Determination of concentrations of U and Th in their mixed oxides by INAA methods

Uranium and thorium mixed oxides are being prepared using natural U and Th for studies on fuels for Advanced Heavy Water Reactors, wherein composition of U and Th is specific and requires strict control in terms their contents and homogeneity. Chemical quality control necessitates accurate and precise compositional characterization of the fuel material by a suitable analytical method. Among various analytical methods for U and Th, instrumental neutron activation analysis (INAA) is one of the best methods for their simultaneous determination without chemical dissolution and separation. INAA methods using reactor neutrons namely thermal NAA and epithermal NAA were standardized for the determination of U and Th in their mixed oxides. Standards, synthetic samples and U–Th mixed oxide samples, prepared in cellulose matrix, were irradiated at pneumatic carrier facility of Dhruva reactor as well as at self serve facility of CIRUS reactor under cadmium cover (0.5 mm). Radioactive assay was carried out using a 40% relative efficiency HPGe detector. Both activation and daughter products of ²³⁸U (²³⁹U and ²³⁹Np) and ²³²Th (²³³Th and ²³³Pa) were used for their concentration determination. The method was validated by analyzing synthetic samples of 6–48%U–Th mixed oxides. The standardized method was used for the concentration determination of U and Th in 4–30%U–Th mixed oxide samples. Results of U and Th concentrations including associated uncertainties obtained from the INAA methods are presented in this paper.     

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).     

Measurement of gamma radiation from rocks used as building material in Tiruchirappalli district,Tamil Nadu,India

Tiruchirappalli district is naturally endowed with rich building material resources which are also used in neighboring districts. Hence, measurements of activity concentrations and absorbed dose rate of primordial radionuclides (²³⁸U, ²³²Th and ⁴⁰K) in the rock samples collected from 14 sedimentary rocks and 9 igneous rocks were carried out employing gamma ray spectrometry. In sedimentary rocks the geometric mean activity concentrations of ²³⁸U, ²³²Th and ⁴⁰K were found to be 7.4, 29.5 and 233.6 Bq kg^?1, respectively. On the other hand in igneous rocks geometric mean activity concentrations of ²³⁸U, ²³²Th and ⁴⁰K were distinctly higher and found to be 13.1, 105.7 and 888.8 Bq kg^?1, respectively. The mean radium equivalent activity (Ra_eq) recorded in both sedimentary (20.8 Bq kg^?1) and igneous rocks (245.4 Bq kg^?1) were well within the limit prescribed for dwellings (370 Bq kg^?1) except Vilathupatti (689.3 Bq kg^?1) and Narthamalai (371.6 Bq kg^?1). The mean absorbed dose rate from igneous rock (115 nGy h^?1) exceeded the prescribed limit of 55 nGy h^?1. The mean indoor annual effective dose from the sedimentary rock (0.056 mSv y^?1) and igneous rock (0.580 mSv y^?1) did not exceed the prescribed limit (1 mSv y^?1) except the igneous rock from Vilathupatti (1.51 mSv y^?1). The study concludes that sedimentary and igneous rocks analyzed were radiologically safe when used as building materials except igneous rock from Vilathupatti and Narthamalai.     

Characterization of uranium isotopic abundances in depleted uranium metal assay standard 115

Certified reference material (CRM) 115, Uranium (Depleted) Metal (Uranium Assay Standard), was analyzed using a TRITON Thermal Ionization Mass Spectrometer to characterize the uranium isotope-amount ratios. The certified ²³⁵U/²³⁸U “major” isotope-amount ratio of 0.0020337 (12) in CRM 115 was determined using the total evaporation (TE) and the modified total evaporation (MTE) analytical techniques. In the MTE method, the total evaporation process is interrupted on a regular basis to allow correction of background from peak tailing, internal calibration of the secondary electron multiplier detector versus the Faraday cups, peak-centering, and ion source re-focusing. For the “minor” ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope-amount ratio measurements using MTE, precision and accuracy comparable to conventional analyses are achieved, without compromising the quality of the ²³⁵U/²³⁸U isotope-amount ratios. Characterized values of the ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope-amount ratios in CRM 115 are 0.000007545 (10) and 0.000032213 (84), respectively. The ²³³U/²³⁸U isotope-amount ratio in CRM 115 is estimated to be <5 × 10^?9. The homogeneity of the CRM 115 materials is established through the absence of any statistically significant unit-to-unit variation in the uranium isotope-amount ratios. The measurements leading to the certification of uranium isotope-amount ratios are discussed.     

