EXPERIMENTAL AND COMPUTATIONAL EVALUATION OF EFFECTIVE CENTRE FROM A LONG COUNTER AT NEUTRON METROLOGY LABORATORY IN BRAZIL.

A long counter detector was manufactured by the Institute of Advanced Studies (IEAV) and was characterised in the neutron low scattering room at Brazilian National Ionising Radiation Metrology Laboratory (LNMRI/IRD) to deploy a secondary Standard for neutron fluence. The effective centre was measured experimentally with 252Cf+D2O, 252Cf, 241AmBe and 238PuBe neutron sources, having average energies from 0.55 to 4.16 MeV. The experimental arrangement and detector construction were carefully reproduced in Monte Carlo simulations, and the computational results were found to be in good agreement with those from experiment.

REFERENCE NEUTRON FIELDS IN CALIBRATION LABORATORY; SIMPLE DOSIMETRIC PARAMETERS AND THEIR CHANGES IN TIME.

The calibration laboratory revises periodically the dosimetric properties of its calibration fields. For reference neutron fields based on radionuclide sources, it is due to presence of isotopic impurities in the source ingredients. Consequently, in long term, the admixtures and their decay products become significant. Neglecting the impact of such effect leads to inconsistencies between the neutron emission rate observed during the measurements and the emission rate derived from the decay curve of the main isotope. In the Radiation Protection Measurements Laboratory at the National Centre for Nuclear Research the neutron fields of the bare sources of 252Cf, 241AmBe and 239PuBe have been examined for nearly 30 years, regularly, in fixed geometry. Additionally, at the particular point of a calibration bench, determination of neutron fluence rate, ambient dose equivalent rate and its scattered component, total neutron and gamma dose rate, gamma to total dose ratio, radiation quality factor and total tissue kerma are occasionally determined. In this article, we would like to present recently achieved results and their comparison with the measurement data formerly presented. The growth of the neutron emission of 239PuBe source, as well as discrepancies between the decay curves of relevant isotopes and the emission rate of 252Cf and 241AmBe will be presented.

A rapid method for estimation of Pu-isotopes in urine samples using high volume centrifuge.

The conventional radio-analytical technique used for estimation of Pu-isotopes in urine samples involves anion exchange/TEVA column separation followed by alpha spectrometry. This sequence of analysis consumes nearly 3-4 days for completion. Many a times excreta analysis results are required urgently, particularly under repeat and incidental/emergency situations. Therefore, there is need to reduce the analysis time for the estimation of Pu-isotopes in bioassay samples. This paper gives the details of standardization of a rapid method for estimation of Pu-isotopes in urine samples using multi-purpose centrifuge, TEVA resin followed by alpha spectrometry. The rapid method involves oxidation of urine samples, co-precipitation of plutonium along with calcium phosphate followed by sample preparation using high volume centrifuge and separation of Pu using TEVA resin. Pu-fraction was electrodeposited and activity estimated using 236Pu tracer recovery by alpha spectrometry. Ten routine urine samples of radiation workers were analyzed and consistent radiochemical tracer recovery was obtained in the range 47-88% with a mean and standard deviation of 64.4% and 11.3% respectively. With this newly standardized technique, the whole analytical procedure is completed within 9h (one working day hour).

Certified reference materials and reference methods for nuclear safeguards and security.

Confidence in comparability and reliability of measurement results in nuclear material and environmental sample analysis are established via certified reference materials (CRMs), reference measurements, and inter-laboratory comparisons (ILCs). Increased needs for quality control tools in proliferation resistance, environmental sample analysis, development of measurement capabilities over the years and progress in modern analytical techniques are the main reasons for the development of new reference materials and reference methods for nuclear safeguards and security. The Institute for Reference Materials and Measurements (IRMM) prepares and certifices large quantities of the so-called "large-sized dried" (LSD) spikes for accurate measurement of the uranium and plutonium content in dissolved nuclear fuel solutions by isotope dilution mass spectrometry (IDMS) and also develops particle reference materials applied for the detection of nuclear signatures in environmental samples. IRMM is currently replacing some of its exhausted stocks of CRMs with new ones whose specifications are up-to-date and tailored for the demands of modern analytical techniques. Some of the existing materials will be re-measured to improve the uncertainties associated with their certified values, and to enable laboratories to reduce their combined measurement uncertainty. Safeguards involve the quantitative verification by independent measurements so that no nuclear material is diverted from its intended peaceful use. Safeguards authorities pay particular attention to plutonium and the uranium isotope (235)U, indicating the so-called 'enrichment', in nuclear material and in environmental samples. In addition to the verification of the major ratios, n((235)U)/n((238)U) and n((240)Pu)/n((239)Pu), the minor ratios of the less abundant uranium and plutonium isotopes contain valuable information about the origin and the 'history' of material used for commercial or possibly clandestine purposes, and have therefore reached high level of attention for safeguards authorities. Furthermore, IRMM initiated and coordinated the development of a Modified Total Evaporation (MTE) technique for accurate abundance ratio measurements of the "minor" isotope-amount ratios of uranium and plutonium in nuclear material and, in combination with a multi-dynamic measurement technique and filament carburization, in environmental samples. Currently IRMM is engaged in a study on the development of plutonium reference materials for "age dating", i.e. determination of the time elapsed since the last separation of plutonium from its daughter nuclides. The decay of a radioactive parent isotope and the build-up of a corresponding amount of daughter nuclide serve as chronometer to calculate the age of a nuclear material. There are no such certified reference materials available yet.

