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Uranium particle age dating, aggregation, and model age best estimators

We present important aspects of uranium particle age dating by Large-Geometry Secondary Ion Mass Spectrometry (LG-SIMS) that can introduce bias and increase model age uncertainties, especially for small, young, and/or low-enriched particles. This metrology is important for applications related to International Nuclear Safeguards. We explore influential factors related to model age estimation, including the effects of evolving surface chemistry on inter-element measurements of particles (e.g., Th and U), detector background, and aggregation methods using simulated and actual particle samples. We introduce a new model age estimator, called “mid68”, that supplements 95% confidence intervals, providing a “best estimate” and uncertainty about the most likely age. The mid68 estimator can be calculated using the Feldman and Cousins method or Bayesian methods and provides a value with a symmetric uncertainty that can be used for calculations and approximate aggregation of processed model age values when the raw data and correction factors are not available. For particles yielding low 230 Th counts amidst nonzero detector background, their underlying model age probability distributions are asymmetric, so the mid68 estimator provides additional robust information regarding the underlying model age likelihood. This study provides a comprehensive and timely examination of critical aspects of uranium particle age dating as more laboratories establish particle chronometry capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Argon-isotopic Age Dating Analyses for Eastern Snake River Plain Volcanic Rock Samples

Argon-isotopic age dating analyses were conducted on 25 volcanic rock samples obtained from 22 boreholes and collected at three surface locations in the Eastern Snake River Plain (ESRP). The analyses were conducted to reduce uncertainties for characterizing volcanic hazards at Idaho National Laboratory (INL) as part of the Senior Seismic Hazard Analysis Committee (SSHAC) Level 3 Probabilistic Volcanic Hazards Assessment (PVHA). Results of the argon-isotopic age dating analyses will be used to estimate the recurrence of basaltic and silicic volcanism and for assessing the spatial and temporal distributions of volcanic events in the ESRP.

58 - GEOSCIENCES↗

Creating high-precision reference gas standards of 85Kr for groundwater age-dating

Absolute gas counting (AGC) was applied to two gas blends of 85Kr in argon-methane (P10) counting gas to establish a high-precision specific activity (Bq/cm3) reference value for characterizing 85Kr detection efficiency for groundwater age dating measurements. The AGC or length-compensated technique has been utilized by the metrology community for decades and is an accepted method for developing radioactive gas standards. The AGC capability at Pacific Northwest National Laboratory (PNNL) uses a set of nine unequal-length proportional counters with precisely-measured internal volumes, and a gas loading system with high-precision pressure and temperature sensors. A series of AGC measurements were collected at multiple pressures to determine the inverse pressure relationship (1/P) for 85Kr and define a wall-effect correction that accounts for events decaying into the detector wall and not depositing sufficient energy in the gas to be detected. In addition to the wall-effect, two additional corrections were evaluated and are discussed in detail. Specifically, the threshold effect which accounts for events deposited below the analysis threshold and a detection efficiency as a function of detector volume effect that was observed during analysis. A robust uncertainty model was developed using the Guide to the expression of Uncertainty in Measurements (GUM) approach. The combination of carefully scrutinized correction factors, precise measurements of pressure, temperature and detector volume, and robust counting statistics resulted in the determination of high-precision specific activity values with 0.50% or less total combined uncertainty for two Kr-in-P10 reference gas standards (KP10) that will enable new groundwater age-dating measurements at PNNL.

