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.     

Interpretation of thorium bioassay data

This study is a comparison between bioassay data of thorium-exposed workers from two different facilities. The first of these facilities is a monazite sand extraction plant. Isotopic equilibrium between²³²Th and²²⁸Th was not observed in excreta samples of these workers. The second facility is a gas mantle factory. An isotopic equilibrium between²³²Th and²²⁸Th was observed in excreta samples. Whole body counter measurements have indicated a very low intake of thorium through inhalation. As the concentration of thorium in feces was very high we concluded that the main pathway of entrance of the nuclide was ingestion, mainly via contamination through dirty hands.The comparison between the bioassay results of workers from the two facilities shows that the lack of Th isotopic equilibrium observed in the excretion from the workers at the monazite sand plant possibly occurred due to an additional Th intake by ingestion of contaminated fresh food. This is presumably because²²⁸Ra is more efficiently taken up from the soil by plants, in comparison to²²⁸Th or²³²Th, and subsequently,²²⁸Th grows in from its immediate parent,²²⁸Ra.     

Radionuclide levels and temporal variation in phosphogypsum

Summary Three samples of phosphogypsum of different ages were analyzed for natural radioelements using high-resolution gamma-ray spectrometry. The phosphogypsum samples were taken from the filter of a 10-year old pile, and a 50 year old pile. The distribution of ²²⁶Ra remains relatively constant as a function of storage time (up to 50 years) which confirms the immobility of ²²⁶Ra in the phosphogypsum matrix. However, the concentration of ²³⁸U and ²³² Th have shown a decreasing tendency going from the most recent sample to the oldest. For radionuclides belonging to the ²³² Th series, we noticed an enrichment factor of 1.5 for ²²⁸Ac in the most recent phosphogypsum, whereas the right proportions exist for the other two samples. This is due to the fact that most of the thorium fractionates to the phosphoric acid during the production process and the equilibrium between ²³² Th and its descendants is not yet reached for fresh phosphogypsum.     

Thorium series disequilibrium and geochemical processes in estuarine sediments of Mandovi river

The measurements of natural radioactivity due to thorium isotopes have been carried out in estuarine sediments of Mandovi river (Goa). The geochemical behaviour of these sediments has been studied by leaching the samples with 5 % ethylenediaminetetraacetic acid at pH 3.0 in order to investigate the processes occurring on the surface of the sediment particles and the distribution of natural thorium in estuarine sediments. The²²⁸Th/²³²Th activity ratios have been found to be in the range of 2.00 to 2.12. This anomaly between²³²Th and²²⁸Th has been attributed to the preferential leaching of²²⁸Ra by water flowing over these sediments. The activities of²²⁸Ra on the surface labile layers of the sediments have also been determined. The²³⁰Th/²³²Th activity ratios have been found to be in the range of 0.94 to 1.04. These ratios are mainly dependent on the precipitation action of²³⁰Th on adjacent sediments.     

Development of a sequential method for the determination of238U,234U,232Th,230Th,228Th,228Ra,226Ra,and210Pb. in environmental samples

A sequential analytical method for the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th,²²⁸Th,²²⁸Ra,²²⁶Ra and²¹⁰Pb in environmental samples was developed. Uranium and thorium isotopes are first chromatographically sepaaated using tri-n-octyl phosphine oxide (TOPO) supported on silica gel. The uranium isotopes are determined by alpha-spectrometry following extraction with TOPO onto a polymeric membrane. Thorium isotopes are co-precipitated with lanthanum fluoride before counting in an alpha spectrometer. Radium isotopes and²¹⁰Pb are separated by co-precipitation/precipitation with mixed barium/lead sulphate. Radium-226 is determined by gross alpha counting of the final BaSO₄ precipitate and²²⁸Ra by gross beta counting of the same source. Lead-210 is determined through beta counting of its daughter product²¹⁰Bi.     

New radiochemical procedures for environmental actinide measurements and data quality control

Suitable separation techniques were prepared for actinide,⁹⁰Sr and²²⁶Ra determinations in environmental and industrial samples. Extraction chromatography with tri-n-octylphosphine oxide (TOPO) and di(2-ethylhexyl) phosphoric acid (HDEHP) solutions was used. IN some cases, a powder of Microthene (Microporous polyethylene) supporting solid TOPO was prepared thus obtaining a material showing better storing and column preparation features.Uranium and²²⁶Ra were determined in phosphorites, phosphoric acid and phosphogypsum.Uranium, thorium and²²⁶Ra were also measured in the low specific activity scales of hydrocarbon production equipment:²²⁶Ra was found to concentrate in some parts of the plant so causing a radiation protection problem.Plutonium and⁹⁰Sr were measured either in some Mediterranean Sea samples or in environmental samples collected in Antarctica. Some interesting sea sediment profiles were also obtained.All the chemical methods were verified by: a) adding some yield tracers (²³²U,²²⁸Th,²⁴²Pu); b) analyzing some certified samples supplied by IAEA and NIST; c) participating in some international intercomparison runs; d) using, when possible, both an analytical and a radiometric method and e) following the radioactivity decay or growth (⁹⁰Y and²²⁶Ra).     