Preparation of proton rich radionuclides in support of radiochemical analysis.

The production of proton rich radionuclides supports a wide range of radiochemical analyses via radioactive yield tracers ((95m)Tc and (236)Pu). In recent years, NPL and the University of Birmingham cyclotron have collaborated to produce these, and other, radionuclides.

Absolute standardization of 241Pu by the TDCR technique and effect of the beta spectral shape.

The NMISA participated in the 2010 international key comparison of (241)Pu, standardizing the inter-comparison solution by the TDCR efficiency calculation technique. Special attention was paid to ensure accurate efficiency calculation for this low-energy, pure beta-emitter: in particular the effect of low-energy stopping powers on the calculation of ionization quenching was assessed and an optimal value for the quench parameter, kB, was determined. In addition, phototube efficiency mismatch was accounted for by a software minimization technique. The effect of the beta spectral shape on the activity extracted from data analysis was assessed and found to be significant. Based on the results of this work we propose a new value for the average beta-particle energy.

Determination of plutonium isotopes in seawater reference materials using isotope-dilution ICP-MS.

We analyzed the activities of (239)Pu, (240)Pu, (239+240)Pu, (241)Pu, the ratio of number of atoms (atom ratio) for (240)Pu/(239)Pu, and the activity ratio of (241)Pu/(239+240)Pu in seawater reference materials, IAEA-443 and IAEA-381, using a highly sensitive isotope dilution sector field inductively coupled plasma mass spectrometry method. With a mean chemical yield of 65% determined with (242)Pu as a tracer, we found that the experimentally established values in IAEA-443 for (239)Pu, (240)Pu, (241)Pu and (239+240)Pu activities are almost the same as those in IAEA-381. Regarding the (239+240)Pu activity, we provided the most precise and accurate result among the twelve laboratories, which participated in the interlaboratory comparison. In addition, for the (240)Pu/(239)Pu atom ratio, our results for IAEA-381 (0.2315±0.0008) and IAEA-443 (0.2325±0.0008) are in good agreement with the IAEA information value (0.229±0.006), but have much smaller uncertainty. Since the new seawater reference material, IAEA-443, is commercially available, it can be used not only for method validation for seawater plutonium isotope ratio and activity analysis, but also for more general use as a plutonium isotope standard for mass discrimination correction for other environmental samples.

Ultra-low level plutonium isotopes in the NIST SRM 4355A (Peruvian Soil-1).

For more than 20 years, countries and their agencies which monitor radionuclide discharge sites and storage facilities have relied on the National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) 4355 Peruvian Soil. Its low fallout contamination makes it an ideal soil blank for measurements associated with terrestrial-pathway-to-man studies. Presently, SRM 4355 is out of stock, and a new batch of the Peruvian soil is currently under development as future NIST SRM 4355A. Both environmental radioanalytical laboratories and mass spectrometry communities will benefit from the use of this SRM. The former must assess their laboratory procedural contamination and measurement detection limits by measurement of blank sample material. The Peruvian Soil is so low in anthropogenic radionuclide content that it is a suitable virtual blank. On the other hand, mass spectrometric laboratories have high sensitivity instruments that are capable of quantitative isotopic measurements at low plutonium levels in the SRM 4355 (first Peruvian Soil SRM) that provided the mass spectrometric community with the calibration, quality control, and testing material needed for methods development and legal defensibility. The quantification of the ultra-low plutonium content in the SRM 4355A was a considerable challenge for the mass spectrometric laboratories. Careful blank control and correction, isobaric interferences, instrument stability, peak assessment, and detection assessment were necessary. Furthermore, a systematic statistical evaluation of the measurement results and considerable discussions with the mass spectroscopy metrologists were needed to derive the certified values and uncertainties. The one sided upper limit of the 95% tolerance with 95% confidence for the massic (239)Pu content in SRM 4355A is estimated to be 54,000 atoms/g.

