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Analytical Methods for Ruthenium-106 in Marine Samples

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Analytical Methods for Ruthenium-106 in Marine Samples Analytical Methods for Ruthenium-106 in Marine Samples IWASHIMA, K. Department of Radiological Health, Institute of Public Health, Tokyo, 108 (Received, May 8, 1972) ABSTRACT Analyses of ruthenium-106 in marine environmental samples, which are useful for monitoring within a control context, have been developed. The quantity and the quality of the samples applied for the analyses are as follows : two l of sea water filtered through a millipore filter of 0.45 E.cm pore size ; two g (wet weight) of bottom sediments prepared by sieving in sea water ; or the edible part of marine organisms equivalent to ca. 1 g ash. In order to equilibrate 106Ru in the samples with ruthenium carrier and to dissolve the samples completely, marine organisms and sediments are ashed at 400•[500•Ž, and then fused with a mixture of potassium hydroxide and potassium nitrate. Sea water is heated in the presence of an oxidant in an alkaline medium. Ruthenium is extracted with carbon tetrachloride as ruthenium tetroxide, and then back-extracted with sodium hydroxide solution containing a reducing agent. Hydrous ruthenium oxides are precipitated from the extract and subjected to ƒÀ-activity measurement with a low background gas-flow counter by use of a 40 mg/cm2 aluminum absorber. The loss of ruthenium throughout ashing and chemical procedures was found to be negligibly small by a tracer experiment. Chemi cal yields were 89•}5 % and the ratio of chemical and radiochemical yields was 0.98•}0.03. Sen sitivity of the method (3ƒÐ) is 0.2 pCi and the whole chemical procedure takes 3•`4 hours. De contamination factors for the other activities were: > 3 •~ 104 for 54Mn and 59Fe, 3 •~ 103 for 60Co, 85Sr and 131I , 2•~103 for 137Cs, 1•~103 for 65Zn and 95Zr-95Nb, and approximately 102 for radio nuclides of thorium and uranium series. A rapid ƒÁ-spectrometric technique for 106Rh has also been developed in which 106Ru was coprecipitated with cobalt sulfide from sea water. INTRODUCTION The first reprocessing plant of nuclear fuels in Japan is expected to be in ope 岩 島 清:国 立 公 衆 衛 生 院 放 射 線 衛 生 学 部 港 区 白金 台4-6-1,〒108 ration in 1973. The reprocessing produces low level liquid waste containing a va riety of fission products and other radioactive nuclides which are removed in part before the discharge into water areas. The chemistry of ruthenium in solution is quite complicated and the complete removal can not be effected easily.1.2) The principal chemical forms of ruthenium in nitric acid solutions of irradiated fuel are nitrosyl complexes such as nitrato and nitro complexes of nitrosylruthenium (RuNO), free RuNO3+ ion, and Ru-O-Ru complexes.') These complexes are persistently pre sent in the various subsequent reprocessing stages and are detected in rinsing waters, extraction solvents etc. used in the reprocessing.3) Ruthenium-106, especially because of its long half-life (1.0y), is found abun dantly in the radioactive effluents from nuclear fuel reprocessing plants, being a critical radionuclide for some waste disposal operations,4'5) so that this radionuclide is one of the most important nuclides in the context of controlling marine radio active contamination.1-8) For example, the waste discharged daily from the above mentioned reprocessing plant in Japan is planned to contain 1 Ci total f3-activity of which 0.2 Ci is '(16Ru when the cooling time is set longer than 150 days and 1 ton of fuel is treated daily.9) Preoperational researches on the effects of waste re lease into sea were coordinated by the Japan Atomic Energy Safety Research As sociation and the first report of the Evaluation Committee pointed out that the critical radionuclide would be 1°6Ru and the critical pathways through shellfish such as clams and oyster which are popularly consumed in this country. Thus, a simple method of 106Ru determination in the marine environmental samples is urgently needed for wide use in a control context. Few methods for radiochemical determination of 106Ru in marine environmental samples have been reported. Furthermore, in most cases preliminary treatments of samples have not sufficiently been examined. Considering the situation that our knowledge on the chemical and physical states of radioruthenium in the marine environment is quite limited,"' 14) the following points should be examined carefully : how to treat the suspended materials in sea water, how to preserve water samples or how to extract ruthenium completely from organisms and sediments. A method proposed by the WHO/FAO/IAEA Meeting15) is very tedious and requires much skillfulness. Tsuruga'6.17) proposed a method of fusing ash of organisms with the mixture of potassium hydroxide, potassium carbonate and potassium nitrate, pre