Radiochemical separation of 224Ra from 232U and 228Th sources for 224Ra/212Pb/212Bi generator.

The application of diagnostic and therapeutic radionuclides in nuclear medicine has grown significantly and has translated into the increased interest in radionuclide generators and their development. 224Ra and its shorter-lived daughters, 212Pb and 212Bi, are very interesting radionuclides from Targeted Alpha Therapy point of view for treatment of small cancers or metastatic forms. The purpose of the present work was to develop a simple generator for rapid elution of carrier-free 224Ra from 232U or 228Th sources by radiochemical separation based on extraction chromatography with the utilization of a home-made material. The bis(2-ethylhexyl) hydrogen phosphate (HDEHP) extractant was immobilized on polytetrafluroethylene (PTFE) grains and its ability to selectively adsorb 232U and 228Th, with simultaneous high elution recovery of 224Ra, was checked over few years. The 224Ra was quantitatively eluted with small volume (3-5 mL) of 0.1 M HNO3 with low breakthrough (<0.005%) and was used for further milking of 212Bi and 212Pb from DOWEX 50WX12 by 0.75 M and 2.0 M HCl, respectively. The elaborated here methods allowed high recovery of 224Ra, 212Pb and 212Bi radionuclides and their application in radiolabeling of various biomolecules.

Quantification of U, Th and specific radionuclides in coal from selected coal fired power plants in South Africa.

Most of South Africa's energy is derived from the combustion of coal in pulverized coal-fired power plants (CFPP). However, when compared with the rest of the world, limited information regarding the main radioactive elements (U and Th) and specific radionuclides of interest (K40, Ra226 and Th232) from South African CFPP is available in the public domain. This paper aims to quantify the U, Th and specific radionuclides found in the coal used in selected South African CFPP in comparison to world averages found in literature. The U and Th concentrations were obtained by ICP-MS. The main radionuclides, K40, Ra226 and Th238, were quantified using gamma spectrometry. The U concentration and Th concentrations for the coal used in all the power plants was above the world average of 1.9 mg/kg and 3.2 mg/kg respectively. The coals with the highest Th content originated from the Mpumalanga power plant, while the U content in the Freestate power plant samples was the highest of the three. The concentrations of the K40 were between 88.43±10.75-110.76±8.92 Bq/kg, which are in-line with world averages of 4-785 Bq/kg. Similarly, the Ra226 and Th232 values were between 21.69±2.83-52.63±4.04 Bq/kg and 19.91±1.24-22.97±1.75 Bq/kg respectively, which are also in line with the world averages of 1-206 Bq/kg and 1-170 Bq/kg respectively. Radiological hazard indices such as radium equivalent (Raeq); external hazard index (Hex) and internal hazard index (Hin), that were estimated from these average radionuclide concentrations were less than the prescribed values found in literature. This indicated that no significant health risk was posed by the coal being used from these coal fields.

Application of Doehlert experimental design for the removal of radium from aqueous solution by cross-linked phenoxycalix[4]pyrrole-polymer using Ba(II) as a model.

Ra-226 is a naturally occurring radionuclide that is derived from uranium-238 series, and it is present at low concentrations in rocks, soil, and groundwater. Many efforts have been exerted for the decontamination of radium from aqueous media in order to meet the increasing water demand of the population. To this aim, a new polymer based on cross-linked phenoxycalix[4]pyrrole was designed and employed in solid/liquid extractions in order to remove radium from aqueous solutions. Preliminary experiments have highlighted the capability of this polymer to extract 22% of Ra-226 from aqueous acidic solution. The optimization of the extraction experimental factors in the direction to attend the maximum removal of Ra-226 from water was carried out employing Ba2+ due to its similar chemical behavior as radium, in order to minimize the consumption of Ra-226 solutions and the risk of radioactive contamination. Doehlert experimental plan was then applied to determine the optimal conditions (pH, time, temperature) for the removal of Ba2+ from aqueous solutions.

Removal of radium in a working drinking water treatment plant: Radiological hazard assessment and waste management.