Kr-85↗

Developing a Th Resonance Ionization Scheme: for Future Use in Age Dating SNM by Resonance Ionization Mass Spectrometry

We report the development of a Th resonance ionization scheme (RIS) for analyzing Th isotopes by resonance ionization mass spectrometry (RIMS) to enable age-dating via the 230 Th/ 234 U inter-elemental pair. This report summarizes the work that completes the first of two tasks that are required for developing U-Th dating via RIMS at the Laser Ionization of Neutrals (LION) laboratory at Lawrence Livermore National Laboratory (LLNL). The first task involves choosing and vetting an appropriate Th RIS for the LION instrument and simultaneous U and Th analysis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Plutonium Age Dating Interlaboratory Comparison Overview - Project Design, Sample Preparation, and Results [Slides]

Project Design – How do you validate measured Pu model age? There are no certified reference materials (CRMs) that are certified for Pu model age or purification dates. There are no Am isotopic CRMs - IRMM 0243 243 Am spike has 241 Am impurity that can be used; Community working toward "consensus ages." This project executed and evaluated results from a Pu age dating interlaboratory comparison with six IAEA NWAL participant laboratories. It also ran the first quality control evaluation of single-picogram to sub-picogram scale interlaboratory 241 Am assay measurements from cotton swipe matrices. Results are promising, with a majority of 241 Am/ 241 Pu model age results agree to within 1 to 4 years. The calculated 241 Am assay results show interlaboratory variability, expanded percent uncertainties on calculated consensus 241 Am concentrations were: PuAge-S1 = 3.1 %, PuAge-S2 = 23 %, and PuAge-S3 = 26 %. Data can be used to investigate laboratory methods and improve precision and accuracy of 241 Pu and 241 Am assay for future campaigns.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Raman signatures from age-dating PuO 2 since last calcination

The self-irradiation of PuO 2 has been shown to affect the attributes of fifteen vibrational bands in the Raman spectrum. The vibrational bands correspond to the Raman allowed vibrational mode T 2g , overtones, defects, and bands from electronic origin. Defects in the crystal lattice from low-calcination temperature and alpha decay origins are responsible for the changes in the band attributes (band position, full-width half maximum (FWHM), intensity). Crystal lattice defects are also responsible for the growth of the defect bands. The temporal behavior of the vibrational bands can be used to estimate the age of the material since last calcination. Laser annealing was used to reset the material to full crystallinity prior to the aging study. 240 PuO 2 , with an alpha decay rate of 3.67 greater than the decay rate of 239 PuO 2 , was primarily used to assess the alpha decay-induced damage within 3 years. The aging study focused on the time-dependent properties of the T 2g band and the growth of defect bands. The FWHM of the T 2g band and the ratio of the areas of the defect bands/T 2g band were measured through a time period in excess of 3 years. The data from this study were found very close to the data describing the temporal evolution of the lattice constant measured with the X-ray diffraction (XRD) technique. The local physical properties of the material measured with Raman spectroscopy and the lattice parameter constant measured with XRD indicates a strong correlation between the two techniques. Although both techniques provide similar age-dating information, in contrast to the few milligram quantities required for XRD, Raman spectroscopy requires a 10 µm diameter PuO 2 particle to provide an estimate of the material age since last calcination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Noble Gas Analysis for Mars Robotic Missions: Evaluating K-Ar Age Dating for Mars Rock Analogs and Martian Shergottites

The purpose of this noble gas investigation was to evaluate the possibility of measuring noble gases in martian rocks and air by future robotic missions such as the Mars Science Laboratory (MSL). The MSL mission has, as part of its payload, the Sample Analysis at Mars (SAM) instrument, which consists of a pyrolysis oven integrated with a GCMS. The MSL SAM instrument has the capability to measure noble gas compositions of martian rocks and atmosphere. Here we suggest the possibility of K-Ar age dating based on noble gas release of martian rocks by conducting laboratory simulation experiments on terrestrial basalts and martian meteorites. We provide requirements for the SAM instrument to obtain adequate noble gas abundances and compositions within the current SAM instrumental operating conditions, especially, a power limit that prevents heating the furnace above approx.1100 C. In addition, Martian meteorite analyses from NASA-JSC will be used as ground truth to evaluate the feasibility of robotic experiments to constrain the ages of martian surface rocks.

