Efficacy of zeolites in radon adsorption: state of the art and development of an optimized approach.

Radon is a radioactive noble gas omnipresent in the environment, being part of the 238U and 232Th decay chains present in the Earth's crust. The gas can easily leak through the ground but also be present in natural construction materials and migrate into indoor places where it can be a carcinogen when inhaled. Studying the content and removal of indoor radon is crucial for the evaluation and mitigation of its radiological risks to public health. For more than 100 years, the removal by adsorption of the radon has been performed on activated charcoal. There is little progress in the field of radon adsorption at ambient conditions; the main progress is in the use of zeolite materials, having well-defined three-dimensional porous structures and radiation resistance. This study concerns a report on the state of the art of the application of zeolites in radon adsorption. Furthermore, an optimized approach for measuring the radon content in indoor environments and, consequently, its removal has been proposed. Adsorption systems based on zeolites have the potential to replace activated charcoal as a material of choice, allowing to facilitate the development of simple and compact radon adsorption systems.

Reduction of detection limits in monitoring of internal exposures by a combined evaluation of emissions and spectra.

Routine monitoring of internal exposures requires the detection of effective doses of at most 1 mSv per calendar year. For some radionuclides, this requirement cannot be satisfied by a conventional evaluation of the spectra that are gained in alpha or gamma spectrometry. However, since several measurements are conducted per calendar year on a regular basis, a combined evaluation of measurements, i.e. the evaluation of sum spectra, is possible. Additionally, radionuclides that feature several emissions of alpha or gamma radiation allow a combined evaluation of their emissions. Both methods can lead to significantly smaller detection limits as compared to a separate evaluation of spectra in many cases. However, the variation of parameters that influence the evaluation such as the measurement efficiency, abundance and chemical yield requires specific calculations and treatments of the spectra as well as a manipulation of the channel contents: In a combination of emissions, energy regions are summed and evaluated with a combined efficiency that is weighted by the abundances. In a combination of spectra, the channel contents must be scaled by the ratio of the calibration factors before the summation of the spectra. In the routine monitoring of short-lived radionuclides that feature a variety of emissions such as 225Ac, these combinations are particularly effective in reducing the detectable annual effective dose. For alpha spectrometry of 225Ac, both methods applied together can lead to a detectable effective dose of about 1 mSv per year as compared to a dose of about 90 mSv with a conventional separate evaluation.

Actinium-225 as an example for monitoring of internal exposure of occupational intakes of radionuclides in face of new nuclear-medical applications for short-lived alpha emitting particles.

Monitoring of internal exposure to short-lived alpha-emitting radionuclides such as actinium-225 (225Ac), which are becoming increasingly important in nuclear medicine, plays an important role in the radiation protection of occupationally exposed persons. After having tested gamma spectrometry, liquid scintillation counting and alpha spectrometry for monitoring of internal exposure, the focus of the present study was on solid phase extraction of 225Ac from urine in combination with alpha spectrometry. The development of the method was based on recent findings from the literature on this topic. The method was used in a pilot phase to monitor internal exposure of four workers who were directly or indirectly involved in the manufacture and/or use of 225Ac. The monitoring protocol allowed a relatively short 24-hour urine sample analysis with excellent recovery of the internal standard, but it did not allow for a detection limit of less than 1 mBq nor a sufficient yield of 225Ac. Based on these results it is concluded that an in vitro excretion analysis alone is not appropriate for monitoring internal exposure to 225Ac. Instead, different radiation monitoring techniques have to be combined to ensure the radiation protection of employees.

A baseline of natural radionuclides in water and sediment of a pristine coastal ecosystem: The Xcalak and Mahahual coral reef lagoons in the western Caribbean.

In ecosystems, natural radionuclides are present in the environment and living organisms. The 238U natural decay chain produces multiple radioactive elements, such as 234U, 226Ra, 210Pb, and 210Po. These radionuclides can be found in air, water, rocks, soil, and other biotic and abiotic components, mainly derived from minerals, such as zircon and apatite. In this study, we determined the activity concentration of radionuclides from the 238U decay chain in the sediment of a coastal ecosystem on the southern Mexican coast in the western Caribbean, an ecosystem minimally affected by industrial activities. Methods included high-resolution gamma-ray spectrometry and alpha-particle spectrometry. Results showed that the sediment samples had an activity concentration range of 18.2-36.6 Bq/kg for 238U, 25.0-41.4 Bq/kg for 234U, 10.1-37.3 Bq/kg for 210Pb, and 29.9-46.0 Bq/kg for 210Po. Water samples ranged between 17.9 and 36.3 mBq/L and 27.9-66.0 mBq/L for 238U and 234U, respectively. The activity concentration of these radionuclides in the sediment and water of this area is compared with that of other coral reefs worldwide, providing a radiometric baseline for comparison purposes.