Spectrophotometric determination of plutonium in highly radioactive liquid waste using an internal standardization technique with neodymium(III).

A simple and rapid spectrophotometric method has been developed for the determination of Pu in highly radioactive liquid waste. This method uses Nd(III) as an internal standard, which enables us to determine the concentration of Pu and to authenticate the whole analytical scheme as well. A Nd(III) standard mixed with a sample solution and Pu was quantitatively oxidized to Pu(VI) with Ce(IV) in a nitric acid medium, having the maximum absorbance at 830 nm. A spectrophotometric measurement of Pu(VI) was subsequently performed to determine the concentration compared with the maximum absorbance of Nd(III) at 795 nm. It was estimated that the relative expanded uncertainty for a real sample is less than 10%. The limit of detection was calculated to be 1.8 mg/L (3 sigma). The proposed method was also validated through comparison experiments with isotope dilution mass spectrometry, and was successfully applied to analysis for nuclear waste management at spent nuclear fuel reprocessing plants.

Preparation and activity measurement of electrodeposited alpha-emitting sources.

Alpha-emitting 238Pu and 241Am sources on stainless steel substrates have been prepared using a new electrodeposition method based on an ammonium oxalate-ammonium sulfate electrolyte containing diethyl triamino pentaacetic acid. The deposition yield is determined by measuring the activity of the sources using a high-efficiency 2pi alpha proportional counter and a backscattering chamber designed and fabricated for this purpose. Optimal electrodeposition parameters have been determined for 241Am, enabling manufacture of standard alpha-emitting sources with minimal radioactive waste.

Standardization of 125I and 238Pu.

A simple distance-variable detection table on which two detectors can be mounted and moved back and forth facing each other centred on a sample source has been constructed for photon-photon and alpha-photon coincidence counting for 125I and 238Pu, respectively. Two NaI(Tl) detectors were used for the standardization of 125I. A Si detector and an NaI(Tl) detector were employed for the standardization of 238Pu. The NaI(Tl) detectors have a very thin aluminium window for measuring low-energy photons from 125I and 238Pu while the Si-detector is a usable-in-air ion-implanted detector for alpha particles from 238Pu. A thin collodion film was used for 238Pu samples, whereas a thick polyester film was used for 125I samples to prevent 125I from leaking from the sample. The key comparison result of 125I showed good agreement, and the result of 238Pu was also compared with that of liquid scintillation counting.

Results of the international Pu-2000 exercise for plutonium isotopic composition measurements.

An international comparison for plutonium isotopic composition measurement, known as the Pu-2000 exercise, was organized by the ESARDA NDA-WG (European Safeguards Research and Development Association, Working Group on Techniques and Standards for Non-Destructive Assay). The aim of this comparison was to test X- and gamma-ray spectrometry methods over a large range of isotopic ratios. These methods are based on the complex analysis of several X- and gamma-rays in the KX region of the plutonium spectrum and also in the 120-700 keV energy range. The results obtained by the participants with their corresponding uncertainties are presented in this document and compared to the declared values. The main conclusions of the work are also given. No important bias due to an inadequate knowledge of the nuclear data for plutonium isotopes was observed.

Determination of pu isotopes in seawater by an on-line sequential injection technique with sector field inductively coupled plasma mass spectrometry.

An on-line sequential injection (SI) system combined with sector field inductively coupled plasma mass spectrometry was developed for the determination of ultratrace level 239Pu and 240Pu in seawater. The potential of this method is the substantial reduction of a sample volume and rapidity in the determination of Pu isotopes. A chemical purification and preconcentration of Pu isotopes were accomplished by the on-line SI system with two microcolumns of solid-phase extraction resins, Sr-Spec and TEVA-Spec. The MCN-6000 microconcentric nebulizer was used as a sample introduction system because of low interference effect and good sample utilization. With this method, it was possible to analyze ultratrace levels of Pu isotopes in only 5 L of surface seawater with an analysis speed of 4 h/sample. The precision of the measurement for the 239Pu and 240Pu was less than 3.4 (n = 7) and 5% (n = 7) for 5 L of seawater. The detection limits for 239Pu and 240Pu were 0.64 (1.5 microBq/mL) and 0.19 fg/mL (1.6 microBq/mL), respectively. The accuracy of this method was verified by using the reference seawater (IAEA-381) as well as by the comparison with the a-spectrometry.