environmental radioactivity have been obliged to participate in measurement comparisons organised by the European Commission. After a short review of comparisons conducted during the 1990s, the approach of IRMM organising these comparisons since 2003 is presented. It relies on the provision of comparison samples with reference values traceable to the International Reference System for radionuclides (SIR). The results of the most recent comparison, the determination of (40)K, (90)Sr and (137)Cs in milk powder, are presented. The influence of repetitive participation in measurement comparisons on laboratory performance is studied on the basis of data from more than 20 laboratories having participated in several exercises during the last 15 years.

EC intercomparisons for laboratories monitoring environmental radioactivity.

International measurement comparisons are organised regularly for EU laboratories involved in monitoring radioactivity, with emphasis on meeting routine measurement conditions. Using the recent comparison of 137Cs in air filters as an example, the whole cycle is described: establishment of traceable reference values, spiking of individual filters for the comparison and their quality assurance, treatment and measurement of filters in the participating laboratories and evaluation of comparison results. The treatment of an individual result, deviating widely from the reference value, is discussed. Monte-Carlo simulations allow to estimate the maximum errors possibly made due to a non-suitable measurement geometry.

Analyte transport efficiencies in electrothermal vaporization for inductively coupled plasma mass spectrometry.

A modified graphite furnace for solid-sampling atomic absorption spectrometry as an electrothermal vaporizer (ETV) was coupled to a Perkin-Elmer/Sciex ELAN 6000 ICP mass spectrometer. The integrals obtained from electrothermal vaporization of aliquots containing As, Cd, Cu, Co, Fe, Mn, Pb, Se, and Zn were compared with those obtained from pneumatic nebulization of the same aqueous standard solution. The pneumatic nebulizer was calibrated by weighing the mass of aqueous aerosol trapped on a filter. With "wet plasma" conditions maintained also for measurements with the ETV and reference signals for analyte signals obtained with the calibrated pneumatic nebulization, the transport efficiency of the ETV system, e.g. the ratio of the analyte amount introduced into the plasma to that amount dosed into the vaporizer, was determined. The transport efficiency of two different tube and interface designs has been evaluated. Investigations with and without the use of trifluoromethane as reactive gas, with different furnace heating rates, and with varying gas flows were performed. In general, the tube equipped with a nozzle led to generally higher transport efficiency than the standard tube. Without trifluoromethane transport efficiencies ranged from 10% to 35% with the standard tube and from 15% to 50% with the nozzle-type tube. With addition of 2 mL min(-1) trifluoromethane to the argon flow of 400 mL min(-1) through the tube, transport efficiencies from 20% to 70% and from 70% to 100% were achieved with the standard and nozzle-type tubes, respectively.

Development of an electrothermal vaporization ICP-MS method and assessment of its applicability to studies of the homogeneity of reference materials.

A method has been developed for measurement of the homogeneity of analyte distribution in powdered materials by use of electrothermal vaporization with inductively coupled plasma mass spectrometric (ETV-ICP-MS) detection. The method enabled the simultaneous determination of As, Cd, Cu, Fe, Mn, Pb, and Zn in milligram amounts of samples of biological origin. The optimized conditions comprised a high plasma power of 1,500 W, reduced aerosol transport flow, and heating ramps below 300 degrees C s(-1). A temperature ramp to 550 degrees C ensured effective pyrolysis of approximately 70% of the organic compounds without losses of analyte. An additional hold stage at 700 degrees C led to separation of most of the analyte signals from the evaporation of carbonaceous matrix compounds. The effect of time resolution of signal acquisition on the precision of the ETV measurements was investigated. An increase in the number of masses monitored up to 20 is possible with not more than 1% additional relative standard deviation of results caused by limited temporal resolution of the transient signals. Recording of signals from the nebulization of aqueous standards in each sample run enabled correction for drift of the sensitivity of the ETV-ICP-MS instrument. The applicability of the developed method to homogeneity studies was assessed by use of four certified reference materials. According to the best repeatability observed in these sample runs, the maximum contribution of the method to the standard deviation is approximately 5% to 6% for all the elements investigated.

Contribution of ICP-IDMS to the certification of antimony implanted in a silicon wafer--comparison with RBS and INAA results.

A thin-layer reference material for surface and near-surface analytical methods was produced and certified. The surface density of the implanted Sb layer was determined by Rutherford backscattering spectrometry (RBS), instrumental neutron activation analysis (INAA), and inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) equipped with a multi-collector. The isotopic abundances of Sb (121Sb and 123Sb) were determined by multi-collector ICP-MS and INAA. ICP-IDMS measurements are discussed in detail in this paper. All methods produced values traceable to the SI and are accompanied by a complete uncertainty budget. The homogeneity of the material was measured with RBS. From these measurements the standard uncertainty due to possible inhomogeneities was estimated to be less than 0.78% for fractions of the area increments down to 0.75 mm2 in size. Excellent agreement between the results of the three different methods was found. For the surface density of implanted Sb atoms the unweighted mean value of the means of four data sets is 4.81 x 10(16) cm(-2) with an expanded uncertainty (coverage factor k = 2) of 0.09 x 10(16) cm(-2). For the isotope amount ratio R (121Sb/123Sb) the unweighted mean value of the means of two data sets is 1.435 with an expanded uncertainty (coverage factor k = 2) of 0.006.