Hokutolite collected from riverbed at Peitou Hot Spring in Taiwan: With emphasis on radiochemical studies

Summary Hokutolite, and hot spring water and river water collected recently at Peitou Hot Spring in Taiwan were analyzed for U, Th, Ra and ²¹⁰Pb isotopes. Concentrations of major chemical elements were also measured. Hokutolite had its typical chemical composition make-up for this area. The concentrations of ²³⁸U, ²³⁴U, ²³² Th, ²³⁰ Th, ²²⁸ Th, ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb in samples scrapped into 7 layers from the surface to the bottom of a hokutolite specimen were 0.0021-0.0068, 0.0022-0.0075, 1.47-2.07, 1.00-1.29, 1.56-1.97, 56.7-68.6, 1.46-2.06 and 25.9-36.0 Bq/g, respectively. All the radionuclides exhibited a relatively uniform distribution, and radioequilibrium was confirmed among ²³² Th, ²²⁸Ra and ²²⁸ Th. From the relationship between the decay and growth of Th-series nuclides it was considered that the hokutolite studied was isolated from the stream water at least 70-80 years ago. The U/Th-series radionuclides in the hot spring water were in rather high concentrations and the enrichment of ²²⁸Ra and ²²⁸ Th to ²³² Th was the most prominent feature. Evaluation of the distribution coefficients (K_d) using the data on hot spring water or river water and hokutolite indicated that Th (K_d = 10⁴-10⁵) in water was likely to be precipitated (and/or co-precipitated) with BaSO₄ as Th(SO₄)₂ with a relatively high concentration into hokutolite, together with Ra (K_d = 10⁶-10⁷).     

A generator for preparation of carrier-free224Ra

The construction of a dynamic generator for the separation of carrier-free²²⁴Ra is described. The mother²²⁸Th was extracted on the top of the column with di-(2-ethylhexyl)phosphoric acid on hydrophobized Chromosorb W DMCS. The function of the generator was checked during 6 months by measuring the decontamination of²²⁴Ra from²²⁸Th. Simultaneously the yield of²²⁴Ra was determined as a function of the HCl concentration and of the means of milking. The best results were obtained with 0.01–0.1M HCl; the yield was about 75% of the theoretical value, and the²²⁴Ra contained less than 0.01% of²²⁸Th.     

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.     

Accurate determination of naturally occurring radionuclides in Philippine coal-fired thermal power plants using inductively coupled plasma mass spectrometry and γ-spectroscopy

There is an increased interest in measuring naturally occurring radioactive materials (NORM) like coal, fly ash considering health hazards caused by naturally occurring radionuclides. This paper presents activity concentration (AC) of ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁸U and ⁴⁰K in feed coal, bottom and fly ash samples from Philippines coal-fired thermal power plants using inductively coupled plasma mass spectrometry (ICP-MS) and high-purity germanium gamma spectroscopy (HPGe γ-spectroscopy). Coal, bottom and fly ash samples were digested using a microwave oven with a mixture of HNO₃, HClO₄ and HF. Uranium (²³⁸U) and thorium (²³²Th) ACs were also analyzed from samples using ICP-MS. A good correlation was found for the measurement of U and Th using both techniques (R² = 0.97 and 0.94 respectively). ICP-MS measurements showed the highest AC of ²³²Th and ²³⁸U in fly ash and lowest for feed coal samples. With HPGe γ-spectroscopy measurements, highest AC (in Bq kg^{− 1}) of ²²⁶Ra, ²²⁸Ra, ²²⁸Th and ⁴⁰K, were noticed in fly ash followed by bottom ash and feed coal. ICP-MS method is rapid for the measurement of uranium and thorium in comparison to γ-spectroscopy as secular equilibrium is not required. Activity concentrations of bottom and fly ash samples were found to be within the reported values worldwide and below the International Atomic Energy Agency recommended values for regulatory control.     

