Influence of freezing on physicochemical forms of natural and technogenic radionuclides in Chernozem soil

Sharp variations of different climatic parameters influence the transport, transfer, and deposition of contaminants in nature. Investigations of the impact of environmental temperature on the fractionation of radionuclides in soil are necessary for adequate assessment of their distribution and bioavailability in case of a nuclear accident. The impact of a sharp decrease of environmental temperature shortly after radioactive contamination on the physicochemical fractionation of natural and technogenic radionuclides in Chernozem soil and its influence on their potential migration ability and bioavailability in case of subsequent warming were evaluated. The soil was contaminated in a laboratory with ²⁴¹Am, ⁶⁰Co, ¹³⁷Cs, ²²⁸Ra, ²³⁴Th, and U and two temperature regimes were used for storage. Changes of the radionuclides association with various soil phases in the first weeks after contamination were studied. Physicochemical forms of ²⁴¹Am, ⁶⁰Co, ²²⁸Ra, ²³⁴Th, and U were determined using two sequential extraction procedures. The ion-exchangeable forms of ¹³⁷Cs were evaluated by single extraction with 1 M NH₄NO₃. The data showed that the freezing, following the radioisotope contamination of the soil, causes an increase of the amount of potentially mobile forms of radiocobalt, radiocesium, radium, and thorium and has an insignificant impact on the fractionation of americium and uranium.     

Effect of soil properties on radioactivity concentrations and dose assessment

This study evaluated the correlation between radioactivity concentrations and soil properties, and determined the total annual effective dose near an underground geologic repository for transuranic wastes. Soil samples were collected from two historical monitoring areas (Near Field and Cactus Flats). Alpha-particle spectrometry was used for the analysis of ²⁴¹Am, ^239+240Pu and ²³⁸U, while ¹³⁷Cs, ⁴⁰K, ²³²Th and ²²⁶Ra were detected by gamma ray spectrometry. Higher radioactivity concentrations and stronger positive correlations between radioactivity concentrations and soil properties were obtained in Cactus Flats compared to Near Field. The total annual effective dose was lower than the recommended limit of 1 mSv y^??1.

     

Geochemical partitioning of actinides, 137Cs and 40K in a Tyrrhenian sea sediment sample: Comparison to stable elements

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

Determination of U and Th in soil and plants obtained from a high natural radiation area in China using ICP-MS and γ-counting

This study was carried out for the determination of ²³⁸U and ²³²Th concentrations in soil and various foods obtained in high natural radiation areas in China for estimating the internal radiation doses caused by these radionuclides. Knowledge of the daily dietary intakes of the nuclides through foods is essential to evaluate the internal radiation dose. Several analytical methods were evaluated for their applicability and quality assurance. The accuracy and precision of ICP-MS is considerably better for determining trace elements like U and Th in fine powder samples. The estimated annual effective dose is 0.302 μ Sv/y for ²³⁸U and 1.86 μ Sv/y for ²³²Th in the high natural radiation area, and 0.0101 μ Sv/y for ²³⁸U and 0.177 μ Sv/y for ²³²Th in the control area. Received: 25 September 1998 / Revised: 3 December 1998 / Accepted: 8 December 1998     

Radiochemical separation of Pu, U, Am and Sr isotopes in environmental samples using extraction chromatographic resins

This study presents a rapid and quantitative sequential radiochemical separation method for Pu, U, Am and Sr isotopes in environmental samples with extraction chromatographic resins. After radionuclides were leached from the samples with 6 M HNO₃, Pu and U isotopes were adsorbed onto the UTEVA column and Am isotopes were adsorbed onto the TRU column connected with the UTEVA column. Also, ⁹⁰Sr was adsorbed onto the Sr column connected with the TRU column. Pu and U isotopes were purified from other nuclides through the UTEVA column. In addition, Am isotopes were separated from other nuclides with the TRU column. Finally, ⁹⁰Sr was purified with the Sr resin. After α source preparation for the purified Pu, U and Am isotopes with micro-coprecipitation method, Pu, U and Am isotopes were measured using alpha spectrometry. On the other hand, ⁹⁰Sr was measured using a low level liquid scintillation counter. The radiochemical procedure for Pu, U, Am and Sr nuclides investigated in this study has been applied to environmental samples after validating the simulated samples.     

