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At least 19 records

Precision spectroscopy and laser-cooling scheme of a radium-containing molecule

Molecules containing heavy radioactive nuclei are predicted to be extremely sensitive to violations of the fundamental symmetries of nature. The nuclear octupole deformation of certain radium isotopes massively boosts the sensitivity of radium monofluoride molecules to symmetry-violating nuclear properties. Moreover, these molecules are predicted to be laser coolable. In this article, we report measurements of the rovibronic structure of radium monofluoride molecules, which allow the determination of their laser cooling scheme. We demonstrate an improvement in resolution of more than two orders of magnitude compared to the state of the art. Our developments allowed measurements of minuscule amounts of hot molecules, with only a few hundred per second produced in a particular rotational state. The combined precision and sensitivity achieved in this work offer opportunities for studies of radioactive molecules of interest in fundamental physics, chemistry and astrophysics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Radium Dial Workers: Back to the Future

This report reviews the history of the radium dial workers in the United States, summarizes the scientific progress made since the last evaluation in the early 1990s, and discusses current progress in updating the epidemiologic cohort and applying new dosimetric models for radiation risk assessment. The discoveries of radiation and radioactivity led quickly to medical and commercial applications at the turn of the 20th century, including the development of radioluminescent paint, made by combining radium with phosphorescent material and adhesive. Workers involved with the painting of dials and instruments included painters, handlers, ancillary workers, and chemists who fabricated the paint. Dial painters were primarily women and, prior to the mid to late 1920s, would use their lips to give the brush a fine point, resulting in high intakes of radium. The tragic experience of the dial painters had a significant impact on industrial safety standards, including protection measures taken during the Manhattan Project. The dial workers study has formed the basis for radiation protection standards for intakes of radionuclides by workers and the public. The mortality experience of 3,276 radium dial painters and handlers employed between 1913-1949 is being determined through 2019. The last epidemiologic follow-up was 30 years ago when most of these workers were still alive. Nearly 65% were born before 1920, 37.5% were teenagers when first hired, and nearly 50% were hired before 1930 when the habit of placing brushes in mouths essentially stopped. Comprehensive dose reconstruction techniques are being applied to estimate organ doses for each worker related to the intake of 226Ra, 228Ra, and associated photon exposures. Time dependent dose-response analyses will estimate lifetime risks for specific causes of death. The study of radium dial workers is part of the Million Person Study of low-dose health effects that is designed to evaluate radiation risks among healthy American workers and veterans. Despite being one of the most important and influential radiation effects studies ever conducted, shifting programmatic responsibilities and declining funding led to the termination of the radium program of studies in the early 1990s. Renewed interest and opportunity have arisen. With scientific progress made in dosimetric methodology and models, the ability to perform a study over the entire life span, and the potential applicability to other scenarios such as medicine, environmental contamination and space exploration, the radium dial workers have once again come to the forefront.

61 RADIATION PROTECTION AND DOSIMETRY↗

Sputter sample preparation for ion beam delivery of radium-223 at ATLAS

A radium-223 ion beam was delivered to an experiment from the electron cyclotron resonance ion source, ECR2, at the Argonne Tandem Linac Accelerator System (ATLAS). Here, the radium-223 material was in a nitrate salt form within a vial, prior to being converted to a usable sputter sample. The sputter sample was produced using a new sample preparation method, where the radium nitrate was dissolved into a solution and pipetted onto pressed aluminum powder. This sample was then allowed to dry, distributing the radium-223 material throughout the sputter sample. Ion source operation using the radium sputter sample is described with the operating parameters listed. The intensity and energy requirements for this ion beam were 1 × 10 6 particles/s and 1.07 GeV, respectively. Because the intensity is relatively low compared to most experiments at ATLAS, previously developed accelerator mass spectrometry methods were used Scott et al. to avoid the need for tuning of the low-intensity beam of interest. Handling of the radium material, as well as loading and unloading of the sputter sample from ECR2, required collaboration with Health Physics. Procedures were used and dry runs were carried out before, during, and after the experiment to ensure the safety of the workers. The processes used and lessons learned are described within.