Radon Exhalation Rate: A Metrological Approach for Radiation Protection.

Radon, a radioactive inert gas that comes from the decay of naturally occurring radioactive species, poses a substantial health risk due to its involvement in lung cancer carcinogenesis. This work proposes a metrological approach for determining radon exhalation rates from diverse building materials. This methodology employs an electrostatic collection chamber for alpha spectrometry of radon isotopic decay products. Experimental evaluations were conducted particularly focusing on volcanic gray tuff from Sant'Agata de' Goti (Campania region, Italy), a material commonly utilized in construction, to assess radon exhalation rates. The study aligns with Legislative Decree 101/2020, a transposition of European Directive 59/2013/Euratom, highlighting the need to identify materials with a high risk of radon exhalation. Moreover, this work supports the goals of the Italian National Radon Action Plan related to the aforementioned decree, aiming to develop methodologies for estimating radon exhalation rates from building materials and improving radioprotection practices.

An alternative approach to efficiency tracking in thorium determination in fertilizers by alpha spectrometry.

Fertilizers play a key role in increasing crop yield per unit land answering the growing demand for food production. However, excessive or improper use of fertilizers can lead to several environmental issues including soil contamination. One of the known contaminants attributed to fertilizers are radionuclides. The goal of this study was to determine the concentration of thorium isotopes in several types of commonly used fertilizers produced in Poland. The methodology included the use of an alternative tracer (namely 228Th) to evaluate chemical recovery. The correctness of the proposed method was confirmed by analyzing certified reference materials. The obtained results showed that the activity concentration of 232Th was ranged from <0.34 Bq kg-1 for nitrogenous fertilizer up to 97 ± 22 Bq kg-1 for pure phosphate fertilizer.

Accelerator mass spectrometry measurements of 233U in groundwater, soil and vegetation at a legacy radioactive waste site.

Low-level radioactive wastes were disposed at the Little Forest Legacy Site (LFLS) near Sydney, Australia between 1960 and 1968. According to the disposal records, 233U contributes a significant portion of the inventory of actinide activity buried in the LFLS trenches. Although the presence of 233U in environmental samples from LFLS has been previously inferred from alpha-spectrometry measurements, it has been difficult to quantify because the 233U and 234U α-peaks are superimposed. Therefore, the amounts of 233U in groundwaters, soils and vegetation from the vicinity of the LFLS were measured using accelerator mass spectrometry (AMS). The AMS results show the presence of 233U in numerous environmental samples, particularly those obtained within, and in the immediate vicinity of, the trenched area. There is evidence for dispersion of 233U in groundwater (possibly mobilised by co-disposed organic liquids), and the data also suggest other sources of 233U contamination in addition to the trench wastes. These may include leakages and spills from waste drums as well as waste burnings, which also occurred at the site. The AMS results confirm the historic information regarding disposal of 233U in the LFLS trenches. The AMS technique has been valuable to ascertain the distribution and environmental behaviour of 233U at the LFLS and the results demonstrate the applicability of AMS for evaluating contamination of 233U at other radioactive waste sites.

Standardization of Rn-222 concentration using the multi-electrode proportional counter.

Standardization of the concentration of gaseous 222Rn based on a multi-electrode proportional counter (MEPC) is under development as a primary standard in Japan. In this study, the concept and evaluation of its performance are reported. The latter consists of a preliminary result for the uncertainty budget associated with the measurement of the MEPC and compensation of the electric field distortion in the MEPC. Moreover, an ionization-chamber-based gas circulation system was added for the calibration of radon monitors in the air.

Measurement of the intensities of the long-range alpha particles from 212Po.

212Bi partially decays by ß- populating excited levels of 212Po. Some of these excited states of 212Po decay with very low probability by direct alpha-particle emissions instead of a gamma-alpha cascade. This effect was known since the earliest times after the discovery of radioactivity. Emission energies of these long-range alpha particles were measured in the past, but the activity ratios were not accurately determined. Relative intensities for these decays have now been experimentally determined. Results agree with data previously reported. It is the first time that an uncertainty estimate is provided for such experiment.

Biodistribution of naturally occurring radionuclides and radiocesium in wild European perch (Perca fluviatilis).