cipitating ruthenium as sulfide, and reducing it to metallic state. However no in formation on the radiochemical purity was given, and the procedure takes a long time. Two methods have been reported on the separation of ruthenium. One is re precipitation as sulfide from an acid solution (3 M hydrochloric acid-0.1 M hydrofluoric acid)18'19) and another is distillation of ruthenium as tetroxide.2°-22> One of the disad vantages in the former is incomplete extraction with the acid solution. In the latter a disadvantage is a difference in the distillation rate between ruthenium in samples and that added as the carrier. Furthermore, the distillation technique is very com plicated. In the case of treating bottom sediments, there has been completely lack ing in the consideration on the removal of naturally occurring radionuclides of thorium and uranium series. 14.23.24) Preliminary concentration of ruthenium from sea water for the radiochemical analysis was effected by coprecipitation with magnesium hydroxide and subsequent extraction with carbon tetrachloride,25) or by coprecipitation with iron (III) hydroxide and subsequent distillation or extraction .26> These methods are rather complicated. The sulfide precipitation seems the most promising method of the preliminary con centration for the r-spectrometric determination. However, the effect of chemical form of ruthenium on the recovery in this sulfide method has not been examined. 27,28) In the case of comparatively high levels of radioruthenium, simple procedures such as drying of organisms or sediments and evaporation to dryness of sea water are sufficient for subsequent r-ray spectrometry, 29-31>while, in the case of the low levels, it should be mentioned that chemical procedures are required in some stages of the determination of radioruthenium. Scope of the method of analysis In view of lacking in information about the relation between chemical forms of radioruthenium and its recovery and about radiochemical purity of the final pre cipitate, this study also tries to establish a simple and reliable method in the routine determinations in a control context. In considering a scheme of analysis, it is essential to have some ideas on the required lower limit of detection for a radionuclide concerned in order to determine sample size to be analyzed and to select instruments of radiations measurements to be used. On the basis of the ICRP recommendations on the dose-limit to general public, the minimum consumption rates for important groups of marine foodstuffs and the concentration factors in these organisms, the required lower limits of detec tion in environmental samples can be derived. An example of such limits for a variety of fission products and induced radionuclides was established by a panel organized by the International Atomic Energy Agency (IAEA).32> In Table 1 are shown the data for lo6Ru derived from the literature. 32~ It is possible to estimate Table 1. Required lower limit of detection of 106Ru in sea water in waste dis posal operations * ICRP value for the public . * Lower limit is defined as 1 % of the concentration of sea water in equilibrium with or ganisms contaminated at level compatible with permissible ICRP value. The lowest concentration among those derived from three types of organisms. the concentration of 106Ru in sea water in equilibrium with organisms contaminated at level compatible with the permissible ICRP value, and the required lower limit of detection is defined as 1 % of this concentration. The size of various samples are determined in the following way. Sea water: By the use of a low-background gas-flow counter with a 47r type detector, (3-ray from 106Rh can be measured by a counting efficiency of 66.4 through Al-absober (40 mg/cm2), and when the activity is measured for 100 min., 0.32 pCi of 106Rh can be determined with a statistical error of ±0.10 pCi,, or 0.4± 0.13 pCi in original sample can be determined when the chemical yield is 80 %. Consequently, the lower limit of detection of 0.2 pCi/l can be covered by taking 2 liters of sea water sample for the analysis. Marine organisms : The lower limit of detection for edible sea organisms can be derived from 1 % of the permissible daily intake of 106Ru (2.2 x 104 pCi) divided by the maximum consumption of each organism (1,000g for fish, 500g for seaweed and 100g for shellfish). The limits are 0.2, 0.4 and 2.2 pCi/g fresh of fish, seaweed and shellfish, respectively. Practically, a procedure with one gram ash is thought to be desirable for the sample preparation and the radioactivity measurement. Sediments : The concentration factors in sediment have been reported as 11,000 for silt,33) or larger than 103.34) When 103 is taken for the sake of safety, the re quired lower limit for sediment which is in equilibrium with the activity of sea water (0.2 pCi/l) is 0.2 pCi/g.
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