Occurrence of radium in drinking water may pose a radiological hazard. It is one of the most radiotoxic radionuclides and a major contributor to the Indicative Dose (ID), regulated parameter in UE. Its removal at Drinking Water Treatment Plants (DWTPs) can be considered a preventive action, as it cannot reach the final consumer nor be accumulated in distribution pipes. A filtration system based on greensand designed for radium removal was tested in an actual DWTP. Removal effectiveness depended on the spatial velocity water passed through the filter, range 65-100%. The lower the spatial velocity, the greater contact time, and the longer high removal percentages were achieved. The radium removed from the water was mainly associated to easily reducible fraction in greensand. So radium accumulation in the filter may pose a radiological hazard for the workers in the DWTP. Dose rate was assessed in the worst case scenario for this case study, being about 0.22 mSv/y, significantly lower than reference value 1 mSv/y. Radium accumulated in the greensand filter can be extracted in order to ease waste management, and subsequently, the filtration system can be regenerated showing similar capacity to extract radium as a new one.

Green approach for radium isotopes removal from TENORM waste using humic substances as environmental friendly.

Humic substances (HS) of the dark-colored are found in all soils and sediments as natural organic matter (NOM). HS has high affinity interacted with various organic and inorganic pollutants. Therefore, the HS were isolated from agriculture soil and their potential to remove radium species (226+228Ra) from TENORM scale waste produced from oil production was investigated. Different factors affecting on the efficient removal of radium species by natural humic and natural fulvic acids (NHA and NFA) were investigated by batch technique. These parameters include contact time, concentration of HS, pH, successive leaching as well as the influence of mixed ratio of NHA and NFA. The experimental results indicate that, higher pH and concentration of HS is capable of leaching out 95.2% and 90.2% from TENORM scale waste by the NHA and NFA, respectively, through 3 successive leaching process. Admixture of NHA and NFA solution has been removed 93% of 226+228Ra from scale waste. It is a novel approach for efficient removal Ra isotopes level from TENORM scale waste by economic and eco-friendly that could be help for design a semi-pilot plant for scale-up test in forthcoming study.

Extraction of 223Radium by haemodialysis after treatment of metastatic castration-resistant prostate cancer.

AIM: 223Radium-dichloride (223Ra) administration is an upcoming therapeutic option in patients with castration-resistant metastatic prostate cancer (mCRPC), whose renal and faecal excretion of 223Ra has been primarily estimated from data of a phase-I clinical trial in patients with normal renal function. In the rare case of concomitant renal insufficiency requiring haemodialysis (HD), an estimation of the contamination of dialysate would be beneficial. METHODS: The excretion of 223Ra and its concentration in the dialysate in a patient with mCRPC and end-stage renal disease was examined for six consecutive treatment cycles. Dialysate samples were measured using a commercial system with NaI-scintillation detector. RESULTS: HD showed a residual activity level in the remaining dialysate. The excreted activity was a median of 46.1 kBq (range = 42.0- 83.4 kBq) and 11.2 kBq (range = 8.4- 19.9 kBq) for the first (24 h post injection p.i.) and second HD (96 h p.i.), respectively. The activity concentration decreased significantly from a median of 4.18 kBq/l (range = 2.98-5.14 kBq/l) to 0.85 kBq/l (range = 0.69- 1.31 kBq/l, p < 0.0001). For all consecutive time points, the activity concentration further decreased significantly (p < 0.0001). The activity concentration of dialysate from HD performed 125.4 h p.i. [95 % confidence interval = 120.5-130.4 h p.i.] reached the threshold for unrestricted waste disposal. CONCLUSION: The observed extraction of 223Ra by HD exceeded the data determined from the phase-I study. The activity concentration in the dialysate observed for the first HD's p.i. was above the threshold for unrestricted disposal of radioactive waste in Germany. Therefore, the specific requirement for waste handling has to be followed to fulfil the radiation protection regulations.

226Ra dynamic lixiviation from phosphogypsum samples by an automatic flow-through system with integrated renewable solid-phase extraction.

The release of 226Ra from phosphogypsum (PG) was evaluated by developing a novel tool for fully automated 226Ra lixiviation from PG integrating extraction/pre-concentration using a renewable sorbent format. Eight leached fractions (30mL each one) and a residual fraction were analyzed allowing the evaluation of dynamic lixiviation of 226Ra. An automatic system allows this approach coupling a homemade cell with a 226Ra extraction/pre-concentration method, which is carried out combining two procedures: Ra adsorption on MnO2 and its posterior co-precipitation with BaSO4. Detection was carried out with a low-background proportional counter, obtaining a minimum detectable activity of 7Bqkg-1. Method was validated by analysis of a PG reference material (MatControl CSN-CIEMAT 2008), comparing the content found in fractions (sum of leached fractions + residual fraction) to the reference value. PG samples from Huelva (Spain) were studied. 226Ra average activity concentration of the sum of leached fractions with artificial rainwater at pH 5.4±0.2 was 105±3Bqkg-1d.w. representing a 226Ra lixiviation of 37%; while at pH 2.0±0.2, it was 168±3Bqkg-1 d.w., which represents a 50%. Also, static lixiviation, maintaining the same experimental conditions, was carried out indicating that, for both considered pH, the 226Ra release from PG is up to 50% higher in a dynamic leaching that in a static one, may have both environmental and reutilization implications.

