Environmental Molecular Sciences Laboratory

A DOE Office of Science User Facility

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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 High resolution, high sensitivity NMR systems that provide one-dimensional and multidimensional data for biological...
Custodian(s): Nancy Washton
Located in RadEMSL (Radiochemistry Annex), the JEM-ARM200CF transmission electron microscope (TEM) enables atomic resolution of biogeochemical...
Custodian(s): Scott Lea
The Bruker Elexsys 580 electron paramagnetic resonance (EPR) spectrometer performs continuous wave and pulsed magnetic resonance using electron spins...
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...

Science Highlights

Posted: September 22, 2016
Plutonium is a highly complex element. Scientists at Pacific Northwest National Laboratory and Washington State University used RadEMSL, EMSL’s...
Posted: March 22, 2016
The Science A recent study examined in unprecedented detail the structural and thermodynamic properties of uranium (U(v)) containing compounds called...
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 structures...

Instruments

There are no related projects at this time.

Related Videos

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:

Sulfidation of magnetite with incorporated uranium

Abstract: 

Uranium (U) is a radionuclide of key environmental interest due its abundance by mass within radioactive waste and presence in contaminated land scenarios. Ubiquitously present iron (oxyhydr)oxide mineral phases, such as (nano)magnetite, have been identified as candidates for immobilisation of U via incorporation into the mineral structure. Studies of how biogeochemicalprocesses, such as sulfidation from the presence of sulfate-reducing bacteria, may affect iron (oxyhydr)oxides and impact radionuclide mobility are important in order to underpin geological disposal of radioactive waste and manage radioactively contaminated land. Here, this study utilised a highly controlled abiotic method for sulfidation of U(V) incorporated into nanomagnetite to determine the fate and speciation of U. Upon sulfidation, transient release of U into solution occurred (~8.6 % total U) for up to 3 days, despite the highly reducing conditions. As the system evolved, lepidocrocite was observed to form over a period of days to weeks. After 10 months, XAS and geochemical data showed all U was partitioned to the solid phase, as both nanoparticulate uraninite (U(IV)O2) and a percentage of retained U(V). Further EXAFS analysis showed incorporation of the residual U(V) fraction into an iron (oxyhydr)oxide mineral phase, likely nanomagnetite or lepidocrocite. Overall, these results provide new insights into the stability of U(V) incorporated iron (oxyhydr)oxides during sulfidation, confirming the longer term retention of U in the solid phase under complex, environmentally relevant conditions.

Citation: 
Townsend L., K. Morris, R. Harrison, B. Schacherl, T. Vitova, L. Kovarik, and C.I. Pearce, et al. 2021. "Sulfidation of magnetite with incorporated uranium." <i>Chemosphere</i> 276. PNNL-SA-160714. doi:10.1016/j.chemosphere.2021.130117
Authors: 
Libor Kovarik,
Townsend
Luke;Morris
Katherine;Harrison
Robert;Pearce
Carolyn I;Kovarik
Libor;Mosselmans
JFW;Shaw
Samuel;Schacherl
Bianca;Vitova
Tonya
Facility: 

Mechanisms of Manganese(II) Oxidation by Filamentous Ascomycete Fungi Vary with Species and Time as a Function of Secretome

Abstract: 

Manganese (Mn) oxides are among the strongest oxidants and sorbents in the environment, and Mn(II) oxidation to Mn(III/IV) (hydr)oxides includes both abiotic and microbially-mediated processes. While white-rot Basidiomycete fungi oxidize Mn(II) using laccases and manganese peroxidases in association with lignocellulose degradation, the mechanisms by which filamentous Ascomycete fungi oxidize Mn(II) and a physiological role for Mn(II) oxidation in these organisms remain poorly understood. Here we use a combination of chemical and in-gel assays and bulk mass spectrometry to demonstrate secretome-based Mn(II) oxidation in three phylogenetically diverse Ascomycetes that is mechanistically distinct from hyphal-associated Mn(II) oxidation on solid substrates. We show that Mn(II) oxidative capacity of these fungi is dictated by species-specific secreted enzymes and varies with secretome age, and we reveal the presence of both Cu-based and FAD-based Mn(II) oxidation mechanisms in all 3 species, demonstrating mechanistic redundancy. Specifically, we identify candidate Mn(II)- oxidizing enzymes as tyrosinase in Stagonospora sp. SRC1lsM3a, bilirubin oxidase in Stagonospora sp. and Paraconiothyrium sporulosum AP3s5-JAC2a, and GMC oxidoreductase in all 3 species, including Pyrenochaeta sp. DS3sAY3a. Furthermore, we demonstrate that secretome-based Mn(II) oxidative capacity is induced by the presence of Mn(II) in Stagonospora sp. and Pyrenochaeta sp., suggesting a physiological role for Mn(II) oxidation in these Ascomycetes. The diversity of the candidate Mn(II)-oxidizing enzymes identified in this study suggests that the ability of fungal secretomes to oxidize Mn(II) may be more widespread than previously thought.

