A new reference material for radionuclides in the mussel sample from the Mediterranean Sea (IAEA-437)

A new Reference Material (RM) for radionuclides in mussel (Mytilus galloprovincialis) from the Mediterranean Sea (IAEA-437) is described and the results of the certification process are presented. Four radionuclides (⁴⁰K, ²³⁴U, ²³⁸U, and ^239+240Pu) have been certified, and information values on massic activities with 95% confidence intervals are given for nine radionuclides (¹³⁷Cs, ²¹⁰Pb(²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²²⁸Th, ²³⁰Th, ²³²Th, ²³⁵U, and ²⁴¹Am). Results for less frequently reported radionuclides (⁹⁰Sr, ¹²⁹I, ²³⁸Pu, ²³⁹Pu, and ²⁴⁰Pu) are also reported. The RM can be used for quality assurance/quality control of the analysis of radionuclides in mussel samples, for the development and validation of analytical methods and for training purposes. The material is available in 200 g units.     

A certified reference material for radionuclides in the water sample from Irish Sea (IAEA-443)

A new certified reference material (CRM) for radionuclides in sea water from the Irish sea (IAEA-443) is described and the results of the certification process are presented. Ten radionuclides (³H, ⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁴U, ²³⁵U, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am) have been certified, and information values on massic activities with 95% confidence intervals are given for four radionuclides (²³⁰Th, ²³²Th, ²³⁹Pu and ²⁴⁰Pu). Results for less frequently reported radionuclides (⁹⁹Tc, ²²⁸Th, ²³⁷Np and ²⁴¹Pu) are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in water samples, for the development and validation of analytical methods and for training purposes. The material is available in 5 L units from IAEA (http://nucleus.iaea.org/rpst/index.htm).     

Distribution of environmental radionuclides in sediment cores of the Jinheung catchment

Sediment core samples taken from the Jinheung catchment located in the middle of the Korean Peninsula were used to know environmental radionuclide distribution. The grain sizes of the sediment cores were found at depth of about 17 cm suggesting that it might have occurred during a dry period of 1969. The radionuclides, ¹³⁷Cs, ²³⁷Np, ²³⁹Pu, ²⁴⁰Pu, ²³⁴U, ²³⁸U, ²²⁸Th, ²³⁰Th, ²³²Th, were analyzed by sector type ICP-MS and gamma-spectrometry. The Cs and Pu distribution changed with the depth, in which the maximum ranged from 14 to 22 cm. This was due to the high activity of the results of nuclear bomb tests in the air from 1960s and showed different distribution pattern on the soil surface. The average activity ratio of ²⁴⁰Pu/²³⁹Pu and ²³⁷Np/²³⁹Pu was 0.173 and 0.45, respectively. These values were similar to the north hemisphere global fallout ratio of ²⁴⁰Pu/²³⁹Pu (0.18) and ²³⁷Np/²³⁹Pu (0.45). The ²³⁷Np/²³⁹Pu ratio showed a higher value than the global fallout ratio above 14 cm depth. The U, Th and their daughter radionuclides kept secular equilibrium in the sediment core because the average activity ratios were nearly 1.     

Certified reference material for radionuclides in seawater IAEA-381 (Irish Sea Water)

A certified reference material (CRM) for radionuclides in seawater, IAEA-381 (Irish Sea Water), is described and the results of certification are presented. The material has been certified for nine radionuclides (⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁷Np, ²³⁸Pu, ²³⁹Pu,²⁴⁰Pu, ^239,240Pu and ²⁴¹Am). Information on massic activities with the corresponding 95% confidence intervals are given for eight radionuclides (³H, ¹²⁵Sb, ²³⁴U, ²³⁵U, ²³⁶U, ²³⁸U, ²⁴¹Pu and ²⁴⁴Cm). Less reported radionuclides include ⁶⁰Co, ⁹⁹Tc, and ²⁴²Pu. The CRM may be used for quality assurance/quality control of the analysis of radionuclides in environmental water samples, for the development and validation of analytical methods and for training purposes. The material is available from the IAEA in 5 kg units.     

