Radiochemistry Annex

EMSL’s Radiochemistry Annex is designed to accelerate scientific discovery and deepen the understanding of the chemical fate and transport of radionuclides in terrestrial and subsurface ecosystems.

The annex offers experimental and computational tools uniquely suited for actinide chemistry studies. The spectroscopic and imaging instruments at this facility are ideally designed for the study of contaminated environmental materials, examination of radionuclide speciation and detection of chemical signatures. The annex houses nuclear magnetic resonance instruments and surface science capabilities, such as X-ray photoelectron spectroscopy, electron microscopy, electron microprobe, transmission electron microscopy and scanning electron microscopy. Annex users also have access to expert computational, modeling and simulation resources and support.

The annex is an environment where multiple experimental approaches are encouraged. Investigating problems at an integrated, cross-disciplinary level encourages holistic understanding, which ultimately provides policy makers the information they need to make sound remediation choices.

Like all of EMSL's capabilities, those housed in the annex are available to the scientific community at typically no cost for openly published research. Scientists gain access to instruments and collaborate with onsite microscopy experts through a peer-reviewed proposal process. Research conducted in the annex requires special information and handling. Prior to submitting a proposal, potential users should familiarize themselves with the guidance for using and shipping radioactive material to the annex.

Radiochemistry Annex videos on EMSL's YouTube channel - Learn about the individual instruments in the Radiochemistry Annex and specifically how they advance subsurface and terrestrial ecosystem science.

And don't miss the virtual tour of our Radiochemistry Annex.

Research applications Samples containing paramagnetics Soils (SOM and NOM) Metal oxide materials for catalysis applications Researchers may operate...
Custodian(s): Herman M Cho
EMSL's Bruker wide-bore 750 MHz solids/liquids/imaging spectrometer is dedicated to radiological and environmental samples. Housed in the EMSL...
Custodian(s): David Hoyt
The Bruker EMX electron paramagnetic resonance (EPR) spectrometer performs continuous-wave magnetic resonance using electron spins to selectively...
Custodian(s): Eric Walter
EMSL's Digital Instruments Radiological BioScope™ Atomic Force Microscope (AFM) allows radiological samples to be examined in fluids or air with...
Custodian(s): Kevin M. Rosso
Housed in EMSL's Radiochemistry Annex, the field emission electron microprobe (EMP) enables chemical analysis and imaging of radionuclides with high...
Custodian(s): Bruce Arey
Posted: July 06, 2011
Scientists from Pacific Northwest National Laboratory and Rai Enviro-Chem, LLC, recently published first-ever results that illustrate the importance...

EMSL’s Radiochemistry Annex is designed to accelerate scientific discovery and deepen the understanding of the chemical fate and transport of radionuclides in terrestrial and subsurface ecosystems.

The annex offers experimental and computational tools uniquely suited for actinide chemistry studies. The spectroscopic and imaging instruments at this facility are ideally designed for the study of contaminated environmental materials, examination of radionuclide speciation and detection of chemical signatures. The annex houses nuclear magnetic resonance instruments and surface science capabilities, such as X-ray photoelectron spectroscopy, electron microscopy, electron microprobe, transmission electron microscopy and scanning electron microscopy. Annex users also have access to expert computational, modeling and simulation resources and support.

The annex is an environment where multiple experimental approaches are encouraged. Investigating problems at an integrated, cross-disciplinary level encourages holistic understanding, which ultimately provides policy makers the information they need to make sound remediation choices.

Like all of EMSL's capabilities, those housed in the annex are available to the scientific community at typically no cost for openly published research. Scientists gain access to instruments and collaborate with onsite microscopy experts through a peer-reviewed proposal process. Research conducted in the annex requires special information and handling. Prior to submitting a proposal, potential users should familiarize themselves with the guidance for using and shipping radioactive material to the annex.

Radiochemistry Annex videos on EMSL's YouTube channel - Learn about the individual instruments in the Radiochemistry Annex and specifically how they advance subsurface and terrestrial ecosystem science.

And don't miss the virtual tour of our Radiochemistry Annex.

7 Å Resolution in Protein 2-Dimentional-Crystal X-Ray Diffraction at Linac Coherent Light Source.