Radionuclide activities and elemental concentrations in sediments from a polluted marine environment (Saronikos Gulf-Greece)

The levels and depth distributions of the natural radionuclides ²³⁸U, ²³²Th, ²²⁶Ra, ⁴⁰K and the man-made ¹³⁷Cs were analyzed by γ-ray spectrometry, while the concentrations of 26 chemical elements were measured by INAA in sediment samples collected from the organic mud layer that covers the Keratsini–Psitalia strait, Saronikos gulf (Greece). The average activity concentration values of ²²⁶Ra, ²³²Th and ⁴⁰K were lower when compared, whereas that of ²³⁸U was comparable to the average Greek and world values. The elemental contamination of the sediments was estimated on the basis of the calculated EF values. The results revealed high EF values of As, Br, Cr, Ni, Sb, Se, Zn ranging from 160 for Br to 10 for Cr, whose main sources are probable related to contaminated sewage outfall from the area of Athens and the Piraeus Harbour.

     

Validation of the quantification of natural radionuclides in raw materials and by-products using gamma-ray spectrometry

The validation of a method for the indirect quantification for ²³⁸U, ²²⁶Ra, and ²³²Th activity and the direct quantification for ⁴⁰K activity using gamma-ray spectrometry was performed in view of consistency, reliability, and accuracy of the results. The gas tightness of Al containers used to confine the radon gas was verified from the establishment of the secular equilibrium between ²²⁶Ra and its indicator. To evaluate validation parameters such as linearity, range, and accuracy, it was important to verify the equilibrium state of the reference materials (RM) for U and Th, because the ingrowth of progenies in the uranium decay series can affect the quantification of ²²⁶Ra activity even if based on a certified reference material (CRM), while the ingrowth of ²²⁸Ra from the thorium decay series should be secured in order to use ²²⁸Ac as an indicator of ²³²Th. In addition, the ruggedness of the method regarding different materials was checked using two kinds of CRM, namely bauxite as an example of a raw material and coal fly ash as a by-product.     

Concentration of 238U and 232Th among constituent minerals of two igneous plutonic rocks exhibiting elevated natural radioactivity levels

The concentrations of ²³⁸U and ²³²Th of the constituent minerals in two plutonic rock samples, from N. Greece, exhibiting elevated levels of bulk rock natural radioactivity were determined by using LA-ICP-MS. The available data of whole rock ²³⁸U and ²³²Th concentrations were also used. The minerals were separated using a combination of heavy liquids of various densities, shaking table and magnetic separation techniques. The great variation in the concentrations of ²³⁸U and ²³²Th is probably indicative of the different distribution of U and Th within the same rock, as well as to secondary post-magmatic processes that were responsible for the redistribution of U and Th. An estimation of the contribution of each mineral constituent to the natural radioactivity levels of the bulk rock is attempted. Thorite and zircon contribute the most to the whole rock ²³⁸U and ²³²Th content, while the contribution of apatite is moderate. The contribution of the rest of the minerals examined (fluorite, quartz, plagioclase, K-feldspar, amphibole, pyroxene, magnetite and biotite) is not important.     