07 ISOTOPE AND RADIATION SOURCES↗

Extraction of radium and actinium with dibenzo-21-crown-7 resin and Rose Bengal

The extraction of 224 Ra and 228 Ac with dibenzo-21-crown-7 resin was studied in solutions with Rose Bengal and identical solutions without Rose Bengal (blanks) from pH 3 to 12. Batch studies demonstrated that actinium is extracted at high pH (> 10) from both solutions but with a significantly higher extraction from the Rose Bengal solutions (maximum extraction ~ 60,000) than the blank solutions (maximum extraction ~ 2,000). In the Rose Bengal solutions, there was a weak extraction of actinium at lower pH (4–10) as well. There was no uptake of radium from the blank solutions, and a weak extraction at all pH levels from the Rose Bengal solutions. Kinetics studies were performed for actinium only, as radium had no significant extraction. Two column studies are demonstrated for the separation of radium from actinium. These separations are moderately effective with ~ 78% of the actinium recovered with no detectable radium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Evaluation of chromatographic resins for high efficacy separation of radium from chemical analogues

The separation of Radium (Ra) from interfering chemical analogues is of major importance for both the accurate measurement of Ra-226 in environmental samples and the preparation of radium targets destined for medical isotope production. The adsorption behavior of Ra, Barium (Ba), and Strontium (Sr) was investigated on multiple crown-ether-based proprietary extraction chromatographic resins developed by TrisKem Int. Among these, the TK101 resin, characterized by a novel room-temperature ionic liquid (RTIL) dual extractant–solvent system, demonstrated enhanced affinity and selectivity, particularly at low acid concentrations, achieving a D w of 3477 ± 73 for Ra in 0.04 M HNO₃, whereas the maximum Ra D w obtained with the traditional Sr resin in 8 M HNO 3 was only 12.33 ± 0.4. In 0.04 M HNO 3 , a Ra distribution ratio (D w ) of 776 was achieved within 1 min, indicating rapid uptake kinetics. The adsorption capacities were estimated at 19.6 ± 0.1 mg/g for Ba and 12.0 ± 0.2 mg/g for Sr. However, competing alkali metals significantly reduced alkaline earth metal uptake, indicating that the TK101 resin is best suited for radium purification following a preconcentration step to minimize matrix effects in high salinity samples. Dynamic column studies confirmed the strong chromatographic performance of the TK101 resin, with no significant Ba or Sr breakthrough in the Ra fraction and a Ra recovery of 87 ± 2.8%. These results demonstrate the potential of the TK101 resin for selective radium separation in analytical and radiochemical applications.

and nuclear chemistry↗

Radium Inputs Into the Arctic Ocean From Rivers: A Basin‐Wide Estimate

Abstract Radium isotopes have been used to trace nutrient, carbon, and trace metal fluxes inputs from ocean margins. However, these approaches require a full accounting of radium sources to the coastal ocean including rivers. Here, we aim to quantify river radium inputs into the Arctic Ocean for the first time for 226 Ra and to refine the estimates for 228 Ra. Using new and existing data, we find that the estimated combined (dissolved plus desorbed) annual 226 Ra and 228 Ra fluxes to the Arctic Ocean are [7.0–9.4] × 10 14 dpm y −1 and [15–18] × 10 14 dpm y −1 , respectively. Of these totals, 44% and 60% of the river 226 Ra and 228 Ra, respectively are from suspended sediment desorption, which were estimated from laboratory incubation experiments. Using Ra isotope data from 20 major rivers around the world, we derived global annual 226 Ra and 228 Ra fluxes of [7.4–17] × 10 15 and [15–27] × 10 15 dpm y −1 , respectively. As climate change spurs rapid Arctic warming, hydrological cycles are intensifying and coastal ice cover and permafrost are diminishing. These river radium inputs to the Arctic Ocean will serve as a valuable baseline as we attempt to understand the changes that warming temperatures are having on fluxes of biogeochemically important elements to the Arctic coastal zone.