Abstract: 

Membrane proteins arranged as two-dimensional (2D) crystals in the lipid en- vironment provide close-to-physiological structural information, which is essential for understanding the molecular mechanisms of protein function. X-ray diffraction from individual 2D crystals did not represent a suitable investigation tool because of radiation damage. The recent availability of ultrashort pulses from X-ray Free Electron Lasers (X-FELs) has now provided a mean to outrun the damage. Here we report on measurements performed at the LCLS X-FEL on bacteriorhodopsin 2D crystals mounted on a solid support and kept at room temperature. By merg- ing data from about a dozen of single crystal diffraction images, we unambiguously identified the diffraction peaks to a resolution of 7 °A, thus improving the observable resolution with respect to that achievable from a single pattern alone. This indicates that a larger dataset will allow for reliable quantification of peak intensities, and in turn a corresponding increase of resolution. The presented results pave the way to further X-FEL studies on 2D crystals, which may include pump-probe experiments at subpicosecond time resolution.

Citation: 
Pedrini B, CJ Tsai, G Capitani, C Padeste, M Hunter, NA Zatsepin, A Barty, H Benner, S Boutet, GK Feld, S Hau-Riege, R Kirian, C Kupitz, M Messerschmidt, JI Ogren, T Pardini, B Segelke, GJ Williams, JC Spence , R Abela, MA Coleman, JE Evans, G Schertler, M Frank, and XD Li.2014."7 Å Resolution in Protein 2-Dimentional-Crystal X-Ray Diffraction at Linac Coherent Light Source."Philosophical Transactions of the Royal Society of London Series B, Biological Sciences 369(1647):Article No. 20130500. doi:10.1098/rstb.2013.0500
Authors: 
B Pedrini
CJ Tsai
G Capitani
C Padeste
M Hunter
NA Zatsepin
A Barty
H Benner
S Boutet
GK Feld
S Hau-Riege
R Kirian
C Kupitz
M Messerschmidt
JI Ogren
T Pardini
B Segelke
GJ Williams
JC Spence
R Abela
MA Coleman
JE Evans
G Schertler
M Frank
XD Li
Instruments: 
Publication year: 
2014

In situ molecular imaging of hydrated biofilm in a microfluidic reactor by ToF-SIMS.

Abstract: 

The first results of using a novel single channel microfluidic reactor to enable Shewanella biofilm growth and in situ characterization using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in the hydrated environment are presented. The new microfluidic interface allows direct probing of the liquid surface using ToF-SIMS, a vacuum surface technique. The detection window is an aperture of 2 m in diameter on a thin silicon nitride (SiN) membrane and it allows direct detection of the liquid surface. Surface tension of the liquid flowing inside the microchannel holds the liquid within the aperture. ToF-SIMS depth profiling was used to drill through the SiN membrane and the biofilm grown on the substrate. In situ 2D imaging of the biofilm in hydrated state was acquired, providing spatial distribution of the chemical compounds in the biofilm system. This data was compared with a medium filled microfluidic reactor devoid of biofilm and dried biofilm samples deposited on clean silicon wafers. Principle Component Analysis (PCA) was used to investigate these observations. Our results show that imaging biofilms in the hydrated environment using ToF-SIMS is possible using the unique microfluidic reactor. Moreover, characteristic biofilm fatty acids fragments were observed in the hydrated biofilm grown in the microfluidic channel, illustrating the advantage of imaging biofilm in its native environment.

Citation: 
Hua X, XY Yu, Z Wang, L Yang, B Liu, Z Zhu, AE Tucker, WB Chrisler, EA Hill, S Thevuthasan, Y Lin, S Liu, and MJ Marshall.2014."In situ molecular imaging of hydrated biofilm in a microfluidic reactor by ToF-SIMS."Analyst 139:1609-1613. doi:10.1039/C3AN02262E
Authors: 
X Hua
XY Yu
Z Wang
L Yang
B Liu
Z Zhu
AE Tucker
WB Chrisler
EA Hill
S Thevuthasan
Y Lin
S Liu
MJ Marshall
Instruments: 
Publication year: 
2014

Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses.

Abstract: 

Chemical durability is not a single material property that can be uniquely measured. Instead it is the response to a host of coupled material and environmental processes whose rates are estimated by a combination of theory, experiment, and modeling. High-level nuclear waste (HLW) glass is perhaps the most studied of any material yet there remain significant technical gaps regarding their chemical durability. The phenomena affecting the long-term performance of HLW glasses in their disposal environment include surface reactions, transport properties to and from the reacting glass surface, and ion exchange between the solid glass and the surrounding solution and alteration products. The rates of these processes are strongly influenced and are coupled through the solution chemistry, which is in turn influenced by the reacting glass and also by reaction with the near-field materials and precipitation of alteration products. Therefore, those processes must be understood sufficiently well to estimate or bound the performance of HLW glass in its disposal environment over geologic time-scales. This article summarizes the current state of understanding of surface reactions, transport properties, and ion exchange along with the near-field materials and alteration products influences on solution chemistry and glass reaction rates. Also summarized are the remaining technical gaps along with recommended approaches to fill those technical gaps.

