Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling.

Herein, we report the synthesis and structural characterization of K8[(CO3)3Pu]2(µ-η2-η2-O2)2·12H2O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M8[(CO3)3A]2(µ-η2-η2-O2)2·xH2O (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na8[(CO3)3Pu]2(µ-η2-η2-O2)2·12H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8[(CO3)3A]2(µ-η2-η2-O2)2·12H2O complexes, described below, has produced crystals of Na8[(CO3)3Ce]2(µ-η2-η2-O2)2·12H2O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M8[(CO3)3Ce]2(µ-η2-η2-O2)2·xH2O have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide Op-Op stretch (Op = O atoms of the peroxide bridges) with each of the cations studied: Na+ [1.492(3) Å/847 cm-1], Rb+ [1.471(1) Å/854 cm-1], Cs+ [1.474(1) Å/859 cm-1], and K+ [1.468(6) Å/870 cm-1]. The trends observed in the Op-Op bond distances appear to relate to supermolecular interactions between the neighboring cations.

Using Atmospheric Dispersion Theory to Inform the Design of a Short-lived Radioactive Particle Release Experiment.

Atmospheric dispersion theory can be used to predict ground deposition of particulates downwind of a radionuclide release. This paper uses standard formulations found in Gaussian plume models to inform the design of an experimental release of short-lived radioactive particles into the atmosphere. Specifically, a source depletion algorithm is used to determine the optimum particle size and release height that maximizes the near-field deposition while minimizing both the required source activity and the fraction of activity lost to long-distance transport. The purpose of the release is to provide a realistic deposition pattern that might be observed downwind of a small-scale vent from an underground nuclear explosion. The deposition field will be used, in part, to study several techniques of gamma radiation survey and spectrometry that could be used by an On-Site Inspection team investigating such an event.

PRex: An Experiment to Investigate Detection of Near-field Particulate Deposition from a Simulated Underground Nuclear Weapons Test Vent.

A radioactive particulate release experiment to produce a near-field ground deposition representative of small-scale venting from an underground nuclear test was conducted to gather data in support of treaty capability development activities. For this experiment, a CO2-driven "air cannon" was used to inject (140)La, a radioisotope of lanthanum with 1.7-d half-life and strong gamma-ray emissions, into the lowest levels of the atmosphere at ambient temperatures. Witness plates and air samplers were laid out in an irregular grid covering the area where the plume was anticipated to deposit based on climatological wind records. This experiment was performed at the Nevada National Security Site, where existing infrastructure, radiological procedures, and support personnel facilitated planning and execution of the work. A vehicle-mounted NaI(Tl) spectrometer and a polyvinyl toluene-based backpack instrument were used to survey the deposited plume. Hand-held instruments, including NaI(Tl) and lanthanum bromide scintillators and high purity germanium spectrometers, were used to take in situ measurements. Additionally, three soil sampling techniques were investigated and compared. The relative sensitivity and utility of sampling and survey methods are discussed in the context of on-site inspection.