Wild European perch (Perca fluviatilis) is one of the most important freshwater fish species, in Sweden, due to its widespread and his value for recreational fishing. Little it is known regarding the biodistribution of naturally occurring radionuclides such as 238U, 234U, 226Ra, 210Po in perch. Therefore, in this study, perches from five lakes located in different counties in Sweden were collected to investigate the biodistribution of 238U, 234U, 226Ra, 210Po and 137Cs in organs and tissues of perch as well as their radiological impact. The results showed that uranium radionuclides ranged between 0.1 and 6 Bq/kg with an average value of 1.1 ± 1.5 Bq/kg. 226Ra varied from 0.4 to 8 Bq/kg with a mean concentration of 1.7 ± 1.9 Bq/kg. The ranged of 210Po was 0.5 - 250 Bq/kg, with an average value of 24 ± 52 Bq/kg. On the other hand, the highest activity concentration of 137Cs, 151 ± 1 Bq/kg, was detected in muscle samples of perch from Redsjösjön lake. For uranium radionuclides and 226Ra uptake from water is the main source whereas for 210Po and 137Cs the uptake is controlled by the perch diet. Regarding naturally occurring radionuclides, the perch tended to accumulated uranium radionuclides in fins, gills, and skin; 226Ra in bones, fins and skin and 210Po in the organs linked to digestive system. Finally, in case of consumption, it is advised the consumption of skinned fillets of perch due to the higher bioaccumulation of the radionuclides investigated in the skin and scales.

Experimental optimization of physicochemical factors for spontaneous deposition of 210Po using newly designed deposition kit.

A simple spontaneous deposition kit for 210Po determination using alpha spectrometry was newly designed, and polonium deposition characteristics under various physicochemical conditions were evaluated using it. The high-purity silver disc (99.99%) showed high deposition efficiencies of over 85.1% in the HCl concentration range of 0.01-6 M. Optimal physicochemical factors were determined to be a temperature of 90 °C, deposition time of 90 min, and the use of ascorbic acid as a reducing agent in an amount similar to that of the interfering element (Fe).

Increasing the recovery and selectivity of 238U, 235U, and 234U extraction with tri-n-butyl phosphate in mine tailing samples with a high copper content.

Abandoned Cu mine tailings may be associated high concentrations of U. However, the presence of stable cations such as Cu, Fe, Al, Ca, or Mg, etc. in high concentrations can reduce the chemical efficiency of the liquid-liquid extraction method with tri-n-butyl phosphate (TBP); it can also inhibit the electrodeposition of U on the stainless steel planchet where the sample is measured. In this work we studied an initial stage of complexation with ethylenediaminetetraacetic acid (EDTA) and a back extraction with different solutions: H2O, Na2CO3, and (NH4)2CO3 at room temperature and at 80 °C. The sensitivity of the method was 4.9·10-4 Bq for 238U and 234U, and 2.3·10-5 Bq for 235U. The validation of the method achieved 95% of the results when using a |ζ-score| ≤ ± 2.0 and a relative bias (RB[%]) ≤ ± 20% as the acceptance criteria. The recoveries obtained with the proposed method were higher than those achieved with the extraction method without initial complexation and re-extraction with H2O for water samples. Finally, this method was applied in practice to study the tailing of an abandoned Cu mine and the activity concentrations of 238U and 235U were compared with those obtained by gamma spectrometry for 234Th and 235U. The means and variances of both methods showed no significant differences between these two isotopes.

An innovative method for determination of uranium isotopes in soils by alpha-spectrometry coupled with Microthene-TOPO column separation.

In the new procedure for determination of uranium isotopes by α-spectrometry, silica in the leachate of fused soil samples was coated with polyethylene glycol 2000 and eliminated through filtration, and uranium isotopes were separated from other α-emitters with a Microthene-TOPO column and electrodeposited on a stainless steel disc for measurement. It was observed that treatment with HF has negligible contribution on the release of uranium from the leachate containing silicates, so the use of HF for mineralization can be avoided. The reference material IAEA-315 marine sediment was analysed, and the obtained 238U, 234U and 235U concentrations are in good agreement with the certified values. The detection limit for soil samples was 0.23 Bq kg-1 for 238U or 234U and 0.08 Bq kg-1 for 235U if 0.5 g of samples were analysed. Method application shows that (1) the yields are high and stable, and (2) no interference from other α-emitters are observable in the final spectra.

Alpha spectrometry isotopic ratios indications in the Paleozoic sedimentary rock of El Gor area, Southwestern Sinai, Egypt: insights on uranium mobility age.