Bullock, Emma J.↗

Bioaccumulation Factor for Radium in Rio Grande Biota

The Los Alamos National Laboratory (LANL or Laboratory) Environmental Protection and Compliance Division’s Environmental Stewardship Group (EPC-ES) performs the radiological analysis portion of biota dose assessments using the computer program RESRAD-Biota (DOE 2004, DOE 2020). RESRAD-Biota uses a default bioaccumulation factor, B iv , for radium in aquatic animals. This bioaccumulation factor, also listed in Department of Energy (DOE) Standard, DOE-STD-1153-2019, is the ratio of a radionuclide concentration in fresh weight biota to the environment in which it resides, which for aquatic animals is water. DOE-STD-1153-2019 offers conservative values for these ratios that are specific to the radiological contaminant, the biota, and the environment. The B iv in RESRAD-Biota can be used for general screening (Level 1 screening). If the factor proves to be too conservative, then a site-specific B iv may be used. The biota dose assessment of fish from the northern New Mexico region of the Rio Grande fail the general screen, which indicates that further analysis is necessary. Level 2 analysis is site-specific but still has conservative limitations. Level 3 analysis is a more realistic and representative, sitespecific analysis. The purpose of this paper is to use data specific to the Rio Grande to calculate a new aquatic animal radium B iv . This B iv can then be used for Level 3 analysis of aquatic animals specifically in the northern New Mexico region of the Rio Grande. The calculated radium B iv is a useful value for performing detailed, accurate biota dose assessments and calculating dose to fish using RESRAD-Biota when only sediment data are available.

54 ENVIRONMENTAL SCIENCES↗

Archival records housed at USTUR support radium dial worker dosimetry

The American radium dial worker (RDW) cohort of over 3200 persons is being revisited as part of the Million Person Study (MPS) to include a modern approach to RDW dosimetry. An exceptional source of data and contextualization in this project is an extensive collection of electronic records (digitized from existing microfilm and microfiche) housed at the United States Transuranium and Uranium Registries (USTUR). Although the type, extent, and quality (e.g. legibility) of record(s) varies between individuals, the remarkable occupational, medical and demographic data include in vivo radiation measurements (e.g. radon breath, whole body counts), autopsy results, medical records (including copies of radiographs), interviews over the years, and correspondence. Of particular dosimetric interest are the details of radiation measurements. For example, there are some instances where hand-written and transcribed values are both available, along with notes providing context for why a particular measurement in a series of measurements was chosen to assign an intake, or if there were concerns about a particular measurement. Born prior to 1935, RDW have nearly all passed away. Thus, the updated dosimetry, especially for the skeletal tissues, will allow the correlation of lifetime cumulative dose with radiation risk. Here we review typical information available in this collection of historical records and highlight some interesting finds. Additionally, we discuss the relevance to current and ongoing work related to updating the dosimetry of the RDW in the MPS, including providing an example of the usefulness of information contained in these records. The RDW cohort provides a unique historical perspective on occupational exposure to radium, making it a valuable dataset for understanding long-term health effects and improving current radiation protection standards.

Million Person Study↗

Polyoxometalate-Assisted Crystallization: A General Strategy Enabling Structural Characterization of Molecular Radium Complexes

A fundamental understanding of radium (Ra) coordination chemistry has been hindered by the scarcity and radiological hazards of 226 Ra, leaving the structural characterization of molecular Ra complexes almost entirely unexplored. Here, we introduce a polyoxometalate (POM)-assisted crystallization strategy that enables single-crystal X-ray diffraction analysis of Ra–chelator complexes from microgram-scale samples. Employing the plenary Keggin anion [SiW 12 O 40 ] 4– , we isolated and structurally characterized Ra 2+ complexes of 18-crown-6 and the bis-picolinate macrocycle macropa, together with their Sr 2+ and Ba 2+ analogues. The resulting structures reveal systematic, size-dependent trends in coordination number and metal-donor distances across the alkaline earth series and provide the first direct experimental measurements of Ra–N and Ra–OCOO bond distances. Together, these results establish POM-assisted crystallization as a robust approach for obtaining solid-state structural information on Ra 2+ complexes of organic chelators, opening new opportunities to advance the coordination chemistry needed to fully realize radium’s potential in isotope production and targeted radiotherapy. More broadly, this approach expands the experimental toolkit available for studying scarce, highly radioactive elements accessible only in microgram quantities.