Continuous separation of Sr, Y and some actinides by mixed solvent anion exchange and determination of 89,90Sr, 238,239Pu and 241Am in soil and vegetation samples

Methodology for the determination of ^89,90Sr, Am and Pu isotopes in complex samples is given. Methodology is based on simultaneous isolation of Sr, Y and actinides from samples by mixed solvent anion exchange chromatography, mutual separation of ^89,90Sr and ⁹⁰Y from actinides, mutual separation of Th, Pu and Am by extraction chromatography, quantitative determination of ^89,90Sr by Cherenkov counting and quantitative determination of Pu and Am isotopes in soil and vegetation samples by alpha spectrometry. It is shown that Y and Sr can be efficiently separated from alkaline, alkaline earth and transition elements as well as from lanthanides and actinides on the column filed by strong base anion exchanger in nitrate form and 0.25?M HNO₃ in mixture of ethanol and methanol as eluent. It is also shown that Pu, Am and Th strongly binds on the mentioned column, can be separated from number of elements and easily be eluted from column by water. After elution actinides were mutually separated on TRU column and electrodeposited on stainless steel disc. Examination of conditions of electrodeposition was shown that chloride-oxalate electrolyte with addition of DTPA in presence of sodium hydrogen sulphate in cell with cooling and rotating platinum anode enables deposition of actinides within 1?h by 0.8?A?cm^?2 current density. Obtained peaks FWHM for Pu, Am and Th isotopes are between 27 and 40?keV. Scanning electron microscopy picture and ED XRF analysis of electroplated discs showed that actinide deposition is followed by iron oxide formation on disc surface. The methodology was tested by determination of ^89,90Sr, Am and Pu isotopes in ERA proficiency testing samples (low level activity samples). Obtained results shows that ^89,90Sr, ²⁴¹Am and ^238,239Pu can be simultaneously separated on anion exchange column, ^89,90Sr can be determined by Cherenkov counting with a satisfactory accuracy and limit of determination within 1?C3?days after separation. ²⁴¹Am and ^238,239Pu can easily be separated on TRU column and determined after electrodeposition with acceptable accuracy within 1?day.     

Distribution of uranium,plutonium, and <Superscript>241</Superscript>Am in soil samples from Idaho National Laboratory

Soil materials used were collected in the early 1970s at Idaho National Laboratory near the Subsurface Disposal Area (SDA). Samples from a depth of 0–4 and 4–8 cm at two different sites located on the northeast corner of the SDA perimeter were analyzed. The concentration of ²³⁴U, ²³⁵U, ²³⁶U, and ²³⁸U in soil digests were measured by mass spectrometry. Uranium isotopic composition of the soil at the two sample sites and depths is compared to previously measured concentrations of ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu, and ²⁴¹Am. Implications for remediation of contaminated soils surrounding the SDA are discussed.     

Improved separation method for determining actinides in soil samples

Radionuclides have been identified as a significant source of contamination at many United States Department of Energy (DOE) sites. As a result, reliable and accurate methods to determine actinide content in environmental samples have become increasingly important. Therefore, an improved analytical scheme using a series of actinide-selective extraction chromatography (Tru-Spec, Teva-Spec) and ion-exchange (Diphonix) resins was designed to satisfy the requirements of both alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). Alpha spectrometry required the sequential isolation of the actinides, whereas ICP-MS required only a group separation of the actinides. The separation schemes were designed to allow analysis of the actinides in soil, whether the soils were acid leached or totally dissolved through fusion. For those analytes present as contaminants (^239/240Pu,²⁴¹Am), the laboratory results agreed favorably with the accepted values for several reference soils. However, for the acid digestion procedure, the results for matrix constitutents (²³⁸U,²³⁴U,²³²Th) were quite low because the silicate matrix was not decomposed. The sodium hydroxide fusion technique described allowed accurate analysis of both matrix constituents and contaminants because a total dissolution was achieved.     

Evaluation of the 153Sm-EDTMP radiochemical purity using three chromatographic methods

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

Biosorptive behavior of some dead biomasses in the removal of Sr(85+89) from aqueous solutions

The knowledge of radioactive and stable elements partitioning to natural sediment systems is essential for modelling their environmental fate. A sequential extraction method consisting of six operationally-defined fractions has been developed for determining the geochemical partitioning of natural (U, Th, ⁴⁰K) and antropogenic (Pu, ²⁴¹Am, ¹³⁷Cs) radionuclides in a 10 cm deep sediment sample collected in the Tyrrhenian sea (Gaeta Gulf, Italy) in front of the Garigliano Nuclear Power Plant. ¹³⁷Cs and ⁴⁰K were measured by gamma-spectrometry. Extraction chromatography with Microthene-TOPO (U, Th), Microthene-TNOA (Pu) and Microthene-HDEHP (Am) was used for the chemical separation of the alpha-emitters: after electrodeposition alpha-spectrometry was carried out. Some stable elements (Fe, Mn, Al, Ca, Pb, Ba, Ti, Sr, Cu, Ni) were also determined in the different fractions to get more information about the chemical association of the radionuclides.     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