MSFIA-LOV system for (226)Ra isolation and pre-concentration from water samples previous radiometric detection.

An automatic system based on multisyringe flow injection analysis (MSFIA) and lab-on-valve (LOV) flow techniques for separation and pre-concentration of (226)Ra from drinking and natural water samples has been developed. The analytical protocol combines two different procedures: the Ra adsorption on MnO2 and the BaSO4 co-precipitation, achieving more selectivity especially in water samples with low radium levels. Radium is adsorbed on MnO2 deposited on macroporous of bead cellulose. Then, it is eluted with hydroxylamine to transform insoluble MnO2 to soluble Mn(II) thus freeing Ra, which is then coprecipitated with BaSO4. The (226)Ra can be directly detected in off-line mode using a low background proportional counter (LBPC) or through a liquid scintillation counter (LSC), after performing an on-line coprecipitate dissolution. Thus, the versatility of the proposed system allows the selection of the radiometric detection technique depending on the detector availability or the required response efficiency (sample number vs. response time and limit of detection). The MSFIA-LOV system improves the precision (1.7% RSD), and the extraction frequency (up to 3 h(-1)). Besides, it has been satisfactorily applied to different types of water matrices (tap, mineral, well and sea water). The (226)Ra minimum detectable activities (LSC: 0.004 Bq L(-1); LBPC: 0.02 Bq L(-1)) attained by this system allow to reach the guidance values proposed by the relevant international agencies e.g. WHO, EPA and EC.

Co-precipitation of radium with barium and strontium sulfate and its impact on the fate of radium during treatment of produced water from unconventional gas extraction.

Radium occurs in flowback and produced waters from hydraulic fracturing for unconventional gas extraction along with high concentrations of barium and strontium and elevated salinity. Radium is often removed from this wastewater by co-precipitation with barium or other alkaline earth metals. The distribution equation for Ra in the precipitate is derived from the equilibrium of the lattice replacement reaction (inclusion) between the Ra(2+) ion and the carrier ions (e.g., Ba(2+) and Sr(2+)) in aqueous and solid phases and is often applied to describe the fate of radium in these systems. Although the theoretical distribution coefficient for Ra-SrSO4 (Kd = 237) is much larger than that for Ra-BaSO4 (Kd = 1.54), previous studies have focused on Ra-BaSO4 equilibrium. This study evaluates the equilibria and kinetics of co-precipitation reactions in Ra-Ba-SO4 and Ra-Sr-SO4 binary systems and the Ra-Ba-Sr-SO4 ternary system under varying ionic strength (IS) conditions that are representative of brines generated during unconventional gas extraction. Results show that radium removal generally follows the theoretical distribution law in binary systems and is enhanced in the Ra-Ba-SO4 system and restrained in the Ra-Sr-SO4 system by high IS. However, the experimental distribution coefficient (Kd') varies widely and cannot be accurately described by the distribution equation, which depends on IS, kinetics of carrier precipitation and does not account for radium removal by adsorption. Radium removal in the ternary system is controlled by the co-precipitation of Ra-Ba-SO4, which is attributed to the rapid BaSO4 nucleation rate and closer ionic radii of Ra(2+) with Ba(2+) than with Sr(2+). Carrier (i.e., barite) recycling during water treatment was shown to be effective in enhancing radium removal even after co-precipitation was completed. Calculations based on experimental results show that Ra levels in the precipitate generated in centralized waste treatment facilities far exceed regulatory limits for disposal in municipal sanitary landfills and require careful monitoring of allowed source term loading (ASTL) for technically enhanced naturally occurring materials (TENORM) in these landfills. Several alternatives for sustainable management of TENORM are discussed.

Treatment of NORM contaminated soil from the oilfields.