The study area is located between longitude 33° 18' 00" - 33° 21' 00" E and latitude 28° 59' - 29° 01' N and covers approximately 700 km2. Uranium and thorium isotopes were determined by alpha spectrometry. The activity concentrations of 238U, 234U and 235U were ranged between 245.5 ± 8.3-465.2 ± 15.2 Bq.kg-1 with an average 345.5 ± 10.4-452.5 ± 9.3 Bq.kg-1 and 890.5 ± 21.3 Bq.kg-1 with an average 632.3 ± 14.9-11.40 ± 0.5 Bq.kg-1 and 21.50 ± 1.4 Bq.kg-1, respectively. The activity concentration of 232Th, 230Th and 228Th were ranged between 153.1 ± 0.3-318.1 ± 2.9 Bq.kg-1, 149.5 ± 0.7-280.8 ± 2.2 Bq.kg-1 and 36.9 ± 0.1-60.5 ± 0.9 Bq.kg-1. The 230Th/232Th activity ratios in all samples were lower than 20, indicating that these samples have been contaminated by detrital 230Th. Th/U ratio varied between 1.3 and 2.1 with an average 1.8; all values were lower than 3.5, indicated enrichment of uranium. 234U/238U activity ratios that higher than unity indicates that an isotope of uranium has migrated within the rock. From the isotopes of uranium and thorium and their activity ratios, the isochron age for the collected samples was about 58.96 ka.

A new methodology based on TRU resin to measure U-, Th-isotopes and 210Po by alpha-particle spectrometry.

This report presents a new methodology to isolate and measure 210Po, as well as uranium and thorium isotopes. This new methodology reduces the standard time of operation, the minimum amount of chemical reagents and the quantity of resin used in comparison with other standard and well-established procedures for alpha spectrometry. Thus, the amount of chemicals reagent was lower than the amount used in other standard radiochemical processes: only 6 mL of 1 M HCl was used for the thorium elution, and 2 mL of H2O and 1 mL of Ammonium Oxalate (0.05 M) (3 mL in total) for the uranium elution. Likewise, many samples of various activities and materials (liquids and solids) were used to validate the method.

Polyamidoxime-based membranes for the rapid screening of uranium isotopes in water.

Traditional radiochemistry approaches for the detection of trace-level alpha-emitting radioisotopes in water require lengthy offsite sample preparations and do not lend themselves to rapid quantification. Therefore, a novel platform is needed that combines onsite purification, concentration, and isotopic screening with a fieldable detection system. This contribution describes the synthesis and characterization of polyamidoxime membranes for isolation and concentration of uranium from aqueous matrices, including high-salinity seawater. The aim was to develop a field portable screening method for the rapid quantification of isotopic distribution by alpha spectroscopy. Membranes with varying degree of modification were prepared by chemical conversion of nitrile groups to amidoxime groups on the surface of polyacrylonitrile ultrafiltration (UFPAN) membranes. Attenuated total reflectance Fourier-transform infrared spectroscopy was used to analyze changes in surface chemistry. Flow through filtration experiments conducted using deionized (DI) water and simulated seawater solutions indicated that the modified membrane was effective in capturing more than 95% of the uranium in the solution prior to breakthrough even in the presence of salt ions. Batch uptake experiments were conducted and compared with the flow through experimental data to elucidate likely binding mechanisms. Alpha spectra of uranium loaded membranes were analyzed, and the effects of solution matrix and degree of modification on peak energy resolution were studied. Peak energy resolutions of 24 ± 2 keV and 32 ± 6 keV full width at half maximum (FWHM) were obtained by loading uranium from DI and seawater solutions onto modified membranes. Full width at 10% maximum of the same spectra were calculated to be 63 ± 9 keV and 160 ± 34 keV to quantify differences seen in peak tailing. Calculations performed based on the results show that it would take less than 3 h of analysis time to screen a sample provided enough volumes of solution are available. This work offers a facile method to prepare polyamidoxime-based membranes for uranium separation and concentration at circumneutral pH values, enabling the rapid, onsite screening of unknown samples.

Radioactivity evaluation and radiation dosimetry assessment in Greek honey.

Greek honey was examined for 238U, 234U, 210Pb, 210Po, 40K, and 137Cs levels. 238U was calculated from 0.013 ± 0.007 Bq kg-1 to 0.10 ± 0.02 Bq kg-1 while 234U ranged from 0.017 ± 0.009 Bq kg-1 to 0.11 ± 0.03 Bq kg-1. 210Pb measured from 0.04 ± 0.02 Bq kg-1 to 1.70 ± 0.26 Bq kg-1 whereas 210Po activity determined between 0.02 ± 0.01 Bq kg-1 and 2.31 ± 0.34 Bq kg-1. 40 K found at the range of 7.9 ± 1.6 Bq kg-1 to 102.2 ± 19.7 Bq kg-1 and 137Cs 0.3 ± 0.1 Bq kg-1 up to 0.8 ± 0.1 Bq kg-1. Uranium isotopes and 210Po were determined via alpha spectrometry. 210Pb was also indirectly determined by alpha spectrometry. 40 K and 137Cs were measured through γ-ray spectrometry. An annual dose calculation was performed for different age groups.