Distribution of 238U, 226Ra, 232Th and 40K in soil samples around Tarapur,India

The radioactivity concentrations of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K in soil samples around Tarapur vary from 11.5 ± 2.6 to 50.3 ± 6.6, 14.9 ± 0.6 to 40.5 ± 1.2, 18.1 ± 0.4 to 75.0 ± 1.5 and 130.1 ± 1.6 to 295.1 ± 2.6 Bq/Kg respectively. The measured activity concentrations for ²³⁸U and ²²⁶Ra were compared and found in good agreement with the Indian as well as world average. The average ²³²Th and ⁴⁰K concentrations in Tarapur were lower than the Indian average value.     

Adsorption and migration of <Superscript>241</Superscript>Am in aerated zone soil

As an important radioisotope in nuclear industry and other fields, ²⁴¹ Am is one of the most serious contamination concerns due to its high toxicity and long half-life. In order to supply useful reference for disposal of ²⁴¹Am waste with low-medium radioactivity, the adsorption and migration behavior of ²⁴¹Am on aerated zone soil were investigated by the static experimental method and column experiments. The results showed that more than 98% of the total ²⁴¹Am could be adsorbed from ²⁴¹Am solution of 0.32·10⁻⁷−1.1·10⁻⁷ mol/l by the soil at pH 4–9. The adsorption of ²⁴¹Am on the soil was a pH-dependent process at pH<4, but for pH>4, the adsorption rate of ²⁴¹Am on the soil changed minutely. The adsorption equilibrium was achieved within 24 hours and no significant effect on adsorption of ²⁴¹Am was observed at liquid-solid ratios of 50:1–500:1. The relationship between concentration of ²⁴¹Am and adsorption capacities of ²⁴¹Am can be described by the Freundlich adsorption equation. Adsorption of ²⁴¹Am on the soil can be inhibited by humic acid, ferric hydroxide colloid, or some anions, such as citric acid anion, saturated EDTA solution, C₂O₄ ²⁻ and CO₃ ²⁻. It was also noted that the adsorption rate of ²⁴¹Am drops in solutions containing Eu³⁺ or Nd³⁺, even 0.5 times above the ²⁴¹Am concentration. A migration distance of 8 mm for ²⁴¹Am(III) is observed only in the aerated zone soil containing ferric colloid, while a migration distance of less than 2 mm is noted in other soil samples after more than 250 days. All these results indicate that the aerated zone soil is an efficient sorbent for ²⁴¹Am and can inhibit the migration of ²⁴¹Am.     

Radiological assessment of natural and fallout radioactivity in the soil of Chamba and Dharamshala areas of Himachal Pradesh,India

This paper presents the results of measurement of natural and fallout radioactivity in soil samples of Chamba and Dharamshala areas in Himachal Pradesh, India. Spatial distribution of ²³⁸U, ²²⁶Ra, ²³²Th, ⁴⁰K, ¹³⁷Cs was determined using High resolution gamma-ray spectrometry. The mean activity concentration in Chamba region due to ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs was 32.3, 58.4, 588.3, and 10.9 Bq kg⁻¹, respectively, whereas in Dharamshala it was 35.7, 61.3, 594.9, 10.0 Bq kg⁻¹, respectively. Absorbed gamma dose rate (D) in air was calculated using appropriate dose conversion factors, which was varying from 45 to 103 nGy h⁻¹. To control the radiation exposure due to natural radioactivity in soil, if it is used as building materials, radium equivalent activity (Ra_eq) and activity index were also evaluated. Radium equivalent activity calculated for the soil ranged from 95.5 to 234.2 Bq kg⁻¹ with average of 171.0 Bq kg⁻¹.The calculated Activity concentration index was ranged from 0.34 to 0.85 with an average value of 0.64. The natural and fallout radioactivity in soil of this region is comparable with Indian average and other parts of the world. The percentage contribution of ²³⁸U, ²³²Th and ⁴⁰K and ¹³⁷Cs to the average external gamma dose rate was 22, 46, 32, 2%, respectively. This shows that the dose contribution due to fallout radioactivity is negligible as compared to the natural radioactivity.     