Gamma-ray spectroscopic and PIXE analysis of selected samples from the phosphorite deposits of Northwestern Saudi Arabia

Phosphorite deposits from northwestern Saudi Arabia were analyzed by natural radioactivity measurements to detect the presence of radioactive elements. PIXE was used to obtain an average elemental composition of these deposits. From the analysis of radiations from ²³⁸U, ²³²Th and ⁴⁰K isotopes, the samples were found to contain U, Th and K in concentrations up to 130 ppm, 30 ppm and 2.5 wt%, respectively. PIXE showed the presence of a number of trace elements such as Ca, V, Cr, Fe, Ni, Cu, Zn, As, Sr, Y and U in concentrations ranging from a few ppm to several hundred ppm. The occurrence of these radioactive and non-radioactive elements are discussed for their geological significance in the phosphorite deposits.     

Study of naturally occurring radioactive material (NORM) in top soil of Punjab State from the North Western part of India

The concentration levels of ²³⁸U, ²³² Th, ⁴⁰K and ¹³⁷Cs in top soils of State of Punjab located in the North Western part of India were measured using conventional low background gamma ray spectrometric setup as well as Compton suppressed gamma ray spectrometric setup. The radioactivity level of ²³⁸U and ²³²Th was found to vary between 15 Bq/kg and 27 Bq/kg and between 16 Bq/kg and 57 Bq/kg respectively. The radioactivity level of ⁴⁰K was found to vary between 266 Bq/kg and 799 Bq/kg. The mean radioactivity level of the NORM in general was found to be similar to what is expected as a result of their normal abundance.     

238U and 232 Th concentrations in various potable waters in Morocco and resulting annual equivalent doses for the population

Summary The ²³⁸U and ²³² Th concentrations were measured in various potable water samples collected from various cities in Morocco using CR-39 and LR-115 type II solid state nuclear track detectors (SSNTDs). The measured ²³⁸U and ²³² Th concentrations ranged from 0.37±0.02 to 13.60±0.97 mBq ^. l^-1 and 0.33±0.02 to 7.10±0.49 mBq ^. l^-1, respectively. Alpha-activities due to annual ²³⁸U and ²³² Th intakes were assessed in various compartments of the human body of adult members of the Moroccan population using ICRP biokinetic models. The equivalent doses due to annual intakes of ²³⁸U and ²³² Th were evaluated. The influence of the target tissue mass and the activities of ²³⁸U and ²³² Th on the annual committed equivalent doses in the compartments of the human body was investigated.     

Geochemistry and health burden of radionuclides and trace metals in shale samples from the North-Western Niger Delta

Organic sedimentary rock samples were collected from three Oil Wells in the North-Western Niger Delta, Nigeria in order to determine their natural radioactivity and elemental geochemistry, with the aim of determining the concentrations of major radionuclides and their radiological and environmental health implication. The PIXE method of IBA technique and an accurately calibrated Si(Li) detector system was used to measure the elemental concentration of the sediment samples. The radionuclides identified belong to the decay series of naturally occurring radionuclides headed by ²³⁸U and ²³²Th along with the non-decay series radionuclide, ⁴⁰K. The activity concentrations of the radionuclides and their derived dose were then calculated. The average activity concentrations of ⁴⁰K were 248 Bq/kg for Well A, 261 Bq/kg for Well B and 273 Bq/kg for Well C. For ²³²Th the activity concentrations were 1,043 Bq/kg for Well A, 1,400 Bq/kg for Well B, 1,434 Bq/kg for Well C. ²³⁸U activity concentrations were 2,210, 3,508 and 250 Bq/kg for the Oil Wells A, B, C, respectively. The equivalent dose ranges from 8.5 ± 1.1 to 24.3 ± 2.1 mSv/year with a mean of 14.5 ± 2.2 mSv/year for Oil Well A, 2.4 ± 0.1–75.0 ± 1.2 mSv/year with a mean of 21.5 ± 1.1 mSv/year for Oil Well B and 3.7 ± 0.2–10.7 ± 0.6 mSv/year with a mean of 9.4 ± 2.5 for Oil Well C. The detected trace metals were majorly V, Ni, Pb, Fe, Cr, Cu, Zn, Co and their concentrations together with those of the radionuclides are compared with the relevant world standard limits. The results obtained were high, and hence, the radioactivity level and trace element content of the sediment samples from the North-Western Niger Delta Oil province could constitute health hazard to occupationally exposed workers, and to the public if not properly disposed. However, despite the careful disposal practice claims by the Oil industries, and given the high concentrations, the sediments could still pose an intrinsic health hazard considering their cumulative effects in the environment.     