Natural radioactivity in bioassay by alpha-spectrometry measurements

Personnel of nuclear facilities are checked regularly for internal contamination by bioassay measurements. Although these persons are generally not involved in any incident, natural radioactivity from U, Th and Ra can be found in their urine or faeces. Uranium total activity in urine has been found with a range of 0.051 to 3.0 mBq/24 h and in faeces from 14.5 to 380 mBq/d. ²³⁴U/²³⁸U ratio for urine is 1.48 but this ratio varies from 0.47 to 19. By comparison, the ²³⁴U/²³⁸U ratio found in urine from workers in volved with natural uranium or 4.5% enriched uranium is 1.0 and around 4.0 respectively. ²³⁰Th, ²²⁸Th and sometimes ²³²Th have also been detected. The total thorium activity varies from 0.137 to 5.6 mBq/24 h in urine and from 9 to 183 mBq/d in faeces. ²²⁸Th has generally been found in excess of ²³²Th. All these measurements were performed by alpha-spectrometry. The few ²²⁶Ra results have been measured using the Lucas or emanation method.     

Message to the participants of the conference

The activity of²³²Th and its daughters in Th-based gas sockets is required for health risk assessment. By absolute measurement of the²²⁸Ac- and²¹²Pb/²⁰⁸Tl-activities, the total activity of the sockets can be assessed. It is governed by²²⁸Ra and²²⁸Th and the product age.     

A study on thorium levels in human femur bones

The incorporation of naturally occurring thorium isotopes in human femur bones was studied by analyzing 28 bone samples. The results show that the activity concentrations of ²³²Th and ²³⁰Th are in the range of the blank values resulting in an upper limit of theirs activity concentrations in human bones. The presence of ²²⁸Th can be attributed, on the basis of model calculations, to the radioactive decay of deposited ²²⁸Ra. We conclude that thorium is not detectably incorporated into human bones.     

Radium,uranium and thorium concentrations in low specific activity scales and in waters of some oil and gas production plants

Low specific activity scales consisting of alkaline earth metal carbonates and sulfates are often present in some gaseous and liquid hydrocarbon plants; these scales contain a certain concentration of radium, uranium and thorium, which can cause a risk of -irradiation and of internal radiocontamination when they must be mechanically removed. That being stated,²³⁸U,²³²Th and²²⁶Ra were determined in scales, sludges and waters coming from different plants.²³⁸U and²³²Th concentrations were found very low; the isotopes²³⁸U and²³⁴U resulted in radioactive equilibrium, whilst²³²Th and²²⁸Th were not always in equilibrium.²²⁶Ra concentration was higher in scales and sludges than in waters.     

Radioactive series disequilibria in underground uranium deposits of the Singhbhum Shear Zone, Eastern India

Radionuclides of the ²³⁸U series (²²⁶Ra, ²¹⁰Pb, ²³⁴Th and ²³⁴U), ²³⁵U series (²²⁷Ac and ²³¹Pa) and ²³²Th series (²²⁸Th and ²²⁸Ra) series were measured by High Resolution Gamma Spectrometry system in twenty-five uranium ore samples from underground uranium deposits in the Singhbhum Shear Zone of Eastern India. The activity concentrations were observed to vary within a wide range in most of the deposits, as is the case in most rocks of crustal origin. The uranium ore from these deposits were not of high ore grade (U concentrations ranged from 0.015 to 0.082%). Activity ratios of key daughter–parent pairs from the decay chains, viz. ²²⁶Ra/²³⁸U, ²²⁶Ra/²¹⁰Pb, ²³¹Pa/²³⁵U, ²²⁷Ac/²³⁵U, ²³⁰Th/²³⁸U, ²³⁴U/²³⁸U, ²²⁶Ra/²³⁰Th and ²²⁸Th/²²⁸Ra indicated migration/accumulation of uranium and radium in some samples. The ²²⁶Ra/²³⁰Th ARs suggested that the deposits were not closed to groundwater movement for a maximum time period of 8ky. Thiel plot of the ²³⁴U/²³⁸U vs. ²³⁰Th/²³⁸U activity ratios indicated uranium accumulation and complex processes of uranium redistribution.     

Natural and Artificial Radionuclides in Selected Lignites from Istanbul

The radioactivity levels of Istanbul environs lignites were determined. The gamma-spectrometric technique has been used for the determination of activity levels of naturally occurring radionuclides ^235+238U, ^228+232Th, ⁴⁰K, ²²⁶Ra and fallout radionuclides ¹³⁷Cs in lignites taken from 7 different parts of Istanbul. Concentration of ²³⁸U, ^228+232Th, ⁴⁰K, ²²⁶Ra ¹³⁷Cs and ²³⁵U were found up to 1.6 ppm, 1.7 ppm, 4.9 ppm, 56.8 Bq/kg, 34 Bq/kg, 1.8 Bq/kg, 1.6 Bq/kg, respectively. In addition total alpha- and beta-activity levels in lignite samples were found to be 7.6 and 15 eps, respectively.     