Citation: 
Zeiner C.A., S.O. Purvine, E.M. Zink, S. Wu, L. Pasa Tolic, D.L. Chaput, and C.M. Santelli, et al. 2021. "Mechanisms of Manganese(II) Oxidation by Filamentous Ascomycete Fungi Vary with Species and Time as a Function of Secretome Composition." <i>Frontiers in Microbiology</i> 12. PNNL-SA-157175. doi:10.3389/fmicb.2021.610497
Authors: 
Zeiner
Carolyn A;Purvine
Samuel O;Zink
Erika M;Wu
Si;Pasa Tolic
Ljiljana;Chaput
Dominique L;Santelli
Cara M;Hansel
Colleen M
Facility: 

Covalency in Fe2O3 and FeO: Consequences for XPS Satellite Intensity

Abstract: 

The covalent character of the interaction between the metal cation and the oxygen ligands has been examined for two Fe oxides with different nominal oxidation states, Fe(II)O and Fe(III)2O3. The covalent character is examined for the initial, ground state configuration and for the ionic states involving removal of a shallow core, Fe 3p, and a deep core, Fe 2p, electron. The covalency is assessed based on novel theoretical analyses of wavefunctions for the various cases. It is found that the covalency is considerably different for different oxidation states and for different ionized and non-ionized configurations. The changes in covalency for the ions are shown to be responsible for important changes in relaxation energies for X-Ray Photoelectron Spectroscopy, XPS, spectra and in the intensity lost from main XPS peaks to shake satellites. While these consequences are not observables themselves, they are important for the interpretation of the XPS spectra; in particular for efforts to extract stoichiometries of these iron oxides from XPS data. This is a finding likely applicable across various 3d transition metal oxide materials.

Citation: 
Bagus P.S., C.J. Nelin, C.R. Brundle, B.V. Crist, N. Lahiri, and K.M. Rosso. 2020. "Covalency in Fe2O3 and FeO: Consequences for XPS Satellite Intensity." <i>Journal of Chemical Physics</i> 153, no. 19:194702. PNNL-SA-158041. doi:10.1063/5.0030350
Authors: 
Bagus
Paul Saul;Nelin
Connie J;Brundle
Christopher R;Crist
B V;Lahiri
Nabajit;Rosso
Kevin M
Facility: 

Towards Data-Driven Next-Generation Transmission Electron Microscopy

Abstract: 

The rapidly evolving field of electron microscopy touches nearly every aspect of mod- ern life, underpinning impactful materials discoveries in applications such as quan- tum information science, energy, and medicine. As the field enters a new decade, a paradigm has begun to emerge in which the convergence of advanced instrumenta- tion, robust in-situ platforms, and data-driven experimentation will help researchers distill observations of ever more complex systems into meaningful physical properties and mechanisms. Here we present the findings from the first in a series of work- shops gathering together scientists and technologists across academia, government laboratories, and industry, with the goal to develop a critical roadmap for next- generation transmission electron microscopy (NexTEM). We provide a perspective on the present and emerging state-of-the-art, highlighting progress and the crucial developments still needed to realize the materials of tomorrow.

Citation: 
Spurgeon S.R., C. Ophus, L. Jones, A.K. Petford-Long, S.V. Kalinin, M.J. Olszta, and R. Dunin-Borkowski, et al. 2021. "Towards Data-Driven Next-Generation Transmission Electron Microscopy." <i>Nature Materials</i> 20. PNNL-SA-152427. doi:10.1038/s41563-020-00833-z
Authors: 
Spurgeon
Steven R;Ophus
Colin;Jones
Lewys;Petford-Long
Ama K;Kalinin
Sergei V;Olszta
Matthew J;Dunin-Borkowski
Rafal;Salmon
Norman;Hattar
Khalid;Yang
Wei-Chang D;Sharma
Renu;Du
Yingge;Chiaramonti
Ann N;Buck
Edgar C;Kovarik
Libor;Penn
R. L;Li
Dongsheng;Zhang
Xin;Murayama
Mitsuhiro;Taheri
Mitra L;Zheng
Haimei
Facility: 

Single Cobalt Atom Sites Coordinated with Nitrogen for High Performance Oxygen Reduction Catalysts in Acidic Media

Abstract: 

