RadEMSL

EMSL’s radiochemistry facility, RadEMSL, is designed to accelerate scientific discovery and deepen the understanding of the chemical fate and transport of radionuclides in terrestrial and subsurface ecosystems.

The facility 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. RadEMSL 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. RadEMSL users also have access to expert computational, modeling and simulation resources and support.

The facility provides 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 RadEMSL 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.

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

And don't miss the virtual tour of RadEMSL.

Additional Information:

Instruments

Highlighted Research Applications EMSL's Bruker wide-bore 750 MHz solids/liquids spectrometer is dedicated to radiological and environmental...
Custodian(s): Nancy Washton
The Bruker EMX electron paramagnetic resonance (EPR) spectrometer performs continuous-wave magnetic resonance using electron spins to selectively...
Custodian(s): Eric Walter
Housed in EMSL's RadEMSL (Radiochemistry Annex), the field emission electron microprobe (EMP) enables chemical analysis and imaging of radionuclides...
Custodian(s): Bruce Arey
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
The environmental scanning electron microscope (ESEM) is a new-generation SEM that can image samples under controlled environments and temperatures...
Custodian(s): Bruce Arey, Scott Lea

Science Highlights

Posted: March 22, 2016
The Science A recent study examined in unprecedented detail the structural and thermodynamic properties of uranium (U(v)) containing compounds...
Posted: September 22, 2015
The Science Uranium dioxide (UO2) contains the less soluble and immobile form of uranium in nature, so it is the desired end product of...
Posted: July 31, 2015
Corrosion in uranium dioxide, a major component of fuel rods in nuclear reactors, causes the rods to expand creating problems during routine...
Posted: April 14, 2015
The Science Scientists found the incorporation of neptunium (V) (NpO2+, neptunyl) and uranium (VI) (UO22+, uranyl) in a variety of mineral...
Posted: July 06, 2011
Scientists from Pacific Northwest National Laboratory and Rai Enviro-Chem, LLC, recently published first-ever results that illustrate the importance...

Instruments

There are no related projects at this time.

EMSL’s radiochemistry facility, RadEMSL, is designed to accelerate scientific discovery and deepen the understanding of the chemical fate and transport of radionuclides in terrestrial and subsurface ecosystems.

The facility 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. RadEMSL 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. RadEMSL users also have access to expert computational, modeling and simulation resources and support.

The facility provides 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 RadEMSL 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.

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

And don't miss the virtual tour of RadEMSL.

Additional Information:

Effect of Graphene with Nanopores on Metal Clusters.

Abstract: 

Porous graphene, which is a novel type of defective graphene, shows excellent potential as a support material for metal clusters. In this work, the stability and electronic structures of metal clusters (Pd, Ir, Rh) supported on pristine graphene and graphene with different sizes of nanopore were investigated by first-principle density functional theory (DFT) calculations. Thereafter, CO adsorption and oxidation reaction on the Pd-graphene system were chosen to evaluate its catalytic performance. Graphene with nanopore can strongly stabilize the metal clusters and cause a substantial downshift of the d-band center of the metal clusters, thus decreasing CO adsorption. All binding energies, d-band centers, and adsorption energies show a linear change with the size of the nanopore: a bigger size of nanopore corresponds to a stronger metal clusters bond to the graphene, lower downshift of the d-band center, and weaker CO adsorption. By using a suitable size nanopore, supported Pd clusters on the graphene will have similar CO and O2 adsorption ability, thus leading to superior CO tolerance. The DFT calculated reaction energy barriers show that graphene with nanopore is a superior catalyst for CO oxidation reaction. These properties can play an important role in instructing graphene-supported metal catalyst preparation to prevent the diffusion or agglomeration of metal clusters and enhance catalytic performance. This work was supported by National Basic Research Program of China (973Program) (2013CB733501), the National Natural Science Foundation of China (NSFC-21176221, 21136001, 21101137, 21306169, and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC).

Citation: 
Zhou H, X Chen, L Wang, X Zhong, G Zhuang, X Li, D Mei, and J Wang.2015."Effect of Graphene with Nanopores on Metal Clusters."Physical Chemistry Chemical Physics. PCCP 17(37):24420-24426. doi:10.1039/c5cp04368a
Authors: 
H Zhou
X Chen
L Wang
X Zhong
G Zhuang
X Li
D Mei
J Wang
Capabilities: 
Volume: 
17
Issue: 
37
Pages: 
24420-24426
Publication year: 
2015

Dynamic Structural Changes of SiO2 Supported Pt−Ni Bimetallic Catalysts over Redox Treatments Revealed by NMR and EPR.