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.     

Evaluation of natural gamma radiation and absorbed gamma dose in soil and rocks of Perambalur district (Tamil Nadu,India)

The activity concentrations and absorbed gamma dose of primordial radionuclides ²³⁸U, ²³²Th and ⁴⁰K were determined employing γ-ray spectrometry in 31 soil samples from the land area earmarked for house construction in Perambalur district and 14 rock samples from quarries that supply stones for the entire district. The soil samples registered relatively a higher mean value of 13.2 Bq kg^?1 for ²³⁸U, 66 Bq kg^?1 for ²³²Th and 340.3 Bq kg^?1 for ⁴⁰K as compared to mean values for rock samples (²³⁸U—8.0 Bq kg^?1; ²³²Th—65.1 Bq kg^?1; ⁴⁰K—199.1 Bq kg^?1). The mean absorbed gamma dose rate for soil (61.4 nGy h^?1) marginally exceeded the prescribed limit of 55 nGy h^?1 while, rocks registered the mean absorbed gamma dose rate of 10.4 nGy h^?1. The mean radium equivalent activity was distinctly higher in soil (130.6 Bq kg^?1) than in rock (20.0 Bq kg^?1). However, these values were lower than the limit (370 Bq kg^?1) set by OECD for building materials. It is evident from the data that the soil and rocks do not pose any radiological risk for house constructions in Perambalur district.     

Natural radioactivity and its gamma dose rate in Mission (Texas) soils

The activity concentration of radionuclides in ²³⁸U, ²³²Th, and ⁴⁰K were determined in Mission (Texas) surface soils through gamma-ray spectrometry measurements using hyper pure germanium detector. Activity concentrations of ²³⁸U, ²³²Th, and ⁴⁰K were 13–32 Bq kg^?1 (mean value: 23 Bq kg^?1), 17–47 Bq kg^?1 (mean value: 31 Bq kg^?1), and 100–460 Bq kg^?1 (mean value: 300 Bq kg^?1) respectively. The absorbed gamma dose rate in air from these soils were found in the range of 23 to 56 nGy h^?1 with an average value of 42 nGy h^?1. The contribution to the absorbed gamma dose rate in air was observed as 26 % from ²³⁸U, 45 % from ²³²Th, and 29 % from ⁴⁰K. The outdoor annual effective dose equivalent varied between 28 and 69 μSv y^?1 with the mean value of 52 μSv y^?1.The evaluated data were compared with the data from different countries and also with the world mean value.     

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.     

Assessment of ingestion dose due to radioactivity in selected food matrices and water near Vizag,India

Activity concentrations of ²³⁸U, ²³²Th, ²²⁶Ra, ⁴⁰K and ¹³⁷Cs were measured in milk, egg, fruit and fish samples collected around a proposed site for setting up nuclear facilities, near Vishakhapatanam. The activity concentrations of the radionuclides ranged from 0.002 to 10.6, 0.002 to 2.8, 0.1 to 7.2, 3 to 110.8, 0.03 to 3 mBq g^?1 for ²³⁸U, ²³²Th, ²²⁶Ra, ⁴⁰K and ¹³⁷Cs considering analysed food matrices. Natural uranium was measured in drinking water samples and the values were below 15 ppb. The average ingestion dose was 2.07 ± 2.01, 2.81 ± 4.38, 7.66 ± 8.24, 1.28 ± 0.84 and 0.04 ± 0.05 μSv year^?1 for ²³⁸U, ²³²Th, ²²⁶Ra, ⁴⁰K and ¹³⁷Cs in milk, egg, fruit, fish and water. The ingestion dose received was the highest for milk, due to its high ingestion rate. It was observed that ²²⁶Ra is the largest contributor of measured radionuclides in this study for the different food matrices analysed due to its high dose conversion factor. The study was carried out as a part of baseline data generation for this region with which future changes in the radiological scenario can be compared.     