Uranium isotopic ratio of black shale and its role in detection of oxic-anoxic conditions of uranium depositions.

The black shale is considered one of the most important rock units in the lower part of Um Bogma Formation, where it contains the uranium, heavy metals and rare earth elements mineralization. The black shale samples were analyzed radiochemically by using alpha spectrometry technique. Most of uranium in the studied samples is authigenic and the Th/U ratio confirms the deposition of uranium in reducing environment. The activity ratios of the studied black shale samples were characterized by 234U/238U > 1 and 230Th/234U < 1, which showed relatively recent precipitation of uranium from water in reducing conditions. 234U/235U and 238U/235U activity ratio was relatively deviated from equilibrium due to the changes in the oxidation-reduction conditions. The disequilibrium of 228Th/232Th can be due to the co-precipitation of 228Ra and the migration of 228Th from the black shale into the percolating water. So, the water was percolated through the paleochannels and caves instead of the rocks causing uranium mobilization and the fractionation of uranium, forming the oxidation-reduction interface in the periods from <6 × 104 to >3 × 105 year.

Occurrence and behavior of uranium and thorium series radionuclides in the Permian shale hydraulic fracturing wastes.

Over the last decade, there has been a rapid growth in the use of hydraulic fracturing (fracking) to recover unconventional oil and gas in the Permian Basin of southeastern New Mexico (NM) and western Texas. Fracking generates enormous quantities of wastes that contain technologically enhanced naturally occurring radioactive materials (TENORM), which poses risks to human health and the environment because of the relatively high doses of radioactivity. However, very little is known about the chemical composition and radioactivity levels of Permian Basin fracking wastes. Here, we report chemical as well as radiochemical compositions of hydraulic fracking wastes from the Permian Basin. Radium, the major TENORM of interest in unconventional drilling wastes, varied from 19.1 ± 1.2 to 35.9 ± 3.2 Bq/L for 226Ra, 10.3 ± 0.5 to 21.5 ± 1.2 Bq/L for 228Ra, and 2.0 ± 0.05 to 3.7 ± 0.07 Bq/L for 224Ra. In addition to elevated concentrations of radium, these wastewaters also contain elevated concentrations of dissolved salts and divalent cations such as Na+ (31,856-43,000 mg/L), Ca2+ (668-4123 mg/L), Mg2+ (202-2430 mg/L), K+ (148-780 mg/L), Sr2+ (101-260 mg/L), Cl- (5160-66,700 mg/L), SO42- (291-1980 mg/L), Br- (315-596 mg/L), SiO2 (20-32 mg/L), and high total dissolved solid (TDS) of 5000-173,000 mg/L compared to background waters. These elevated levels are of radiological significance and represent a major source of Ra in the environment. The recent discovery of large deposits of recoverable oil and gas in the Permian Basin will lead to more fracking, TENORM generation, and radium releases to the environment. This paper evaluates the potential radiation risks associated with TENORM wastes generated by the oil and gas recovery industry in the Permian Basin.

Development of a rapid method for extraction of uranium from uranium bearing materials using ionic liquid as extracting agent from basic media.

The paper presents the development of a rapid method for the direct determination of uranium using liquid scintillation analysis in uranium bearing materials with different uranium concentrations and with different impurity levels (U-ore, Uranium ore concentrate (UOC) and U-metal). Uranium extraction was carried out using hydrophobic ionic liquid Aliquat-336 thiosalicylate, ([A-336][TS]) from diluted samples in basic medium followed by liquid scintillation counting (LSC). Extraction efficiencies for uranium from aqueous medium was studied with very small volumes of ionic liquid under varying volume, pH and uranium concentration of the aqueous medium. Maximum extraction efficiency was achieved near pH 8-11. Uranium was successfully re-extracted from organic medium with nitric acid and electroplated onto stainless steel planchette for alpha spectrometry determination. Maximum re-extraction efficiency with 1 M HNO3 combined with electroplating efficiency observed was 80%. The methodology was applied for real samples. The uranium extraction efficiency using ionic liquid was about 85% for U-metal and UOC samples with comparatively low impurity level; whereas extraction efficiency for U-ore samples was found to be less than 40%. The technique can be applied for nuclear forensic applications as well as nuclear emergency scenarios for a quick initial assessment and isotopic analysis of uranium in the samples.