Park, J.↗

In Situ Radiometric and Exposure Age Dating of the Martian Surface

We determined radiogenic and cosmogenic noble gases in a mudstone on the floor of Gale Crater. A K-Ar age of 4.21 +/- 0.35 billion years represents a mixture of detrital and authigenic components and confirms the expected antiquity of rocks comprising the crater rim. Cosmic-ray-produced 3He, 21Ne, and 36Ar yield concordant surface exposure ages of 78 T 30 million years. Surface exposure occurred mainly in the present geomorphic setting rather than during primary erosion and transport. Our observations are consistent with mudstone deposition shortly after the Gale impact or possibly in a later event of rapid erosion and deposition. The mudstone remained buried until recent exposure by wind-driven scarp retreat. Sedimentary rocks exposed by this mechanism may thus offer the best potential for organic biomarker preservation against destruction by cosmic radiation.

age dating↗

Aspects of Crystal Growth and Atomic-Scale Characterization of U/Th Age-Dating Particles

Trace analysis of particulate material collected on environmental swipe samples continues to be one of the cornerstones of the IAEA’s process of verifying member state compliance as part of the Non-Proliferation Treaty (NPT). While complementary to traditional bulk analysis, the ability to measure individual particles can be far more impactful from a radiochronometry perspective. The 234U/230Th radiochronometer is being evaluated as a means of establishing model ages for discrete particles with sufficient confidence. To support the extension of current capabilities, reference materials with a suitable particle form factor and well-documented purification date are actively sought for development with large geometry secondary ion mass spectroscopy.

Nuclear Safeguards, IAEA, Particle Standards↗

Ar-39-Ar-40 Age Dating Of Two Angrites and Two Brachinites

Angrites are a rare group (approximately 7 known) of igneous meteorites with basalt-like composition, which probably derive from a relatively small parent body that differs from those of other igneous meteorites. Angrites show evidence for extinct Mn-53, Sm-146, and Pu-244, and precise U-Pb, and Pb-Pb ages of 4.558 Gyr for two angrites define the time of early parent body differentiation. The Sm-147-Nd-143 ages of two angrites range between 4.53 +/- 0.04 and 4.56 +/- 0.04 Gyr, but no Ar-39-Ar-40 or Rb-Sr ages have been reported. Most angrites show no evidence for either shock brecciation or metamorphism. Brachinites are another very rare group' of differentiated meteorites consisting primarily of olivine, with minor augite, chromite, Fe-sulfides, and sometimes plagioclase and opx. Presence of excess Xe-129 and excess Cr53 from decay of Mn-53 in some brachinites indicate that they also formed very early. Brachinite petrogenesis is poorly defined. They may be igneous cumulates or metamorphic products of chondritic-like starting material. If after their formation, angrites and brachinites cooled quickly with minimal subsequent heating, then one might expect them to show uniquely old K-Ar ages, at least in comparison to other differentiated meteorites such as eucrites and mesosiderites. Most angrites and brachinites contain very little, if any K-feldspar, which has deterred measurements of their Ar-Ar ages. We made Ar-39-Ar-40 analyses on two angrites, LEW86010 (metamorphosed) and D'Orbigny, and on two brachinites, EET99402 and Brachina. All are finds. Any feldspar in angrites is highly calcic, with expected K concentrations of <100 ppm. We selected LEW86010 and D'Orbigny because they have been the objects of several other studies and because chemical analyses suggested [K] was approximately 70 ppm in both meteorites. Brachina contains approximately 9.9% plagioclase of higher K-content than angrites, and EET99402 is estimated to contain approximately 5% K-poor plagioclase. Other brachinites contain little to no feldspar. We have successfully measured Ar-Ar ages on a few meteorites and lunar anorthosites with [K] <100 ppm.