Determination of Th and U in bone ash by ICP-ion source mass spectrometry

The feasibility of ICP-ion source mass spectrometry (ICP-MS) for the determination of²³²Th and²³⁸U in bone ash was studied. Bone ash samples were further decomposed with concentrated nitric acid under pressure in PTF crucibles. The resultant solution was diluted and subjected directly to the measurement with an ICP mass spectrometer. The effects of diluting and removing matrix elements on ICP-MS measurements of these nuclides were studied. The accuracy of the determinations was evaluated with the measurement of NBS Human Lung (SRM 4351) which was originally certified for alpha activities of²³²Th and²³⁸U.     

Natural radioactivity in rocks of the Modane–Aussois region (SE France)

The activity concentrations of ⁴⁰K, ²³²Th, and ²³⁸U in the characteristic rocks of the Modane-Aussois region (Western Alps, France) were determined using an HPGe gamma-ray spectrometry system. The activity concentrations of ⁴⁰K varied from 18 Bqkg⁻¹ (limestone dolomite) to 392 Bqkg⁻¹ (calcschist), while those of ²³²Th varied from 0.7 Bqkg⁻¹ (limestone dolomite) to 18 Bqkg⁻¹ (calcschist). The activities associated with ²³⁸U ranged from 9 (quartzite) to 29 Bqkg⁻¹ (dolomite). In the investigated rock samples, concentrations of ²³⁸U (ppm) and ⁴⁰K (%) had a strong negative correlation.     

Uranium isotope dilution mass spectrometry using NBL certified reference materials as spikes

The isotope dilution mass spectrometry method of analysis is used to determine the elemental uranium contents in a wide variety of uranium bearing materials. The method is based on the mass spectrometric analysis of a mixture prepared by diluting the sample to be analyzed with a spike of distinctly different isotopic composition to that of the sample. In this work, a beginning is made to identify suitable candidates among the multitude of certified reference materials (CRMs) available at the New Brunswick Laboratory to supplant the use of ²³³U which remains now as the preferred spike nuclide. The results of the study presented here identify CRM 112-A (of normal isotopic composition) and CRM 115 (depleted uranium composition) as suitable candidates to replace ²³³U as spike material for determining uranium in high enriched uranium materials, and CRM 116 (²³⁵U mass fraction of >90 %) for determining uranium in materials of low enrichment.     

Effect of alteration processes on the distribution of radionuclides in uraniferous sedimentary rocks and their environmental impact, southwestern Sinai, Egypt

The contents of natural radionuclides in various types of sedimentary rocks in Um Bogma Formation and base of El Hashash Formation were determined by gamma-ray spectrometry. Three types of lower Carboniferous sedimentary rocks were investigated; sandstone (El Hashash Formation), dolostone and argillaceous sediments (Um Bogma Formation). The alteration processes are dolomitization, dedolomitization, karstification and lateritization. The specific radioactivity of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K determined in different samples, indicate that ²³⁸U and its decay products contribute primarily to the high natural radioactivity of rocks. The maximum concentration of ²³⁸U reached up to 2129.36 ppm in argillaceous sediments. The average concentrations of determined radionuclides (²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K) are 8.34 ppm, 7.88 ppm, 4.68 ppm and 0.3%, respectively in sandstone. In dolostones the average concentrations are 418.69 ppm, 808.75 ppm, 3.14 ppm and 0.29%, respectively. For argillaceous sediments are 276.88 ppm, 419.49 ppm, 11.47 ppm and 0.93%, respectively. The ²³⁸U/²²⁶Ra ratio in sandstone ranges between 0.89 and 1.25, while in dolostones and argillaceous sediments are 0.27–2.63 and 0.27–1.83, respectively. These variations in the concentrations of radioelements and their ratios are due to the action of the alteration processes affected these different sedimentary rocks in different times. Environmentally, the Ra_eq in dolostones and argillaceous sediments exceeds the permitted limits, while in the sandstone samples; it is within the permissible levels.