Enhanced Oxygen Isotope Determination in Uranium Oxides Using BrF5 Fluorination

A new method for accurate determination of oxygen isotopes in uranium oxides encountered in the nuclear fuel cycle was developed using the conventional BrF₅ fluorination technique. Laser‐assisted fluorination was tested for comparison. We focused on fine powders of triuranium octoxide (U₃O₈), uranium dioxide (UO_2±x with 0 ≤ x ≤ 0.25), uranium trioxide (UO₃.nH₂O, with 0.8 ≤ n ≤ 2) and diuranates (M₂U₂O₇.nH₂O, with M = NH₄, Na or Mg_0.5 and 0 ≤ n ≤ 6). Fluorination at room temperature and heating under vacuum at 150 °C are shown to eliminate both adsorbed and structural water from the powder samples. Precision fit for purpose of δ¹⁸O values (± 0.3‰, 1s) and oxygen yields (close to 100%) were obtained for U₃O₈ and UO₂ where oxygen is only bound to uranium. A lower precision was observed for UO₃.nH₂O and M₂U₂O₇.nH₂O where oxygen is both present in the structural H₂O and bonded to uranium and where the extracted O_2(g) can be contaminated by NF₃ and NO_x compounds. Laser‐assisted fluorination gave shifted δ¹⁸O values between +0.8 and +1.4‰ for U₃O₈, around ?0.8‰ for UO₃.nH₂O and between ?3.9 and ?4.5‰ for M₂U₂O₇.nH₂O (± 0.3‰, 1s) compared with the conventional method.     

Constraints on Mercury’s Na exosphere: Combined MESSENGER and ground-based data

We have used observations of sodium emission obtained with the McMath-Pierce solar telescope and MESSENGER’s Mercury Atmospheric and Surface Composition Spectrometer (MASCS) to constrain models of Mercury’s sodium exosphere. The distribution of sodium in Mercury’s exosphere during the period January 12-15, 2008, was mapped using the McMath-Pierce solar telescope with the 5″ × 5″ image slicer to observe the D-line emission. On January 14, 2008, the Ultraviolet and Visible Spectrometer (UVVS) channel on MASCS sampled the sodium in Mercury’s anti-sunward tail region. We find that the bound exosphere has an equivalent temperature of 900-1200 K, and that this temperature can be achieved if the sodium is ejected either by photon-stimulated desorption (PSD) with a 1200 K Maxwellian velocity distribution, or by thermal accommodation of a hotter source. We were not able to discriminate between the two assumed velocity distributions of the ejected particles for the PSD, but the velocity distributions require different values of the thermal accommodation coefficient and result in different upper limits on impact vaporization. We were able to place a strong constraint on the impact vaporization rate that results in the release of neutral Na atoms with an upper limit of 2.1 × 10⁶ cm⁻² s⁻¹. The variability of the week-long ground-based observations can be explained by variations in the sources, including both PSD and ion-enhanced PSD, as well as possible temporal enhancements in meteoroid vaporization. Knowledge of both dayside and anti-sunward tail morphologies and radiances are necessary to correctly deduce the exospheric source rates, processes, velocity distribution, and surface interaction.     

Monte Carlo modeling of sodium in Mercury’s exosphere during the first two MESSENGER flybys

We present a Monte Carlo model of the distribution of neutral sodium in Mercury’s exosphere and tail using data from the Mercury Atmospheric and Surface Composition Spectrometer (MASCS) on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft during the first two flybys of the planet in January and September 2008. We show that the dominant source mechanism for ejecting sodium from the surface is photon-stimulated desorption (PSD) and that the desorption rate is limited by the diffusion rate of sodium from the interior of grains in the regolith to the topmost few monolayers where PSD is effective. In the absence of ion precipitation, we find that the sodium source rate is limited to ∼10⁶-10⁷ cm⁻² s⁻¹, depending on the sticking efficiency of exospheric sodium that returns to the surface. The diffusion rate must be at least a factor of 5 higher in regions of ion precipitation to explain the MASCS observations during the second MESSENGER flyby. We estimate that impact vaporization of micrometeoroids may provide up to 15% of the total sodium source rate in the regions observed. Although sputtering by precipitating ions was found not to be a significant source of sodium during the MESSENGER flybys, ion precipitation is responsible for increasing the source rate at high latitudes through ion-enhanced diffusion.     