Garrison, Daniel↗

Age-dating volcanic and alluvial surfaces with multipolarization data

A false-color multipolarization version of one of the images of Owens Valley area acquired by the JPL Synthetic Aperture Radar (SAR) is given. A geologic map of the alluvial fans there (Gillespie, 1982) is also given for comparison. In general, brightness in the multipolarization images can be seen to be inversely proportional to the age of the surfaces. A more detailed investigation of the relationship between backscatter and age of the surfaces was undertaken with calibrated aircraft SAR data. The quantitative relationship between backscatter coefficient and age for the three polarizations is shown. The straight lines connecting the measured data points imply a steady-state process, although the process or processes leading to this relationship may have operated at rates that varied with climate fluctuations, such as the glacial ages. It is expected that the relationship between radar brightness and age is a consistent one, and that with the wider availability of calibrated radar backscatter data, these relationships can be less well-known areas. The effect of variable such as past climate fluctuations, tectonic disturbance, and rock type must be understood before extension beyond the Mojave Desert region can be attempted.

Farr, T. G.↗

Age Dating Merger Events in Early Type Galaxies via the Detection of AGB Light

A thorough statistical analysis of the J-H vs. H-K color plane of all detected early type galaxies in the 2MASS catalog with velocities less than 5000 km/s has been performed. This all sky survey is not sensitive to one particular galactic environment and therefore a representative range of early type galaxy environments have been sampled. Virtually all N-body simulation so major mergers produces a central starburst due to rapid collection of gas. This central starburst is of sufficient amplitude to change the stellar population in the central regions of the galaxy. Intermediate age populations are given away by the presence of AGB stars which will drive the central colors redder in H-K relative to the J- H baseline. This color anomaly has a lifetime of 2-5 billion years depending on the amplitude of the initial starburst Employing this technique on the entire 2MASS sample (several hundred galaxies) reveals that the AGB signature occurs less than 1% of the time. This is a straightforward indication that virtually all nearby early type galaxies have not had a major merger occur within the last few billion years.

Bothun, G.↗

In Situ Geochemical Analysis and Age Dating of Rocks Using Laser Ablation-Miniature Mass Spectrometer

A miniaturized instrument for performing chemical and isotopic analysis of rocks has been developed. The rock sample is ablated by a laser and the neutral species produced are analyzed using the JPL-invented miniature mass spectrometer. The direct sampling of neutral ablated material and the simultaneous measurement of all the elemental and isotopic species are the novelties of this method. In this laser ablation-miniature mass spectrometer (LA-MMS) method, the ablated neutral atoms are led into the electron impact ionization source of the MMS, where they are ionized by a 70-eV electron beam. This results in a secondary ion pulse typically 10-100 microsecond wide, compared to the original 5-10-nanosecond laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer and measured in parallel by a modified CCD (charge-coupled device) array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LAMMS offers a more quantitative assessment of elemental composition than techniques that detect laser-ionized species produced directly in the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the laser beam, and the ionization energies of the elements. The measurement of high-precision isotopic ratios and elemental composition of different rock minerals by LAMMS method has been demonstrated. The LA-MMS can be applied for the absolute age determination of rocks. There is no such instrument available presently in a miniaturized version that can be used for NASA space missions. Work is in progress in the laboratory for geochronology of rocks using LA-MMS that is based on K-Ar radiogenic dating technique.

Sinha, Mahadeva P.↗

International cooperation in age-dating uranium standards for nuclear forensics using the 231 Pa/ 235 U radiochronometer

During 2017–2018 Los Alamos National Laboratory, Lawrence Livermore National Laboratory and the China Institute of Atomic Energy collaborated in an interlaboratory 231 Pa/ 235 U radiochronometry exercise. The laboratories used different analytical methods to obtain a consensus model purification date for CRM U010 of December 28, 1958 ± 198 days and for CRM U850 of May 20, 1958 ± 363 days. These results agree with previously reported model dates using the 230 Th/ 234 U radiochronometer as well as the production histories of these materials. The concordance of interlaboratory data here confirms the ability of laboratories to make reproducible radiochronometry measurements using distinct analytical approaches.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