Citation: 
Vienna JD, JV Ryan, S Gin, and Y Inagaki.2013."Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses."International Journal of Applied Glass Science 4(4):283-294. doi:10.1111/ijag.12050
Authors: 
JD Vienna
JV Ryan
S Gin
Y Inagaki
Instruments: 
Volume: 
4
Issue: 
4
Pages: 
283-294
Publication year: 
2013

In situ chemical probing of the electrode-electrolyte interface by ToF-SIMS.

Abstract: 

A portable vacuum interface allowing direct probing of the electrode-electrolyte interface was developed. A classical electrochemical system consisting of gold working electrode, platinum counter electrode, platinum reference electrode, and potassium iodide electrolyte was used to demonstrate real-time observation of the gold iodide adlayer on the electrode and chemical species as a result of redox reactions using cyclic voltammetry (CV) and the time-of-flight secondary ion mass spectrometry (ToF-SIMS, a vacuum-based surface analytical technique) simultaneously. This microfluidic electrochemical probe provides a new way to investigate the surface region with adsorbed molecules and region of diffused layer with chemical speciation in liquids in situ by surface sensitive techniques.

Citation: 
Liu B, XY Yu, Z Zhu, X Hua, L Yang, and Z Wang.2014."In situ chemical probing of the electrode-electrolyte interface by ToF-SIMS."Lab on a Chip 14(5):855-859. doi:10.1039/C3LC50971K
Authors: 
B Liu
XY Yu
Z Zhu
X Hua
L Yang
Z Wang
Instruments: 
Volume: 
14
Issue: 
5
Pages: 
855-859
Publication year: 
2014

An international initiative on long-term behavior of high-level nuclear waste glass.

Abstract: 

Nations producing borosilicate glass as an immobilization material for radioactive wastes resulting from spent nuclear fuel reprocessing have reinforced scientific collaboration to obtain consensus on mechanisms controlling the long-term dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research with modern materials science techniques. The paper briefly reviews the radioactive waste vitrification programmes of the six participant nations and summarizes the state-of-the-art of glass corrosion science, emphasizing common scientific needs and justifications for on-going initiatives.

Citation: 
Gin S, A Abdelouas, LJ Criscenti, WL Ebert, K Ferrand, T Geisler, MT Harrison, Y Inagaki, S Mitsui, KT Mueller, JC Marra, CG Pantano, EM Pierce, JV Ryan, JM Schofield, CI Steefel, and JD Vienna.2013."An international initiative on long-term behavior of high-level nuclear waste glass."Materials Today 16(6):243-248. doi:10.1016/j.mattod.2013.06.008
Authors: 
S Gin
A Abdelouas
LJ Criscenti
WL Ebert
K Ferr
T Geisler
MT Harrison
Y Inagaki
S Mitsui
KT Mueller
JC Marra
CG Pantano
EM Pierce
JV Ryan
JM Schofield
CI Steefel
JD Vienna
Instruments: 
Volume: 
16
Issue: 
6
Pages: 
243-248
Publication year: 
2013

Monte Carlo Simulations of the Corrosion of Aluminoborosilicate Glasses.

Abstract: 

Aluminum is one of the most common components included in nuclear waste glasses. Therefore, Monte Carlo (MC) simulations were carried out to investigate the influence of aluminum on the rate and mechanism of dissolution of sodium borosilicate glasses in static conditions. The glasses studied were in the compositional range (70-2x)% SiO2 x% Al2O3 15% B2O3 (15+x)% Na2O, where 0 ≤ x ≤ 15%. The simulation results show that increasing amounts of aluminum in the pristine glasses slow down the initial rate of dissolution as determined from the rate of boron release. However, the extent of corrosion - as measured by the total amount of boron release - initially increases with addition of Al2O3, up to 5 Al2O3 mol%, but subsequently decreases with further Al2O3 addition. The MC simulations reveal that this behavior is due to the interplay between two opposing mechanisms: (1) aluminum slows down the kinetics of hydrolysis/condensation reactions that drive the reorganization of the glass surface and eventual formation of a blocking layer; and (2) aluminum strengthens the glass thereby increasing the lifetime of the upper part of its surface and allowing for more rapid formation of a blocking layer. Additional MC simulations were performed whereby a process representing the formation of a secondary aluminosilicate phase was included. Secondary phase formation draws dissolved glass components out of the aqueous solution, thereby diminishing the rate of condensation and delaying the formation of a blocking layer. As a result, the extent of corrosion is found to increase continuously with increasing Al2O3 content, as observed experimentally. For Al2O3 < 10 mol%, the MC simulations also indicate that, because the secondary phase solubility eventually controls the aluminum content in the part of the altered layer in contact with the bulk aqueous solution, the dissolved aluminum and silicon concentrations at steady state are not dependent on the Al2O3 content of the pristine aluminoborosilicate glass.