The Demeter microsatellite and ground segment

The Demeter program is the first application of the Myriade microsatellite program conducted by the Cnes (French Space Agency) since 1997. The Myriade objective was to benefit from the miniaturization of the technologies to develop a product with a reduced size, weight and cost able to implement either scientific missions, demonstrators or operational applications in different areas: earth observation, astronomy, fundamental physics or telecommunications, within limited financial budget.The Demeter satellite was launched in end of June 2004, from Baikonour, aboard a Dnepr launcher, on a sun synchronous orbit at 710 km altitude. Its main scientific objectives are the detection and characterization of ionosphere electrical and magnetic disturbances in connection with a seismic activity.The scientific payload has been built by French scientific institutes (LPCE, CESR, CETP) involved in external and internal geophysics and by SSD/ESTEC (ESA). It is composed of several electrical and magnetic sensors, an ion spectrometer, an energetic particle analyzer and a Langmuir probe.The Demeter platform is designed in order to offer a high level of performances in terms of power, attitude and orbit control, data storage and transmission, flexibility. For example the large amount of scientific data is transmitted to the ground station with a high data rate telemetry link in X band.This paper describes the Demeter satellite and ground segment. It focuses on the specific design adaptations of the Myriade product for Demeter and it presents the preliminary in orbit platform performances.     

Response of three krill species to hypoxia and warming: an experimental approach to oxygen minimum zones expansion in coastal ecosystems

To understand the adaptation of euphausiid (krill) species to oxygen minimum zones (OMZs), respiratory response and stress experiments combining hypoxia‐reoxygenation exposure with warming were conducted. Experimental krill species were obtained from the Antarctic (South Georgia area), the Humboldt Current System (HCS, Chilean coast) and the Northern California Current System (NCCS, Oregon). Euphausia mucronata from the HCS showed oxyconforming pO₂‐dependent respiration below 80% air saturation (18 kPa). Normoxic subsurface oxygenation in winter posed a ‘high oxygen stress’ for this species. The NCCS krill, Euphausia pacifica, and the Antarctic krill, Euphausia superba, maintained respiration rates constant down to low critical pO₂ values of 6 kPa (30% air saturation) and 11 kPa (55% air saturation), respectively. Antarctic krill had low antioxidant enzyme activities, but high concentrations of the molecular antioxidant glutathione (GSH) and was not lethally affected by 6 h exposure to moderate hypoxia. The temperate krill species (E. pacifica) had higher superoxide dismutase (SOD) values in winter than in summer, which relates to a higher winter metabolic rate. In all species, antioxidant enzyme activities remained constant during hypoxic exposure at the typical temperature for their habitat. Warming by 7 °C above habitat temperature in summer increased SOD activities and GSH levels in E. mucronata (HCS), but no oxidative damage occurred. In winter, when the NCCS is well mixed and the OMZ is deeper, +4 °C of warming combined with hypoxia represents a lethal condition for E. pacifica. In summer, when the OMZ expands upwards (100 m subsurface), antioxidant defences counteracted hypoxia and reoxygenation effects in E. pacifica, but only at mildly elevated temperature (+2 °C). In this season, experimental warming by +4 °C reduced antioxidant activities and the combination of warming with hypoxia again caused mortality of exposed specimens. We conclude that a climate change scenario combining warming and hypoxia represents a serious threat to E. pacifica and, as a consequence, NCCS food webs.     

Metasomatism and graphite formation at a lithological interface in Malaspina (Alpine Corsica, France)

Multiple pieces of geologic evidence suggest that interfaces between contrasted lithologies exert a strong control on the fate of volatiles in subduction zones. Here we present results from a contact between serpentinites and sediments, located in Corsica and metamorphosed in the blueschist facies during the alpine orogeny. It was shown previously that carbonates in the sediments have been reduced to graphitic carbonaceous material within a 5–10-cm-thick reaction zone at the contact with serpentinites. In an effort to investigate the mechanisms governing this unusual process, bulk rock geochemical analyses incorporating a statistical analysis of compositional data are presented. Observations show that the fate of C was decoupled from that of other elements such as O, H, and large-ion lithophile elements—e.g. K, Sr, Ba...,As—that were extensively leached from the reaction zone. Notably, Na is strongly enriched in the reaction zone and structurally linked to pectolite. Reducing conditions, manifested by the depletion of O in the reaction zone compared to the bulk metasediment, were likely maintained by the presence of Fe(II) in the serpentinite. Moreover, thermodynamic calculations show that the low solubility of carbon in COH fluids at high-pressure and low-temperature conditions was the main driver for graphite precipitation synchronously with carbonate destabilization. This may have been kinetically favored by the presence of already existing graphitized carbonaceous material and phengite in the metasediment. Limited lateral flow might have contributed as well to the geochemical and petrological patterns observed in these rocks.