Uncontrolled disposal of oilfield produced water in the surrounding environment could lead to soil contamination by naturally occurring radioactive materials (NORM). Large volumes of soil become highly contaminated with radium isotopes ((226)Ra and (228)Ra). In the present work, laboratory experiments have been conducted to reduce the activity concentration of (226)Ra in soil. Two techniques were used, namely mechanical separation and chemical treatment. Screening of contaminated soil using vibratory sieve shaker was performed to evaluate the feasibility of particle size separation. The fractions obtained were ranged from less than 38 µm to higher than 300 µm. The results show that (226)Ra activity concentrations vary widely from fraction to fraction. On the other hand, leaching of (226)Ra from soil by aqueous solutions (distilled water, mineral acids, alkaline medias and selective solvents) has been performed. In most cases, relatively low concentrations of radium were transferred to solutions, which indicates that only small portions of radium are present on the surface of soil particles (around 4.6%), while most radium located within soil particles; only concentrated nitric acid was most effective where 50% of (226)Ra was removed to aqueous phase. However, mechanical method was found to be easy and effective, taking into account safety procedures to be followed during the implementation of the blending and homogenization. Chemical extraction methods were found to be less effective. The results obtained in this study can be utilized to approach the final option for disposal of NORM contaminated soil in the oilfields.

Radium and barium removal through blending hydraulic fracturing fluids with acid mine drainage.

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60-100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼ 10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A.

[About the contents of 40K, 226Ra and 232Th in forest soils of the Republic of Belarus].

The specific activity of 40K, 232Th and 226Ra in forest soil ecotopes (A2-B2-C2-D2) has been investigated. When the fertility of the soil increases from A2 to D2, then the specific activity of 40K increases in the rooting zone of the soil from 275 ± 6.9 up to 499 ± 11 Bq/kg, 232Th--from 11.8 ± 0.5 to 17.1 ± 1.1 Bq/kg, 226Ra- from 19.2 γ 0.8 to 27.9 ± 1.5 Bq/kg. The calculated capacity of the absorbed dose of γ-radiation conditioned by 40K, 232Th and 226Ra increases from A2 to D2 from 27.5 ± 0.5 to 44.1 ± 1.1 nGy / h at the height of 1 m.

[Evaluation of the partial contribution of naturally occurring radionuclides and nonradioactive chemically toxic elements in formation of biological effects within the Vicia cracca population inhabiting the area contaminated with uranium-radium production wastes in the Komi Republic].

The site contaminated with uranium-radium production wastes in the Komi Republic was studied. The activity concentration of naturally occurring radionuclides (226Ra, 228Th, 238U, 230Th, 232Th, 210Po, and 210Pb), as well as concentrations of nonradioactive chemically toxic elements (Pb, Zn, Cu, As, V, Mo, Sr, Y, and Ba) in the soil samples from the experimental site is 10-183 times higher than reference levels. A chronic exposure to alpha-emitters and nonradioactive chemically toxic elements causes adverse effects in tufted vetch (Vacia cracca L.) both at the cellular (aberration of chromosomes) and population (decrease in the reproductive ability) levels. Radionuclides are the main contributors to the decrease in the reproductive capacity and an increase in the level of the cytogenetic damage in root tip cells of tufted vetch seedlings. As and Pb significantly influence the reproductive capacity of plants. Sr, Zn, Y and P modify the biological effects caused by exposure to radionuclides. Moreover, P and Zn reduce the adverse effects of radionuclides; however, Sr and Y enhance these effects.

Estonian waterworks treatment plants: clearance of residues, discharge of effluents and efficiency of removal of radium from drinking water.

Considerable levels of radium were detected in a certain fraction of the Estonian drinking water supply network. Some of these waterworks have treatment systems for the removal of (mainly) iron and manganese from drinking water. Three of these waterworks and another one equipped with a radium removal pilot plant were examined, and a specific study was conducted in order to assess the environmental compatibility of effluents and residues produced in the plants. (226)Ra and (228)Ra activity concentrations were analysed in both liquid (backwash water) and solid (sand filter and sediment) materials to evaluate their compliance, from the radiological point of view, with current Estonian legislation and international technical documents that propose reference levels for radium in effluents and residues. Also with regard to water treatment by-products, a preliminary analysis was done of possible consequences of the transposition of the European Basic Safety Standards Draft into Estonian law. Radium removal efficiency was also tested in the same plants. Iron and manganese treatment plants turned out to be scarcely effective, whilst the radium mitigation pilot plant showed a promising performance.

Production of high-purity radium-223 from legacy actinium-beryllium neutron sources.