Citation: 
Kerisit SN, JV Ryan, and EM Pierce.2013."Monte Carlo Simulations of the Corrosion of Aluminoborosilicate Glasses."Journal of Non-crystalline Solids 378:273-281. doi:10.1016/j.jnoncrysol.2013.07.014
Authors: 
SN Kerisit
JV Ryan
EM Pierce
Instruments: 
Publication year: 
2013

Cold Crucible Induction Melter Studies for Making Glass Ceramic Waste Forms: A Feasibility Assessment.

Abstract: 

Glass ceramics are being developed to immobilize fission products, separated from used nuclear fuel by aqueous reprocessing, into a stable waste form suitable for disposal in a geological repository. This work documents the glass ceramic formulation at bench scale and for a scaled melter test performed in a pilot-scale (~1/4 scale) cold crucible induction meter (CCIM). Melt viscosity, electrical conductivity, and crystallization behavior upon cooling were measured on a small set of compositions to select a formulation for melter testing. Property measurements also identified a temperature range for melter operation and cooling profiles necessary to crystallize the targeted phases in the waste form. Bench scale and melter run results successfully demonstrate the processability of the glass ceramic using the CCIM melter technology.

Citation: 
Crum JV, V Maio, JS McCloy, C Scott, BJ Riley, B Benefiel, JD Vienna, K Archibald, CP Rodriguez, V Rutledge, Z Zhu, JV Ryan, and MJ Olszta.2014."Cold Crucible Induction Melter Studies for Making Glass Ceramic Waste Forms: A Feasibility Assessment."Journal of Nuclear Materials 444(1-3):481-492. doi:10.1016/j.jnucmat.2013.10.029
Authors: 
JV Crum
V Maio
JS McCloy
C Scott
BJ Riley
B Benefiel
JD Vienna
K Archibald
CP Rodriguez
V Rutledge
Z Zhu
JV Ryan
MJ Olszta
Instruments: 
Volume: 
444
Pages: 
481-492
Publication year: 
2014

Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: application to a nuclear glass

Abstract: 

We report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution-precipitation models for silicate minerals.

Citation: 
Gin S, JV Ryan, DK Schreiber, JJ Neeway, and M Cabie.2013."Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: application to a nuclear glass specimen altered 25 years in a granitic environment ."Chemical Geology 349-350:99-109.
Authors: 
S Gin
JV Ryan
DK Schreiber
JJ Neeway
M Cabie
Instruments: 
Publication year: 
2013

Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses.

Abstract: 

Solid-state NMR is a powerful tool for probing the role and significance of alteration layers in determining the kinetics for the corrosion of nuclear waste glass. NMR methods are used to probe the chemical structure of the alteration layers to elucidate information about their chemical complexity, leading to increased insight into the mechanism of altered layer formation. Two glass compositions were examined in this study: a glass preliminarily designed for nuclear waste immobilization (called AFCI) and a simplified version of this AFCI glass (which we call SA1R). Powdered glasses with controlled and known particles sizes were corroded at 90 °C for periods of one and five months with a surface-area to solution-volume ratio of 100,000 m-1. 1H-29Si CP-CPMG MAS NMR, 1H-27Al CP-MAS NMR, 1H-11B CP-MAS NMR, and 1H-23Na CP-MAS NMR experiments provide isolated structural information about the alteration layers, which differ in structure from that of the pristine glass. Both glasses studied here develop alteration layers composed primarily of [IV]Si species. Aluminum is also retained in the alteration layers, perhaps facilitated by the observed increase in coordination from [IV]Al to [VI]Al, which correlates with a loss of charge balancing cations. 1H-11B CP-MAS NMR observations indicated a retention of boron in hydrated glass layers, which has not been characterized by previous work. For the AFCI glass, secondary phase formation begins during the corrosion times considered here, and these neophases are detected within the alteration layers. We identify precursor phases as crystalline sodium metasilicates. An important finding is that layer thickness depends on the length of the initial alteration stages and varies only with respect to silicon species during the residual rate regime.

Citation: 
Murphy KA, NM Washton, JV Ryan, CG Pantano, and KT Mueller.2013."Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses."Journal of Non-crystalline Solids 369:44-54. doi:10.1016/j.jnoncrysol.2013.03.021
Authors: 
KA Murphy
NM Washton
JV Ryan
CG Pantano
KT Mueller
Instruments: 
Publication year: 
2013

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