Anions↗

Structure and bonding of a radium coordination compound in the solid state

The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra 2+ complex using 226 Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra 2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba 2+ ) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra 2+ and by analogy with Ba 2+ , supporting greater water lability in Ra 2+ complexes than in their Ba 2+ counterparts. In conclusion, barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra 2+ chemistry cannot always be predicted using Ba 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quadrupole and multi-collector ICP-MS analysis of 226 Ra in brain from a radium dial painter

We report two ICP-MS methods were developed to measure the radiotoxic isotope 226 Ra in brain tissues from a radium dial painter worker. The first method was a direct analysis of acid digested samples using quadrupole ICP-MS. The instrumental LOD of 226 Ra was 0.1 ng kg -1 . Polyatomic interferences at m/z 226 were investigated and Pb was identified from a polyatomic interferent in an in-house sample prepared from bovine brain, with a 226/208 formation ratio of 4 × 10 -8 . The quadrupole ICP-MS method was also used to measure levels of beryllium, strontium, and uranium. A second method was developed that included cation-exchange chromatography to separate 226 Ra followed by analysis with sector field MC-ICP-MS. The instrumental LOD for the cation exchange method with MC-ICP-MS detection was 0.5 pg kg -1 (19 mBq kg -1 ). The measured concentrations of 226 Ra in different brain regions ranged from 0.09–0.72 ng kg -1 (3.3–27 Bq kg -1 ) and radium was non-uniformly distributed in the brain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotope Shifts of Radium Monofluoride Molecules

Isotope shifts of 223–226,228 Ra 19 F were measured for different vibrational levels in the electronic transition A 2 II 1/2 ←X 2 Σ + . The observed isotope shifts demonstrate the particularly high sensitivity of radium monofluoride to nuclear size effects, offering a stringent test of models describing the electronic density within the radium nucleus. Ab initio quantum chemical calculations are in excellent agreement with experimental observations. These results highlight some of the unique opportunities that short-lived molecules could offer in nuclear structure and in fundamental symmetry studies.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Characterizing Radium Distributions, Source Attribution and Impacts from Marcellus Produced Water

This presentation characterizes spatial trends in radium (Ra) concentrations, sources, and potential impacts generated from Marcellus Shale produced waters. Here, we combine previously published produced water data with additional Ra activity measurements extracted from residual waste reports submitted to the Pennsylvania Department of Environmental Protection from 2012-2023. This is the largest, spatially referenced compilation of Ra activity measurements from produced water sourced from the Marcellus Shale to date. The median Marcellus Shale produced water Ra activity presented here is 6,906 pCi/L (interquartile range = 12,515 pCi/L). Radium activities in the positively skewed dataset can exceed 30,000 pCi/L in some parts of the state. The regional trends in Ra concentrations and isotopic ratios will be characterized and potential environmental and health implications discussed.

Mackey, Justin↗

Cation exchange separation of radium and actinium using lactic acid DTPA buffer

The separation of actinium ( 228 Ac) from radium ( 223,228 Ra) on cation exchange resin with a diethylenetriaminpentaacetic acid-lactate buffer solution is demonstrated with series of columns. High yield, high radiopurity (~ 100%) separations of Ac from Ra are feasible with small columns in biologically compatible conditions and pHs. As Ac is eluted before Ra on these columns, further studies were performed to determine if this separation system could be applied to Ra/Ac isotope generators, but these were not successful. In conclusion, the separations presented in this work may be relevant for radiopharmaceutical purifications of 225 Ac which is typically obtained from its 225 Ra parent isotope.

and nuclear chemistry↗

Separation of radium and actinium using zirconia

Herein, zirconia was investigated as a radiation-resistant support for radium and actinium aqueous ion separations. Acetate and total metal ion concentrations were experimentally evaluated as factors that could affect retention using La and Ba surrogates. Pseudo-second order rate constants were derived and the uptake of La was determined to be endothermic. Elution profiles containing Ba, La, 228 Ra, 228 Ac, and 212 Pb are presented and discussed.