The NIST natural-matrix radionuclide standard reference material program for ocean studies

In 1977, the Low-level Working Group of the International Committee on Radionuclide Metrology met in Boston, MA (USA) to define the characteristics of a new set of environmental radioactivity reference materials. These reference materials were to provide the radiochemist with the same analytical challenges faced when assaying environmental samples. It was decided that radionuclide bearing natural materials should be collected from sites where there had been sufficient time for natural processes to redistribute the various chemically different species of the radionuclides. Over the succeeding years, the National Institute of Standards and Technology (NIST), in cooperation with other highly experienced laboratories, certified and issued a number of these as low-level radioactivity Standard Reference Materials (SRMs) for fission and activation product and actinide concentrations. The experience of certifying these SRMs has given NIST the opportunity to compare radioanalytical methods and learn of their limitations. NIST convened an international workshop in 1994 to define the natural-matrix radionuclide SRM needs for ocean studies. The highest priorities proposed at the workshop were for sediment, shellfish, seaweed, fish flesh and water matrix SRMs certified for mBq per sample concentrations of ⁹⁰ Sr, ¹³⁷ Cs and ²³⁹ Pu + ²⁴⁰ Pu. The most recent low-level environmental radionuclide SRM issued by NIST, Ocean Sediment (SRM 4357) has certified and uncertified values for the following 22 radionuclides: ⁴⁰ K, ⁹⁰ Sr, ¹²⁹ I, ¹³⁷ Cs, ¹⁵⁵ Eu, ²¹⁰ Pb, ²¹⁰ Po, ²¹² Pb, ²¹⁴ Bi, ²²⁶ Ra, ²²⁸ Ra, ²²⁸ Th, ²³⁰ Th, ²³² Th, ²³⁴ U, ²³⁵ U, ²³⁷ Np, ²³⁸ U, ²³⁸ Pu, ²³⁹ Pu + ²⁴⁰ Pu, and ²⁴¹ Am. The uncertainties for a number of the certified radionuclides are non-symmetrical and relatively large because of the non-normal distribution of reported values. NIST is continuing its efforts to provide the ocean studies community with additional natural matrix radionuclide SRMs. The freeze-dried shellfish flesh matrix has been prepared and recently sent to participating laboratories for analysis and we anticipate receiving radioanalytical results in 2000. The research and development work at NIST produce well characterized SRMs that provide the world's environment-studies community with an important foundation component for radionuclide metrology.     

Age determination of plutonium using inductively coupled plasma mass spectrometry

The age of plutonium is defined as the time since the last separation of the plutonium isotopes from their daughter nuclides. In this paper, a method for age determination based on analysis of ²⁴¹Pu/²⁴¹Am and ²⁴⁰Pu/²³⁶Pu using ICP-SFMS is described. Separation of Pu and Am was performed using a solid phase extraction procedure including UTEVA, TEVA, TRU and Ln-resins. The procedure provided separation factors adequate for this purpose. Age determinations were performed on two plutonium reference solutions from the Institute for Reference Materials and Measurements, IRMM081 (²³⁹Pu) and IRMM083 (²⁴⁰Pu), on sediment from the Marshall Islands (reference material IAEA367) and on soil from the Trinity test site (Trinitite). The measured ages based on the ²⁴¹Am/²⁴¹Pu ratio corresponded well with the time since the last parent-daughter separations of all the materials. The ages derived from the ²³⁶U/²⁴⁰Pu ratio were in agreement for the IRMM materials, but for IAEA367 the determination of ²³⁶U was interfered by tailing from ²³⁸U, and for Trinitite the determined age was biased due to formation of ²³⁶U in the detonation of the “Gadget”.     

Multifarious application of well-type germanium detector

A low-background well-type high-purity germanium detector system, with high counting efficiencies for X-rays and low-energy g-rays, was used to determine several radionuclides of environmental, biomedical, or geological interest. These included ¹²⁵I, ¹²⁹I, ²¹⁰Pb, ²²⁶Ra, ²³⁴Th (daughter of ²³⁸U), ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Am. Methods were devized for their determinations in diverse environmental matrices or under laboratory procedural conditions. Counting efficiencies and minimum detectable activities for each nuclide were determined under the experimental conditions. These methods are being applied to our service analysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemical leaching behavior of237Np from intertidal coastal sediment in the Irish Sea

Chemical leaching experiments of²³⁷Np in the sediments from the Esk Estuary and the Ribble Estuary in the Irish Sea, U. K., have been carried out, in comparison with those of^{239, 240}Pu and²⁴¹Am, to understand the geochemical associations of these long-lived radionuclides with sediment. Experimental results show that partitioning behavior of²³⁷Np is obviously different from those of^{239, 240}Pu and²⁴¹Am.     