Abstract: 

SiO2 supported Pt−Ni bimetallic catalysts with different nickel loadings were prepared and their structural changes after redox treatments were studied by XRD, NMR, and EPR. It is found that the paramagnetic Ni species are mainly located on the surface of silica lattice. The relaxation of detected 29Si nuclei in our samples is mainly governed by a spin-diffusion mechanism. The paramagnetic effects are reflected in the spin−lattice relaxation of Q4 species, with the oxidized samples presenting faster relaxation rates than the corresponding reduced ones. Meanwhile the Q3 species, which are in close contact with the paramagnetic nickel ions, are “spectrally invisible”. In reducing atmosphere Ni gradually diffuses into Pt NPs to form PtNi alloys. While under oxidization treatment, the alloyed Ni atoms migrate outward from the core of Pt NPs and are oxidized. The main EPR spectrum results from reduced nickel species, and the reduced samples show stronger EPR signal than the corresponding oxidized ones. However, in the reduced samples, the superparamagnetic or ferromagnetic metallic Ni particles were inside the PtNi NPs, making their influence on the 29Si relaxation in the SiO2 support weaker than the oxidized samples.

Citation: 
Xu S, ED Walter, Z Zhao, MY Hu, X Han, JZ Hu, and X Bao.2015."Dynamic Structural Changes of SiO2 Supported Pt?Ni Bimetallic Catalysts over Redox Treatments Revealed by NMR and EPR."Journal of Physical Chemistry C 119(36):21219-21226. doi:10.1021/acs.jpcc.5b06344
Authors: 
Xu S
ED Walter
Z Zhao
MY Hu
X Han
JZ Hu
X Bao
Capabilities: 
Volume: 
119
Issue: 
36
Pages: 
21219-21226
Publication year: 
2015

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide.

Abstract: 

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

Citation: 
Loring JS, J Chen, P Benezeth Ep Gisquet, O Qafoku, ES Ilton, NM Washton, CJ Thompson, PF Martin, BP McGrail, KM Rosso, AR Felmy, and HT Schaef.2015."Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide."Langmuir 31(27):7533-7543. doi:10.1021/acs.langmuir.5b01052
Authors: 
Qafoku Odeta
Nancy M Washton
Kevin M Rosso
Loring JS
J Chen
P Benezeth Ep Gisquet
O Qafoku
ES Ilton
NM Washton
CJ Thompson
PF Martin
BP McGrail
KM Rosso
AR Felmy
HT Schaef
Capabilities: 
Volume: 
31
Issue: 
27
Pages: 
7533-7543
Publication year: 
2015

Sealed Rotors for In Situ High Temperature High Pressure MAS NMR.

Abstract: 

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) investigations on heterogeneous samples containing solids, semi-solids, liquid and gases or a mixture of them under non-conventional conditions of a combined high pressure and high temperature, or cold temperature suffer from the unavailability of a perfectly sealed rotor. Here, we report the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are easy to use and are suitable for operation temperatures from below 0 to 250 C and pressures up to 100 bar. As an example of potential applications we performed in situ MAS NMR investigations of AlPO4-5 molecular sieve crystallization, a kinetic study of the cyclohexanol dehydration reaction using 13C MAS NMR, and an investigation of the metabolomics of intact biological tissue at low temperature using 1H HR-MAS NMR spectroscopy. The in situ MAS NMR experiments performed using the reported rotors allowed reproduction of the results from traditional batch reactions, while offering more detailed quantitative information at the molecular level, as demonstrated for the molecular sieve synthesis and activation energy measurements for cyclohexanol dehydration. The perfectly sealed rotor also shows promising application for metabolomics studies using 1H HR-MAS NMR.

Citation: 
Hu JZ, MY Hu, Z Zhao, S Xu, A Vjunov, H Shi, DM Camaioni, CHF Peden, and JA Lercher.2015."Sealed Rotors for In Situ High Temperature High Pressure MAS NMR."Chemical Communications 51(70):13458-13461. doi:10.1039/c5cc03910j
Authors: 
Z Jian
Hu JZ
MY Hu
Z Zhao
S Xu
A Vjunov
H Shi
DM Camaioni
CHF Peden
JA Lercher
Capabilities: 
Volume: 
51
Issue: 
70
Pages: 
13458-13461
Publication year: 
2015

Molecular Dynamics Study of Fe(II) Adsorption, Electron Exchange, and Mobility at Goethite (alpha-FeOOH) Surfaces.

Abstract: 

We present classical molecular simulations of the adsorption free energy profiles for the aqueous Fe(II) ion approaching key low index crystal faces of goethite at neutral surface charge conditions. Calculated profiles show minima corresponding to stable outer- and inner-sphere adsorbed structures. We analyzed the energetics and kinetics of most possible interfacial electron transfer reactions, as well as analyzing the same for subsurface migration pathways of injected electrons through calculating the Marcus free energy surfaces. We conclude that inner-sphere Fe(II)-complex formation is required for the interfacial electron transfer to occur, but the energetic cost of moving from the outer-sphere to inner-sphere geometry may prevent electron injection at some faces. We also show that some surfaces, especially (101), (100) and (001), are more energetically prone toward reduction than others. We demonstrate that subsurface charge migration in directions parallel to the surface, which run along the iron chains, is more energetically plausible than conduction through the resistive crystal bulk phase. Collectively this leads to the conclusion that Fe(II)-catalyzed recrystallization of goethite most likely proceeds by short path length electron migration through specific goethite surfaces along specific directions, until capture at Fe sites structurally susceptible to reduction and release.