07 ISOTOPE AND RADIATION SOURCES↗

Distribution of plutonium and radium in the human heart

Since 1968, the United States Transuranium and Uranium Registries (USTUR) has studied the biokinetics and tissue dosimetry of uranium and transuranium elements in nuclear workers. As part of the USTUR collaboration with the Million Person Study of Low-Dose Health Effects, radiation dose to different parts of the human heart is being estimated for workers with documented intakes of 239 Pu or 226 Ra. The study may be expanded for workers with intakes of 238 U and other radionuclides. The distribution of radionuclides, expressed in terms of concentration (Bq per kg of tissue) serves as an important parameter for estimating radiation dose. Based on available organs from workers who donated their bodies or tissues for research, nine undissected hearts were selected: seven from USTUR registrants with plutonium exposure (males) and two individuals with radium intakes (female and male). For the plutonium workers, estimated 239 Pu systemic deposition ranged from <74 Bq to 1765 Bq. Estimated 226 Ra ‘initial systemic intakes’ were 10.1 MBq and 14.8 kBq for the female patient and male worker, respectively. Organ dissection was based on a heart model published by Borrego et al (2019 J. Radiol. Prot. 39 950–65). This model includes nine cardiac substructures: aorta, left main coronary artery, left atrium, left anterior descending artery, left circumflex artery, left ventricle, right atrium, right coronary artery, and right ventricle. In addition, heart valves, fat attached to epicardium, fluids, and a coronary bypass graft were collected resulting in 111 samples that are currently undergoing radiochemical analyses and mass-spectrometric measurements. The 239 Pu and 226 Ra evaluations are not completed. The results of this study are intended to support radiation worker health studies by improving associated dosimetric and epidemiological models.

USTUR↗

Comparison of measurement techniques and sorption of radium-226 in low and high salinity aqueous samples

Human activities have the potential to redistribute radium (Ra) in the marine environment in a manner that may necessitate monitoring or management of subsequent human or environmental exposures. There is therefore a need to identify accurate and accessible techniques for Ra measurement in high salinity samples and to describe the distribution of Ra in estuarine and marine environments, but most efforts in these areas have focused on low salinity matrices. In addition, rapid and reliable measurements are crucial for time-sensitive samples such as short-lived isotopes or emergency situations. The objective of this study is to describe the limits of detection, cost, and relative ease for measurement of Ra in both low and high salinity aqueous samples via three analytical methods: liquid scintillation counting (LSC), high purity germanium (HPGe) gamma spectrometry, and inductively coupled plasma mass spectrometry (ICP-MS). To contextualize these measurements for real-world scenarios, the partitioning of 226 Ra to substrates relevant to the marine environment was also characterized. Although HPGe detection with solid phase extraction had the lowest limit of detection for low salinity samples (0.27 Bq L −1 ), poor 226 Ra recovery for high salinity samples and high materials costs make this method prohibitive for many users. Limits of detection for high salinity samples were lower for LSC (1.28 Bq L −1 ) than for ICP-MS without dilution (11.4 Bq L −1 ), but significant and unexpected degradation of the high salinity LSC standards was observed after six months. Furthermore, our preferred measurement method for high salinity Ra samples is ICP-MS with sample dilution as necessary to reduce matrix effects.

07 ISOTOPE AND RADIATION SOURCES↗

Electron correlation and relativistic effects in the excited states of radium monofluoride

Highly accurate and precise electronic structure calculations of heavy radioactive atoms and their molecules are important for several research areas, including chemical, nuclear, and particle physics. Ab initio quantum chemistry can elucidate structural details in these systems that emerge from the interplay of relativistic and electron correlation effects, but the large number of electrons complicates the calculations, and the scarcity of experiments prevents insightful theory-experiment comparisons. Here we report the spectroscopy of the 14 lowest excited electronic states in the radioactive molecule radium monofluoride (RaF), which is proposed as a sensitive probe for searches of new physics. The observed excitation energies are compared with state-of-the-art relativistic Fock-space coupled cluster calculations, which achieve an agreement of ≥99.64% (within ~12 meV) with experiment for all states. Guided by theory, a firm assignment of the angular momentum and term symbol is made for 10 states and a tentative assignment for 4 states. The role of high-order electron correlation and quantum electrodynamics effects in the excitation energies is studied and found to be important for all states.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