Estimation of growth rate of hokutolite from Tamagawa hot-spring,Akita, Japan

The concentrations of radium isotopes and the progenies (²²⁶Ra; ²²⁸Ra and ²²⁸Th) in three hokutolite samples from Tamagawa hot-spring were measured. These isotopes were analyzed by a well-type HPGe γ-ray spectrometer for the 351, 911 and 583 keV γ-ray from ²¹⁴Pb, ²²⁸Ac and ²⁰⁸Tl, respectively, each being in radioactive equilibrium with precursors. Concentration of ²²⁶Ra and ²²⁸Ra were observed to be in the range of 52–85 and 7.1–85 Bq/g, respectively. The activity ratios of ²²⁸Ra/²²⁶Ra and ²²⁸Th/²²⁶Ra provided the estimation of the growth rate (0.09–0.15 mm/y). Estimated ²²⁸Ra/²²⁶Ra activity ratios in hot-spring water from surface of three hokutolite were concordant.     

Lichen specie Canoparmelia texana as bioindicator of environmental impact from the phosphate fertilizer industry of São Paulo,Brazil

The Brazilian phosphate industry is the sixth worldwide producer of phosphate rock concentrate generating phosphoric acid, fertilizers, intermediates for fertilizers and other products. Two of the most important of these industries are both located in the city of Cubatão—São Paulo, Brazil, and they are responsible for the production of P₂O₅, generating a residue known as phosphogypsum. The raw material, phosphate rock and products are commonly transported to the industrial complex by a railroad line and present in their composition natural radionuclides from the U and Th series and rare earth elements. Lichens have been used for monitoring atmospheric pollution and radiological contamination for a long time and have proven to be an important tool. This paper aims to highlight the use of the lichen specie Canoparmelia texana (family Parmeliacea) as a bioindicator of atmospheric pollution by the natural radionuclides from the U and Th series and RREs due to the operation of these industries and the storage of their residue in the open air. Samples of these lichen specie were collected in the vicinity of the industries and the railroad. The radionuclides ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb were measured by alpha and beta counting, after radiochemical separation, and ²³⁸U, ²³²Th as well as REEs were determined by instrumental neutron activation analysis. The results showed that the lichens present the same fingerprint as the phosphate rock and phosphogypsum, furthermore the cluster analysis of the results showed that the lichen samples collected near to the railroad line presented the highest values for all the elements studied.     

Natural radionuclides in Italian diet and their annual intake

This study was dedicated to the evaluation of the background activity concentration of natural radionuclides as ²²⁸Ra and ²²⁸Th of ²³²Th family, ²²⁶Ra of ²³⁸U family and ⁴⁰K in the Italian daily diet. These radionuclides were determined by gamma spectrometry. ⁴⁰K activity concentration, in the samples taken into account in the present paper, ranged between 70.5 (milk) and 181.1 Bq kg _ww ^?1 (pasta), ²²⁶Ra activity concentration ranged between 1.1 (milk) and 5.7 Bq kg _ww ^?1 (pasta), ²²⁸Ra and ²²⁸Th activity concentration, in the same samples, ranged between 0.7 (milk) and 3.7 Bq kg _ww ^?1 (pasta) and between 1.4 (milk) and 6.1 Bq kg _ww ^?1 (flours) respectively. The annual intake of every radionuclide from foodstuffs ingestion was also calculated. The 94–95 % of the total intake comes from ⁴⁰K. For adults and children, the highest activity intake of all radioisotopes was from grain products, for infants it was from milk products.     

Determination of228Th,230Th,and232Th in environmental samples from uranium mining and milling operations

A method is described for the determination of²²⁸Th,²³⁰Th, and²³²Th in environmental samples from uranium mining and milling operations. The analytical procedure is based on the direct determination of²²⁸Th in the sample by high resolution γ-spectrometry followed by extraction and purification of the thorium fraction using high molecular weight amines and an anion-exchange technique, respectively, prior to α-spectrometry to determine isotopic ratios. The lowest level of detection for each thorium isotope is 0.01 pCi/g for solid samples and 20 pCi/l for aqueous samples. Replicate analyses of a typical mine waste stream gave a standard deviation of ±3% for²²⁸Th. Standard deviations of the²³⁰Th and²³²Th increased to ±11% apparently due to traces of²¹⁰Po interfering in the α-spectrometry.