Although significant progress has been made in Fe-based platinum group metal (PGM)-
free oxygen reduction reaction (ORR) catalysts, Fenton chemistry caused by the presence of Fe
causes membrane degradation, limiting the use of these catalysts in proton exchange membrane
fuel cells (PEMFCs). Therefore, PGM-free catalysts that are also free of Fe are urgently needed to
enable durable and inexpensive PEMFCs. Here, we report a new type of highly dispersed nitrogencoordinated
single-atom Co site catalyst. This catalyst is derived from Co-doped metal-organic
frameworks through a one-step controlled thermal activation. Co-location of Co-N at the atomic
level was verified directly using aberration-corrected electron microscopy couple with electron
energy loss spectra at atomic level. Such a catalyst with properly controlled Co doping content and
thermal activation shows a half-wave potential of 0.80 V vs. RHE in acids, similar to that of state
of the art Fe-N-C catalysts, and only 60 mV lower than Pt catalysts (60 mgPt/cm2) in acidic
solutions. Exceptional stability was observed in both potential cycling and constant potential (e.g.,
0.7 V) tests. The high ORR performance is attributed to the presence of single CoNx active sites
embedded in the porous carbon matrix without formation of inactive Co aggregates. Single cell
tests further confirmed that the intrinsic high ORR activity and stability translate to highperformance
in fuel cells. This atomic Co catalyst is a promising step toward replacement of Fe in
PGM-free catalysts for advanced fuel cell technologies.

Citation: 
Engelhard M.H., and Y. Shao. 2018. "Single Cobalt Atom Sites Coordinated with Nitrogen for High Performance Oxygen Reduction Catalysts in Acidic Media." <i>Advanced Materials</i>. PNNL-SA-127423. doi:10.1002/adma.201706758
Authors: 
Shao
Yuyan;Engelhard
Mark H
Facility: 
Instruments: 

Building Advanced Materials via Particle Aggregation and Molecular Self-Assembly

Abstract: 

Hierarchical and other advanced materials have attracted increasing attention due to their unique physical and chemical properties, which strongly depend on morphology and size.1-2 These materials have been applied in important technological fields such as energy, catalysis, optical devices, water purification, pollutant removal, CO2 sequestration, and biomedicine.3-7 Particle-based crystallization and self-assembly of molecules are important pathways to synthesize advanced materials of complex structures.8-11 Unlike monomer-by-monomer addition or Ostwald ripening, particle-based crystallization occurs via particle-by-particle addition, to form larger crystals or clusters.8, 12 To date, numerous advanced materials have been synthesized in the lab using particle-based crystallization. Examples include metals such as Pt, Pd, Au, Ag, and Cu;13 alloys such as Pt-Ni, Pt-Cu, Pt-Fe, and Au-Ag;14 metal oxides such as ZnO, TiO2, CuO, and a-Fe2O3, Fe3O4;15-19 and metal sulfides such as PbS, PbSe, ZnS, and CdS.20-21 In addition, particle aggregation-based crystallization has been observed in nature, such as in various geological and biological minerals including calcite, collagen, and others.22-24 Different from the particle-based crystallization, self-assembly of molecules has also been used to build advanced materials such as molecular clusters and nanoparticles. For instance, advanced luminescent materials have been prepared by aggregation-induced emission (AIE) of intrinsically non-emissive molecules.25-26 One of the challenges facing this fast-growing field of advanced materials is to develop a fundamental understanding of the interactions between particles or molecules in a growth medium and the resulting response dynamics.

Citation: 
Zhang X., X. Zhang, and C. Wang. 2019. "Building Advanced Materials via Particle Aggregation and Molecular Self-Assembly." <i>Journal of Materials Research</i> 34, no. 17:2911-2913. PNNL-SA-156264. doi:10.1557/jmr.2019.272
Authors: 
Chongmin Wang,
Zhang
Xin;Zhang
Xianwen;Wang
Chongmin
Facility: 

Electron Transfer Reactions at the Nexus of Water, Minerals, and Contaminant Metals

Abstract: 

The chemistry of natural aquatic systems is fundamentally based on electron
transfer reactions. This includes inorganic, organic, and biologic processes, which
in the natural environment couple together in complex ways to set the prevailing
chemical characteristics of the system. At the molecular scale, electron transfer entails
a redistribution of charge between reactants during mutual encounter, a redistri
-
bution that often breaks or makes new chemical bonds and imparts new properties
to the products. These new properties can come in the form of dramatic changes,
such as transforming a chemical species from toxic to benign, or from mostly watersoluble to insoluble, leading to nearly instantaneous precipitation of solids.

