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Title: Hydrogen and oxygen stable isotope composition of water in metaschoepite mineralization on U3O8

Abstract

When exposed to humidity in an oxidizing atmosphere hydrated uranium oxide grows as a secondary mineral on aged U3O8 and may incorporate the oxygen stable isotope signature of the water vapor into the secondary uranium oxide, as well as hydrogen and oxygen stable isotopes into any mineral hydration water. Because geospatial variation in δ2H and δ18O values of atmospheric humidity and precipitation is well understood, the H and O stable isotope composition of mineral hydration waters can give information on the environment of mineral formation. We exposed powdered U3O8 to humidity with known H and O stable isotope composition at constant 30%, 61% and 91% relative humidity. We sampled and analyzed the U3O8 powders along with any secondary hydrated minerals that had formed on the particle surfaces at various intervals from 1 to 10 days throughout the 180-day humidity exposures. We present stable H and O isotope results of mineral hydration waters in uranium oxide materials analyzed by thermogravimetry-enabled isotope ratio infrared spectroscopy (TGA-IRIS), which uses precise heating by thermogravimetric analyzer to liberate water vapor for subsequent online isotope analysis via a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-raymore » diffraction (XRD) analysis of humidity-exposed U3O8 heated to 350 °C indicates that the U3O8 had a measurable metaschoepite ((UO3)•2H2O) phase along with α-U3O8. After heating to 350 °C, the metaschoepite is eliminated but the α-U3O8 is retained, meaning that the heating successfully extracted the water in the metaschoepite but did not disturb the crystalline structure of the U3O8. Analysis of the bulk oxygen isotope composition by fluorination of these samples before and after heating, indicates that the oxygen isotope value of the U3O8 is also not affected by heating to 350 °C. Precision for δ2H and δ18O values of metaschoepite mineral hydration water stable isotope values yielded by the TGA-IRIS method on metaschoepite are 5.86‰ for δ2H, and 0.34‰ for δ18O. Hydrogen in the various water reservoirs is highly exchangeable and thus the δ2H values of these waters is not easily interpreted. However, oxygen in the separate water reservoirs is much less exchangeable, and thus δ18O values of the metaschoepite mineral hydration water is likely to reflect that of the water vapor the sample was exposed to. Once metaschoepite is formed on the surface of U3O8 particles, the oxygen isotope signature of the mineral hydration water in metaschoepite does not respond to changes in exposure vapor isotopic composition, and thus appears to be fairly durable in this regard. Furthermore, these results suggest that it may be possible to discern information about the provenance and history of an oxidized U3O8 sample from oxygen stable isotope measurements of metaschoepite mineral hydration water.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Merced, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); Office of Defense Nuclear Nonproliferation Research and Development
OSTI Identifier:
1597215
Alternate Identifier(s):
OSTI ID: 1891029
Report Number(s):
LLNL-JRNL-773024
Journal ID: ISSN 0883-2927; 963610; TRN: US2103047
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Applied Geochemistry
Additional Journal Information:
Journal Volume: 112; Journal Issue: C; Journal ID: ISSN 0883-2927
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
07 ISOTOPE AND RADIATION SOURCES; Mineral hydration water; Humidity exposure experiments; Nuclear forensics; Stable isotope hydrology; Isotope exchange

Citation Formats

Oerter, Erik J., Singleton, Michael, Dai, Zurong, Deinhart, Amanda, Thaw, Melissa, and Davisson, M. Lee. Hydrogen and oxygen stable isotope composition of water in metaschoepite mineralization on U3O8. United States: N. p., 2019. Web. doi:10.1016/j.apgeochem.2019.104469.
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Oerter, Erik J., Singleton, Michael, Dai, Zurong, Deinhart, Amanda, Thaw, Melissa, & Davisson, M. Lee. Hydrogen and oxygen stable isotope composition of water in metaschoepite mineralization on U3O8. United States. https://doi.org/10.1016/j.apgeochem.2019.104469
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Oerter, Erik J., Singleton, Michael, Dai, Zurong, Deinhart, Amanda, Thaw, Melissa, and Davisson, M. Lee. Thu . "Hydrogen and oxygen stable isotope composition of water in metaschoepite mineralization on U3O8". United States. https://doi.org/10.1016/j.apgeochem.2019.104469. https://www.osti.gov/servlets/purl/1597215.
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@article{osti_1597215,
title = {Hydrogen and oxygen stable isotope composition of water in metaschoepite mineralization on U3O8},
author = {Oerter, Erik J. and Singleton, Michael and Dai, Zurong and Deinhart, Amanda and Thaw, Melissa and Davisson, M. Lee},
abstractNote = {When exposed to humidity in an oxidizing atmosphere hydrated uranium oxide grows as a secondary mineral on aged U3O8 and may incorporate the oxygen stable isotope signature of the water vapor into the secondary uranium oxide, as well as hydrogen and oxygen stable isotopes into any mineral hydration water. Because geospatial variation in δ2H and δ18O values of atmospheric humidity and precipitation is well understood, the H and O stable isotope composition of mineral hydration waters can give information on the environment of mineral formation. We exposed powdered U3O8 to humidity with known H and O stable isotope composition at constant 30%, 61% and 91% relative humidity. We sampled and analyzed the U3O8 powders along with any secondary hydrated minerals that had formed on the particle surfaces at various intervals from 1 to 10 days throughout the 180-day humidity exposures. We present stable H and O isotope results of mineral hydration waters in uranium oxide materials analyzed by thermogravimetry-enabled isotope ratio infrared spectroscopy (TGA-IRIS), which uses precise heating by thermogravimetric analyzer to liberate water vapor for subsequent online isotope analysis via a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray diffraction (XRD) analysis of humidity-exposed U3O8 heated to 350 °C indicates that the U3O8 had a measurable metaschoepite ((UO3)•2H2O) phase along with α-U3O8. After heating to 350 °C, the metaschoepite is eliminated but the α-U3O8 is retained, meaning that the heating successfully extracted the water in the metaschoepite but did not disturb the crystalline structure of the U3O8. Analysis of the bulk oxygen isotope composition by fluorination of these samples before and after heating, indicates that the oxygen isotope value of the U3O8 is also not affected by heating to 350 °C. Precision for δ2H and δ18O values of metaschoepite mineral hydration water stable isotope values yielded by the TGA-IRIS method on metaschoepite are 5.86‰ for δ2H, and 0.34‰ for δ18O. Hydrogen in the various water reservoirs is highly exchangeable and thus the δ2H values of these waters is not easily interpreted. However, oxygen in the separate water reservoirs is much less exchangeable, and thus δ18O values of the metaschoepite mineral hydration water is likely to reflect that of the water vapor the sample was exposed to. Once metaschoepite is formed on the surface of U3O8 particles, the oxygen isotope signature of the mineral hydration water in metaschoepite does not respond to changes in exposure vapor isotopic composition, and thus appears to be fairly durable in this regard. Furthermore, these results suggest that it may be possible to discern information about the provenance and history of an oxidized U3O8 sample from oxygen stable isotope measurements of metaschoepite mineral hydration water.},
doi = {10.1016/j.apgeochem.2019.104469},
journal = {Applied Geochemistry},
number = C,
volume = 112,
place = {United States},
year = {Thu Nov 14 00:00:00 EST 2019},
month = {Thu Nov 14 00:00:00 EST 2019}
}
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https://doi.org/10.1016/j.apgeochem.2019.104469
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