The natural radioactivity of Brazilian phosphogypsum

Phosphogypsum is a high volume by-product from the phosphoric acidindustries containing naturally occurring radionuclides. Envisaging the usesof phosphogypsum, a characterization of this material in terms of spatialdistribution of radionuclides was carried out by core samples taken from stacksof two important Brazilian phosphoric acid facilities. Samples were analyzedfor ²³⁸U, ²³⁴U, ²³²Th, ²²⁶Ra, ²²⁸Ra, ²¹⁰Pb and ²¹⁰Po using alpha- and gamma-spectrometryand UV-VIS spectrophotometry. Specific activities of ²³⁸U, ²³⁴U, ²²⁶ Ra and ²¹⁰Po obtained were comparablewith data reported in the phosphogypsum literature, while higher values werefound for ²³² Th and ²²⁸Ra.     

Determination of plutonium and its isotopic ratio in marine sediment samples using quadrupole ICP-MS with the shield torch system under normal plasma conditions

An analytical method for determining ²³⁹Pu and ²⁴⁰Pu in marine sediment samples, which uses quadrupole ICP-MS, was developed in this work. A simple anion-exchange chromatography system was employed for the separation and purification of Pu from the sample matrix. A sufficient decontamination factor of 1.4×10⁴ for U, which interferes with the determination of ²³⁹Pu, was achieved. High sensitivity Pu determination was obtained, which led to an extremely low concentration detection limit of ~8 fg/ml (0.019 mBq/ml for ²³⁹Pu; 0.071 mBq/ml for ²⁴⁰Pu) in a sample solution, or an absolute detection limit of 42 fg in a 5 ml sample solution, by using the shield torch technique. Analytical results for the determination of the ^239+240Pu and the ²⁴⁰Pu/²³⁹Pu ratio in IAEA 368 (ocean sediment) reference material indicated that the accuracy of the method was satisfactory. The method developed was successfully applied to a study of Pu behavior in the sediments from Sagami Bay, Japan. The observed high ²⁴⁰Pu/²³⁹Pu ratio in the sediment core indicated that there was additional Pu input derived from close-in fallout in addition to the global fallout.     

Polonium (210Po), uranium (238U) and plutonium (239+240Pu) in the biggest Polish rivers

In the paper the results of determination of ²¹⁰Po, ²³⁸U and ^239+240Pu radionuclides in the biggest Polish rivers are presented. Our results show the Vistula and the Oder as well as three Pomeranian Rivers are important sources of these radionuclides for the southern Baltic Sea.     

Sequential separation and determination of plutonium, americium-241 and strontium-90 in soils and sediments

A sensitive and reliable metbod for the sequential separation and determination of plutonium,²⁴¹Am and⁹⁰Sr in soil samples was developed. Plutonium was separated by a Microthene-TNOA column. Then⁹⁰Y (for⁹⁰Sr determination) was separated from americium by a HDEHP column after elimination of large amounts of interfering stable or radioactive nuclides (iron,²¹⁰Bi and²¹⁰Po etc.) by an oxalate precipitation and a Microthene-TNOA column. Finally americium was purified by another HDEHP column and a PMBP-TOPO extraction. A special attention was paid to the decontamination of Pu and Am from²¹⁰Po and of⁹⁰Y from²¹⁰Bi; the relevant decontamination factors resulted greater than 10⁵, 10⁶ and 10⁴ respectively. The detection limits were 1.2 mBq/kg for Pu and 1.7 mBq/kg for²⁴¹Am and 0.32 Bq/kg for⁹⁰Sr. The procedure was checked by analyzing three certified samples supplied by IAEA. Some Italian soil samples were also analyzed giving average yields of 84.9±7.2% for Pu, 57.8±3.2%for Am and 96.7±1.6% for Y; the^239+240Pu,²³⁸Pu,²⁴¹Am and⁹⁰Sr contents (Bq/kg) ranged from 0.347 to 1.53, from 0.013 to 0.048, from 0.126 to 0.556 and from 2.89 to 11.6 respectively and the average ratios were 0.037±0.017 for²³⁸Pu/^239+240Pu, 0.357±0.040 for²⁴¹Am/^239+240Pu and 7.0±1.2 for⁹⁰Sr/^239+240Pu.     