Citation: 
Rosso K.M. 2020. "Electron Transfer Reactions at the Nexus of Water, Minerals, and Contaminant Metals." <i>Actinide Research Quarterly</i> 2020, no. Second Quarter:37-40. PNNL-SA-156218.
Authors: 
Rosso
Kevin M
Facility: 

Nanoscale Observations of Fe(II)-Induced Ferrihydrite Transformation

Abstract: 

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated in suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. Here, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl-SO4-HCO3 anion effects. Emergence of Lp/ Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions absent HCO3-; whereas Lp and Gt concomitantly nucleate in SO42--rich solutions and also when co-solute HCO3- is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO4) or acicular needle-shaped (in HCO3) Gt crystals nucleate and grow radially outward of Fh aggregates. Stages of transformation monitored by in situ µ XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelming supports dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

Citation: 
Qafoku O., L. Kovarik, M.E. Bowden, E. Nakouzi, A. Sheng, J. Liu, and C.I. Pearce, et al. 2020. "Nanoscale Observations of Fe(II)-Induced Ferrihydrite Transformation." <i>Environmental Science Nano</i> 7, no. 10:2953-2967. PNNL-SA-155340. doi:10.1039/D0EN00730G
Authors: 
Qafoku
Odeta;Kovarik
Libor;Bowden
Mark E;Nakouzi
Elias;Sheng
Anxu;Liu
Juan;Pearce
Carolyn I;Rosso
Kevin M
Facility: 

Low Temperature and Limited Water Activity Reveal a Pathway to Magnesite via Amorphous Magnesium Carbonate

Abstract: 

Forsterite carbonated in thin H2O films to magnesite via amorphous magnesium carbonate during reaction with H2O-bearing liquid CO2 at 25 °C. This reaction pathway contrasts with previous studies on the same system but carried out at higher H2O activity and temperature, where more highly hydrated nesquehonite was the metastable intermediate.

Citation: 
Mergelsberg S.T., S.N. Kerisit, E.S. Ilton, O. Qafoku, C.J. Thompson, and J.S. Loring. 2020. "Low Temperature and Limited Water Activity Reveal a Pathway to Magnesite via Amorphous Magnesium Carbonate." <i>Chemical Communications</i> 56, no. 81:12154-12157. PNNL-SA-154304. doi:10.1039/D0CC04907G
Authors: 
Mergelsberg
Sebastian T;Kerisit
Sebastien N;Ilton
Eugene S;Qafoku
Odeta;Thompson
Christopher J;Loring
John S
Facility: 

Antifungal symbiotic peptide NCR044 exhibits unique structure and multifaceted mechanisms of action that confer plant protection

Abstract: 

In the indeterminate nodules of the model legume Medicago truncatula, ~700 nodule-specific cysteine-rich (NCR) peptides with a conserved cysteine-signature are expressed. NCR peptides are highly diverse in sequence and some of these cationic peptides exhibit antimicrobial activity in vitro and in vivo. However, there is a lack of knowledge regarding their structural architecture, antifungal activity, and modes of action against plant fungal pathogens. Here, the three-dimensional NMR structure of a 36-amino acid NCR peptide, NCR044, was solved. Aside from one four-residue a-helix and one three-residue anti-parallel ß-sheet stabilized by two disulfide bonds, the peptide was otherwise disordered. NCR044 exhibited potent fungicidal activity against multiple plant fungal pathogens including Botrytis cinerea and three Fusarium species. It also inhibited germination in quiescent spores of B. cinerea. In germlings, NCR044 breached the fungal plasma membrane and induced reactive oxygen species generation. NCR044 bound to multiple bioactive phosphoinositides in vitro. In vivo, time-lapse confocal and super-resolution microscopy with NCR044 revealed strong fungal cell wall binding, penetration of the cell membrane at discrete foci followed by gradual loss of turgor, accumulation in the cytoplasm, and elevated levels in nucleoli of germlings. Spray-applied NCR044 significantly reduced gray mold disease symptoms caused by the fungal pathogen B. cinerea in tomato and tobacco plants and post-harvest products. This study highlights a novel structurally unique fungal cell penetrating NCR peptide which localized to multiple compartments in a fungal pathogen. Antifungal properties of the peptide reported here warrant further validation of its potential as a peptide-based fungistat/fungicide.

Citation: 
Velivelli S.L., K. Czymmack, H. Li, J.B. Shaw, G.W. Buchko, and D. Shah. 2020. "Antifungal symbiotic peptide NCR044 exhibits unique structure and multifaceted mechanisms of action that confer plant protection." <i>Proceedings of the National Academy of Sciences of the United States of America</i> 117, no. 27:16043-16054. PNNL-SA-150641. doi:10.1073/pnas.2003526117
Authors: 
Buchko
Garry W;Shah
Dilip;Shaw
Jared B;Velivelli
Siva L;Czymmack
Kirk;Li
Hui
Facility: 

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