An improved actinide separation method for environmental samples

This paper presents a rapid method of separation of five actinide elements (Th, U, Np, Pu, and Am) for aqueous media samples. This separation method utilizes the unique chemistries of the actinides at low concentrations^1,2 and the properties of the EIChroM TRU-Resin^TM extraction resin. In order to cleanly recover the five actinides from aqueous samples or solubilized soil samples, the sample is passed through the column twice. The sample is first loaded in an HCl solution with hydrogen peroxide. This allows the Am and most matrix ions to pass through the column. Then the Th is eluted using dilute HCl followed by the Np and Pu which are eluted together with oxalic acid in dilute HCl solution. Finally, the U is eluted with ammonium oxalate solution. A calcium-oxalate coprecipitation is performed on the original load solution containing the Am ions and the dissolved precipitate is then reloaded onto the TRU-Resin^TM column in HNO₃ with ascorbic acid. The procedure requires approximately 1.5 working days for experienced technicians, greatly reduces waste, and generally results in actinide recoveries of 80–100%.     

Natural radionuclides and metals intake into soya,corn and lettuce grown on soil amended with phosphogypsum

Phosphogypsum is a by-product of the phosphate fertilizer industry. It is produced by precipitation during wet process of phosphate rocks, thus posing serious problems with its utilization and safe disposal. In Brazil, three main industries are responsible for the production and storage of about 5.5?×?10⁶ tons per year. Phosphogypsum may contain trace metals and radionuclides of U and Th series. Since, in Brazil, phosphogypsum has been used for many years as soil amendment, it is important to know its availability in the environment. The main objective of this study is to evaluate the radionuclides and metals transfer in the soil-to-plant system. To accomplish this task an experiment was carried out in a green house, where two major crop groups (soya bean and corn) and leafy vegetables (lettuce) were grown in two types of soil (clay and sandy) amended with phosphogypsum. The transfer-factors were evaluated for the metals (As, Cd, Cu, Ni and Pb, Ba, Co, Cr, Fe, Zn and REE) and for the radionuclides U, Th, ²²⁶Ra, ²²⁸Ra, ²¹⁰Pb and ²¹⁰Po. The addition of PG to the two soils studied, did not significantly alter the TFs values for all the elements studied.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

Determination of plutonium,americium and curium in environmental meterials

A sequential radiochemical scheme for the separation of Pu and Am (along with Cm) from environmental materials is given. Optimum conditions for coprecipitation of these elements on bismuth phosphate and the influence of Fe and Th content of the sample on the recovery of Am were studied. Internal tracers²⁴²Pu and²⁴³Am were used as tracers for Pu and Am, respectively, and estimates were made by alpha-spectrometry. Average recoveries obtained from sea water were 85% and 77% for Pu and Am, respectively. Lower recoveries (<50%) were obtained for Am in sediments. Work carried out as part of the International Atomic Energy Agency Research Contract 1954/RB/RI.     

Determination of Pu,Am, U and Cs in large soil samples in the vicinity of the USDOE Waste Isolation Pilot Plant

The determination of actinides in environmental soil and sediment samples are very important for environmental monitoring. A rapid actinide separation method has been developed and implemented that allows measurement of U, Pu and Am isotopes in large soil samples (10–15 g) with high chemical yields and effective removal of matrix interferences. The radiochemical procedures involve the total dissolution of soil samples, separation on anion-exchange resin, and separation and purification by extraction chromatography, e.g., UTEVA, TEVA, and TRU with measurements of radionuclides by alpha-spectrometry. The validation of the method is performed through the analysis of reference materials or by participating in laboratory intercomparison programs.     

Behavior of uranium and thorium isotopes in soils of the Boréon area, Mercantour Massif (S.E. France): Leaching and weathering rate modeling

Four cores were collected in weathered rocks and soils in the Boréon forest area (1765 m, Mercantour Massif, France). The samples were analyzed for the isotopes ²³⁰Th, ²³²Th, ²³⁴U and ²³⁸U. The activity and isotopic ratio profiles suggest that uranium was mobilized (leaching and precipitation) during the weathering process, as well as thorium but in a much less proportion. A model was drawn up to evaluate the U leaching rate and the time that some levels of the weathered rocks have been subjected to weathering. It utilizes LATHAM and SCHWARCZ’s two equations,¹⁵ expressed as ²³⁴U/²³⁸U and ²³⁰Th/²³⁸U activity ratios, which assume that the alpha recoil effect allows easier leaching for ²³⁴U than ²³⁸U and no Th mobility. But this last assumption does not correspond to the observations made in the Boréon area, since it appears that in some soil deeper layers ²³⁰Th and ²²⁸Th are in radioactive deficit relatively to their parents. As there are four unknown quantities (the time, the leaching rates of ²³⁸U, ²³⁴U, ²³⁰Th), the problem to be solved requires two more equations; these can be obtained utilizing the U activity ratio in water, and taking into account the ²³²Th behavior. In some sites the ²³⁸U leaching rate is high in deeper soil levels (near the fresh rocks); this would correspond to a loss of half the U amount in less than 24 000 years.