Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite

Eric M. Pierce; Kristina Lilova; David M. Missimer; Wayne W. Lukens; Lili Wu; Jeffrey Fitts; Claudia Rawn; Ashfia Huq; Donovan N. Leonard; Jeremy R. Eskelsen; Brian F. Woodfield; Carol M. Jantzen; Alexandra Navrotsky

doi:10.1021/acs.est.6b01879

Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite

Eric M. Pierce, Kristina Lilova, David M. Missimer, Wayne W. Lukens, Lili Wu, Jeffrey Fitts, Claudia Rawn, Ashfia Huq, Donovan N. Leonard, Jeremy R. Eskelsen, Brian F. Woodfield, Carol M. Jantzen, Alexandra Navrotsky

Environmental Sciences Division

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

Treatment and immobilization of technetium-99 (⁹⁹Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na₈[AlSiO₄]₆(ReO₄)₂, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na₈[AlSiO₄]₆(ReO₄)₂ _x(TcO₄)_x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P43n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO₄⁻ anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO₄⁻ anion occupies the center of the sodalite β-cage in Na₈[AlSiO₄]₆(ReO₄)₂. We also demonstrate, for the first time, that the TcO₄⁻ anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of ⁹⁹Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.

Original language	English
Pages (from-to)	997-1006
Number of pages	10
Journal	Environmental Science and Technology
Volume	51
Issue number	2
DOIs	https://doi.org/10.1021/acs.est.6b01879
State	Published - Jan 17 2017

Funding

The powder neutron diffraction data was collected on POWGEN (BL-11A) neutron powder diffractometer at Oak Ridge National Laboratory (ORNL) Spallation Neutron Source (SNS) under proposal numbers IPTS 5857 and 7810. The XAFS data was collected on beamline 20-ID-B at the Advanced Photon Source (APS) at Argonne National Laboratory (ANL) under proposal number GUP-24070, National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL) beamline X27A, and at the Stanford Synchrotron Radiation Lightsource (SSRL). Use of the NSLS, BNL, was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES) under Contract No. DE-AC02-98CH10886. Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the DOE, Office of Science, BES under Contract No. DE-AC02-76SF00515. A portion of this research used resources of the APS, a DOE Office of Science User Facility operated for the DOE Office of Science by ANL under Contract No. DE-AC02-06CH11357. Portions of this work were performed at Lawrence Berkeley National Laboratory under Contract No. DE-AC02-05CH11231. TA portion of this research was performed at ORNL’s SNS was sponsored by the Scientific User Facilities Division, BES, DOE. The ultra STEM imaging was conducted at the Center for Nanophase Material Science under proposal number CNMS2016-R15, which is a DOE Office of Science User Facility. ORNL is managed by UT-Battelle, LLC, for DOE under contract DE-AC05-00OR22725. Support was provided by the Subsurface Biogeochemical Research Program under the US Department of Energy (DOE) Office of Biological and Environmental Research, Climate and Environmental Sciences Division. Portions of this research were supported by Heavy Element Chemistry Program under the Office of Basic Energy Sciences (BES) Chemical Sciences, Biosciences and Geosciences Divisions and the Tank Waste Management Technology Development Program under the Office of Environmental Management. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05−00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan

Funders	Funder number
DOE Office of Science
Office of Basic Energy Sciences
Office of Biological and Environmental Research, Climate and Environmental Sciences Division
SSRL
Scientific User Facilities Division
US Department of Energy
U.S. Department of Energy
Office of Science
Office of Environmental Management
Basic Energy Sciences
Argonne National Laboratory
Oak Ridge National Laboratory	DE-AC05-00OR22725
Brookhaven National Laboratory
American Pain Society
SLAC National Accelerator Laboratory

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Pierce, E. M., Lilova, K., Missimer, D. M., Lukens, W. W., Wu, L., Fitts, J., Rawn, C., Huq, A., Leonard, D. N., Eskelsen, J. R., Woodfield, B. F., Jantzen, C. M., & Navrotsky, A. (2017). Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite. Environmental Science and Technology, 51(2), 997-1006. https://doi.org/10.1021/acs.est.6b01879

@article{3178451a166241b581293b57a25e0be5,

title = "Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite",

abstract = "Treatment and immobilization of technetium-99 (99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2 x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P43n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4− anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4− anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4− anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.",

author = "Pierce, {Eric M.} and Kristina Lilova and Missimer, {David M.} and Lukens, {Wayne W.} and Lili Wu and Jeffrey Fitts and Claudia Rawn and Ashfia Huq and Leonard, {Donovan N.} and Eskelsen, {Jeremy R.} and Woodfield, {Brian F.} and Jantzen, {Carol M.} and Alexandra Navrotsky",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2017",

month = jan,

day = "17",

doi = "10.1021/acs.est.6b01879",

language = "English",

volume = "51",

pages = "997--1006",

journal = "Environmental Science and Technology",

issn = "0013-936X",

publisher = "American Chemical Society",

number = "2",

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Pierce, EM, Lilova, K, Missimer, DM, Lukens, WW, Wu, L, Fitts, J, Rawn, C, Huq, A, Leonard, DN, Eskelsen, JR, Woodfield, BF, Jantzen, CM & Navrotsky, A 2017, 'Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite', Environmental Science and Technology, vol. 51, no. 2, pp. 997-1006. https://doi.org/10.1021/acs.est.6b01879

TY - JOUR

T1 - Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite

AU - Pierce, Eric M.

AU - Lilova, Kristina

AU - Missimer, David M.

AU - Lukens, Wayne W.

AU - Wu, Lili

AU - Fitts, Jeffrey

AU - Rawn, Claudia

AU - Huq, Ashfia

AU - Leonard, Donovan N.

AU - Eskelsen, Jeremy R.

AU - Woodfield, Brian F.

AU - Jantzen, Carol M.

AU - Navrotsky, Alexandra

PY - 2017/1/17

Y1 - 2017/1/17

N2 - Treatment and immobilization of technetium-99 (99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2 x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P43n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4− anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4− anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4− anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.

AB - Treatment and immobilization of technetium-99 (99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2 x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P43n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4− anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4− anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4− anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.

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Structure and thermochemistry of perrhenate sodalite and mixed guest perrhenate/pertechnetate sodalite

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