Citation: 
Zarzycki PP, SN Kerisit, and KM Rosso.2015."Molecular Dynamics Study of Fe(II) Adsorption, Electron Exchange, and Mobility at Goethite (alpha-FeOOH) Surfaces."Journal of Physical Chemistry C 119(6):3111-3123. doi:10.1021/jp511086r
Authors: 
M Kevin
Zarzycki PP
SN Kerisit
KM Rosso
Capabilities: 
Volume: 
119
Issue: 
6
Pages: 
3111-3123
Publication year: 
2015

Impacts of Organic Ligands on Forsterite Reactivity in Supercritical CO2 Fluids.

Abstract: 

Subsurface injection of CO2 for enhanced hydrocarbon recovery, hydraulic fracturing of unconventional reservoirs, and geologic carbon sequestration produces a complex geochemical setting in which CO2-dominated fluids containing dissolved water and organic compounds interact with rocks and minerals. The details of these reactions are relatively unknown and benefit from additional experimentally derived data. In this study, we utilized an in situ X-ray diffraction technique to examine the carbonation reactions of forsterite (Mg2SiO4) during exposure to supercritical CO2 (scCO2) that had been equilibrated with aqueous solutions of acetate, oxalate, malonate, or citrate at 50 °C and 90 bar. The organics affected the relative abundances of the crystalline reaction products, nesquehonite (MgCO3·3H2O) and magnesite (MgCO3), likely due to enhanced dehydration of the Mg2+ cations by the organic ligands. These results also indicate that the scCO2 solvated and transported the organic ligands to the forsterite surface. This phenomenon has profound implications for mineral transformations and mass transfer in the upper crust.

Citation: 
Miller QR, J Kaszuba, HT Schaef, ME Bowden, and BP McGrail.2015."Impacts of Organic Ligands on Forsterite Reactivity in Supercritical CO2 Fluids."Environmental Science & Technology 49(7):4724–4734. doi:10.1021/es506065d
Authors: 
E Mark
Miller QR
J Kaszuba
HT Schaef
ME Bowden
BP McGrail
Volume: 
Issue: 
Pages: 
Publication year: 
2015

Proton Dynamics on Goethite Nanoparticles and Coupling to Electron Transport.

Abstract: 

The surface chemistry of metal oxide particles is governed by the charge that develops at the interface with aqueous solution. Mineral transformation, biogeochemical reactions, remediation, and sorption dynamics are profoundly affected in response. Here we report implementation of replica-exchange constant-pH molecular dynamics simulations that use classical molecular dynamics for exploring configurational space and Metropolis Monte Carlo walking through protonation space with a simulated annealing escape route from metastable configurations. By examining the archetypal metal oxide, goethite (α-FeOOH), we find that electrostatic potential gradients spontaneously arise between intersecting low-index crystal faces and across explicitly treated oxide nanoparticles at a magnitude exceeding the Johnson–Nyquist voltage fluctuation. Fluctuations in adsorbed proton density continuously repolarize the surface potential bias between edge-sharing crystal faces, at a rate slower than the reported electron–polaron hopping rate in goethite interiors. This suggests that these spontaneous surface potential fluctuations will control the net movement of charge carriers in the lattice.

Citation: 
Zarzycki PP, DMA Smith, and KM Rosso.2015."Proton Dynamics on Goethite Nanoparticles and Coupling to Electron Transport."Journal of Chemical Theory and Computation 11(4):1715-1724. doi:10.1021/ct500891a
Authors: 
M Kevin
Zarzycki PP
DMA Smith
KM Rosso
Capabilities: 
Volume: 
11
Issue: 
4
Pages: 
1715-1724
Publication year: 
2015

Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields.

Abstract: 

A combination of molecular dynamics simulations and pulse field gradient nuclear magnetic resonance spectroscopy is used to investigate the role of exogenous electric fields on the solvation structure and dynamics of alkali ions in dimethyl sulfoxide (DMSO) and as a function of temperature. Good agreement was obtained, for select alkali ions in the absence of an electric field, between calculated and experimentally determined diffusion coefficients normalized to that of pure DMSO. Our results indicate that temperatures of up to 400 K and external electric fields of up to 1 V nm-1 have minimal effects on the solvation structure of the smaller alkali cations (i.e. Li+ and Na+) due to their relatively strong ion-solvent interactions, whereas that of the larger alkali cations (i.e. K+, Rb+, and Cs+) is significantly affected. In addition, although the DMSO exchange dynamics in the first solvation shell differ markedly for the two groups, the drift velocities and mobilities are not significantly affected by the nature of the alkali ion. Overall, although exogenous electric fields induce a drift displacement, their presence does not significantly affect the random diffusive displacement of the alkali ions in DMSO and temperature is found to have generally a stronger influence on dynamical properties, such as the DMSO exchange dynamics and the ion mobilities, than the presence of electric fields.

Citation: 
Kerisit SN, M Vijayakumar, KS Han, and KT Mueller.2015."Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields."Journal of Chemical Physics 142(22):224502. doi:10.1063/1.4921982
Authors: 
T Karl
Kerisit SN
M Vijayakumar
KS Han
KT Mueller
Capabilities: 
Facility: 
Volume: 
Issue: 
Pages: 
Publication year: 
2015

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