Radium-223 is a short-lived alpha-particle-emitting radionuclide with potential applications in cancer treatment. Research to develop new radiopharmaceuticals employing (223)Ra has been hindered by poor availability due to the small quantities of parent actinium-227 available world-wide. The purpose of this study was to develop innovative and cost-effective methods to obtain high-purity (223)Ra from (227)Ac. We obtained (227)Ac from two surplus actinium-beryllium neutron generators. We retrieved the actinium/beryllium buttons from the sources and dissolved them in a sulfuric-nitric acid solution. A crude actinium solid was recovered from the solution by coprecipitation with thorium fluoride, leaving beryllium in solution. The crude actinium was purified to provide about 40 milligrams of actinium nitrate using anion exchange in methanol-water-nitric acid solution. The purified actinium was then used to generate high-purity (223)Ra. We extracted (223)Ra using anion exchange in a methanol-water-nitric acid solution. After the radium was separated, actinium and thorium were then eluted from the column and dried for interim storage. This single-pass separation produces high purity, carrier-free (223)Ra product, and does not disturb the (227)Ac/(227)Th equilibrium. A high purity, carrier-free (227)Th was also obtained from the actinium using a similar anion exchange in nitric acid. These methods enable efficient production of (223)Ra for research and new alpha-emitter radiopharmaceutical development.

[Radium in pharmacies! First Part : Pharmaceutical used of radium before the first World War]. / Du radium dans les pharmacies! 1 Première partie: Les usages pharmaceutiques du radium avant la première Guerre mondiale.

The authors present in this part the creation of first radioactiv drugs, since the discovery of radium to the first World War. They present the industrial and chemist Emile Armet de Lisle and the pharmacist Alexandre Antonin Jaboin, first manufacturers of those new way of treatment.

Rapid determination of 226Ra in urine samples.

A new radiochemical separation method has been developed for rapid analysis of (226)Ra in urine samples. In this method, radium is separated from urine matrix using cation and anion exchange column chromatography. A (224)Ra tracer is added, together with its parent in the (228)Th standard, for chemical recovery correction. After separation, the sample is precipitated with hydrous titanium oxide and then prepared for counting by creating a thin-layer counting source using BaSO(4) micro-precipitation. The radium isotopes are then counted by alpha spectrometry. Replicate spike and blank samples were analysed for validation of the procedure. The detection limit was determined to be 0.22 Bq l(-1) with 4 h of counting for 20 ml of urine sample. Using this method, the results can be reported within an 8 h turn-around time. This method is suitable for quick dose assessment of (226)Ra exposure following a radiation emergency.

An emergency radiobioassay method for 226Ra in human urine samples.

A new radioanalytical method was developed for rapid determination of (226)Ra in human urine samples. The method is based on organic removal and decolourisation of a urine sample by a polymeric (acrylic ester) solid phase sorbent material followed by extraction and preconcentration of (226)Ra in an organic solvent using a dispersive liquid-liquid microextraction technique. Radiometric measurement of (226)Ra was carried out using a liquid scintillation counting instrument. The minimum detectable activity for the method (0.15 Bq l(-1)) is lower than the required sensitivity of 0.2 Bq l(-1) for (226)Ra in human urine samples as defined in the requirements for radiation emergency bioassay techniques for the public and first responders based on the dose threshold for possible medical attention recommended by the International Commission on Radiological Protection (ICRP). The accuracy (expressed as relative bias, B(r)) and repeatability of the method (expressed as relative precision, S(B)) evaluated at the reference level (2 Bq l(-1)) were found to be -4.5 and 2.6 %, respectively. The sample turnaround time was <5 h for a single urine sample and <20 h for a batch of six urine samples. With the fast sample turnaround time combined with the potential to carry out the analysis in a field deployable mobile laboratory, the newly developed method can be used for emergency radiobioassay of (226)Ra in human urine samples following a radiological or nuclear accident.

Determination of 226Ra and 228Ra in slightly mineralised natural waters.

A radiochemical method for simultaneous separation of (226)Ra and (228)Ra from natural waters by precipitating the radionuclides in the form of chromates that have low solubility in weak acetic acid has been described. For analytical purposes the change into soluble state was achieved through high-temperature melting the radium chromates precipitate with sodium and potassium carbonates at certain ratios. The chemical yield for radium-226 amounted to 87.1 ± 1.4% at the efficiency of counting 92.8 ± 0.7%. Calculated in series of 20 parallel determinations, reproducibility of the method was 7%. The chemical yield in separating radium-228 made up 63.8 ± 1.1%.