Presence of 137Cs, Pu isotopes and 241Am in ligurian and Tyrrhenian Seas sediments

During the last ten years, the Italian Universities of Parma and Urbino collaborated on a special radioecological program having the aim to study the levels and the distribution of long-lived radionuclides in different marine and terrestrial matrixes. This paper summarizes the results concerning the concentrations of ^239+240Pu and ²³⁸Pu, ²⁴¹Am and ¹³⁷Cs in sediments collected in the Ligurian and South Tyrrhenian Seas (Rapallo Harbour, Vado Ligure Canyon, Eolie Islands). Superficial sediments and sediment cores were collected. For cores the vertical distribution was calculated and the sedimentation rate obtained. ¹³⁷Cs was determined directly by gamma-spectrometry, while ^239+240Pu, ²³⁸Pu and ²⁴¹Am were separated by extraction chromatography, electroplating and determined by alpha-spectrometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Extraction-chromatographic method for the determination of plutonium-239,240 and plutonium-238 in soils with high natural radioactivity

A highly selective method is described for the determination of ^239,240Pu and ²³⁸Pu in soils by extraction chromatography with Microthene-710/tri-n-octylamine. The method is especially suitable for volcanic soils containing high concentrations of natural alpha radionuclides (Th, Po, U, etc.). The detection limit by α-spectrometry is 2.2 mBq kg^?1 for 50-g soil samples. The average chemical yield, obtained by adding ²⁴²Pu as the internal standard, is 69.5 ± 17.1%. An IAEA reference soil was analyzed, with a relative error of 6.7% for ²³⁹Pu. The concentration of ^2239,240Pu in thirteen analyzed soils and sediments ranged from 26.6 to 429 mBq kg^?1.     

Soil and sediment sample analysis for the sequential determination of natural and anthropogenic radionuclides

A new sequential method for the determination of both natural (U, Th) and anthropogenic (Sr, Cs, Pu, Am) radionuclides has been developed for application to soil and sediment samples. The procedure was optimised using a reference sediment (IAEA-368) and reference soils (IAEA-375 and IAEA-326). Reference materials were first digested using acids (leaching), ‘total’ acids on hot plate, and acids in microwave in order to compare the different digestion technique. Then, the separation and purification were made by anion exchange resin and selective extraction chromatography: transuranic (TRU) and strontium (SR) resins. Natural and anthropogenic alpha radionuclides were separated by uranium and tetravalent actinide (UTEVA) resin, considering different acid elution medium. Finally, alpha and gamma semiconductor spectrometer and liquid scintillation spectrometer were used to measure radionuclide activities. The results obtained for strontium-90, cesium-137, thorium-232, uranium-238, plutonium-239+240 and americium-241 isotopes by the proposed method for the reference materials provided excellent agreement with the recommended values and good chemical recoveries. Plutonium isotopes in alpha spectrometry planchet deposits could be also analysed by ICPMS.     

Distribution of radionuclides and elements in Cubatão River sediments

Summary Cubat?o River is located in Santos Basin, S?o Paulo State, Brazil. This region is characterized by the occurrence of estuaries and mangrove. Due to its location, near the coastal line, it is also an important industrial area, where phosphate fertilizer plants, petrol refineries, and chemical and steel industries are present. Such human activities contribute to the enhancement of elemental composition in sediments and, in some cases, also increase the radionuclide concentrations, the so called Technologically Enhanced Natural Occurring Radioactive Materials (TENORM). The contamination of land and sediments by TENORM is of major concern. The activity concentration of U and Th series radionuclides was determined in five sediment samples from Cubat?o River. The activity concentration ratio was also determined. Equilibrium was observed for the ratio ²³⁴U/²³⁸U. The activity ratios of Th/²³⁸U, ²²⁸Ra/²²⁶Ra and ²¹⁰Pb/²²⁶Ra were higher than the unity. In the first two cases, the observed values are due to the higher activity of Th in the sediment and in the last case are probably due to the atmospheric deposition of ²¹⁰Pb.     

Analysis of plutonium isotopes in marine samples by radiometric, ICP-MS and AMS techniques

IAEA reference materials (radionuclides in the marine environment) collected in areas affected by nuclear reprocessing plants and nuclear weapons tests have been analysed by semiconductor alpha-spectrometry (SAS), liquid scintillation spectrometry (LSS) and mass spectrometric techniques (high resolution ICP-MS and AMS) with the aim of developing analytical procedures and to study the geochemical behavior of plutonium in the marine environment. The Pu results obtained by SAS, ICP-MS and AMS were in reasonably good agreement (R ² = 0.99). The mean atom ratios of ²⁴⁰Pu/²³⁹Pu in IAEA reference materials, IAEA-134, 135 and 381 were (0.212±0.010), (0.211±0.004) and (0.242±0.004), respectively. IAEA-384 (Fangataufa Lagoon Sediment) gave a ²⁴⁰Pu/²³⁹Pu mean atom ratio of 0.051±0.001. The results of ²⁴¹Pu obtained by ICP-MS and LSS also show reasonable agreement (R ² = 0.91). Pu isotopic signatures were useful in tracing Pu origin and in interpreting biogeochemical processes involving Pu in the marine environment.     

Simultaneous determination of plutonium and americium in soils by extraction chromatography

A radiochemical method is described for the determination of²³⁸Pu,^239(240)Pu and²⁴¹Am in a single soil sample. Plutonium is separated from a HNO₃ leaching solution by a Microthene-TNOA column; amcricium is coprecipitated by oxalic acid, decontaminated from polonium by a TNOA-column in HCl medium, separated from the rare earth elements by a Microthene-HDEHP column, eluted with a 0.07M DTPA+1M lactic acid solution and finally purified by a PMBP-TOPO extraction. The method supplies a good decontamination of Am and Pu from natural alpha emitters; starting from 50 g soil, the average yields were 75.1±13.4% for plutonium and 57.7±10.8% for Am.^239(240)Pu,²³⁸Pu and²⁴¹Am concentrations (mBq/kg) in three different kinds of soil were the following: 255, 10.4, 81.3 (uncultivated soils); 236, 11.6, 76.7 (cultivated soils); 46, 1.9, 19.8 (river sediment). The average ratios²³⁸Pu to^239(240)Pu and²⁴¹Am to^239(240)Pu were 0.044 and 0.350, respectively.     

Determination of alpha-emitting Pu isotopes in environmental samples

This paper presents an improved radiochemical procedure for the determination of alpha-emitting Pu isotopes in environmental samples (soils, sediments, vegetation) by alpha-particle spectrometry. Quantitative Pu recovery yields were obtained (average 60%), 0.1 mBq being the average minimum detectable activity by the complete technique. Special efforts were made to ensure the removal of traces of different natural alpha-emitting radionuclides, which can interfere with the correct determination of 239+240Pu and 238Pu concentrations. The radiochemical procedure was validated by application to reference material and by participation in intercomparison exercises. This radiochemical procedure was applied to the different layers of a high-resolution sediment core taken from a lake in Sweden. The 239+240Pu and 238Pu/239+240Pu profiles obtained in the high-resolution sediment core correctly reproduced the expected evolution of these quantities as observed historically in the atmosphere, validating the procedure for this purpose and showing the power of these radionuclides for dating purposes.     

Geochemical partitioning of actinides using sequential chemical extractions: Comparison to stable elements

We have developed a sequential extraction technique for determining the geochemical partitioning of Am, Pu, and U in soils and sediments. Stable element analyses were combined with radiometric measurements to determine the most probable geochemical host phases of these actinides in reference sediment IAEA-135.²⁴¹ Am results indicate an association with carbonate minerals and organic matter. The extraction profile of²³⁸U was similar to that of refractory elements Al, Ti, and K.^239/240Pu data suggest a fractionation of Pu into Fe-bearing phases of varying solubility. The reproducibility of the method was quite good (replicates agreed to within 10% at a 95% confidence level).