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At least 505 records · Page 28

Modular Caustic-Side Solvent Extraction Unit (MCU) Improved Solvent Quality and Processing Results - 17496

The Modular Caustic-Side Solvent Extraction (CSSX) Unit (MCU) is a process for Cs-137 removal from legacy nuclear waste. MCU began hot operations in 2008 with an initial planned operating life of three years and a design life of five years. After eight years of operation, MCU has processed more than 23.8 million liters (6.3 million gallons) of waste. The MCU process uses a solvent developed by Oak Ridge National Laboratory (ORNL) to extract the fission product Cs-137 from liquid salt waste, or salt solution (SS), stored in the Tank Farms at Savannah River Site (SRS) after the material has been treated through the Actinide Removal Process (ARP). Batches of SS are prepared and first fed to the ARP, where it is treated to become clarified SS (CSS), then fed to MCU. Once the Cs-137 has been extracted by the solvent, the CSS becomes decontaminated SS (DSS), which is ultimately processed into a cementitious grout at the Saltstone Production Facility (SPF) and subsequently disposed of at the Saltstone Disposal Facility (SDF). The Cs-137 is then stripped from the solvent into an aqueous strip effluent (SE) stream for incorporation into borosilicate glass at the Defense Waste Processing Facility (DWPF). The solvent used in the MCU process is made of four components: the extractant (extracts Cs-137 from CSS), the modifier (increases solubility of extractant and suppressor in the diluent), the suppressor (suppresses the effects of anions and improves stripping), and the diluent (controls density and viscosity). There have been two solvents utilized during the lifetime of MCU. The first solvent was developed by ORNL and was used to design the plant based on its cesium removal capability. Due to the extended life of MCU, in order to continue to minimize the curies disposed at SDF, a new solvent capable of removing more cesium from the CSS was developed by ORNL and implemented at MCU. The second MCU solvent, Next-Generation Solvent (NGS), uses the same modifier and diluent as the original solvent, but a different extractant and suppressor. Subsequent changes to the overall MCU flowsheet were made for the use of NGS. The success of cesium removal from the CSS is often presented as the cesium decontamination factor (DF) achieved for each batch processed. The DF is the ratio of the concentration of cesium in the CSS to the cesium concentration in the DSS. The BOBCalixC6 based solvent was capable of achieving DFs between 100 and 400 for each DSS batch. The NGS solvent is capable of achieving DFs greater than 40,000 for each DSS batch. The NGS blend solvent is currently meeting the goals of the pure NGS solvent. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Part 3: Solid phase extraction of Russian VX and its chemical attribution signatures in food matrices and their detection by GC-MS and LC-MS [Extraction and Detection of Russian VX and its Chemical Attribution Signatures in Food and Environmental Matrices at LLNL]

Chemical attribution signatures indicative of O-isobutyl S-(2-diethylaminoethyl) methylphosphonothioate (Russian VX) synthetic routes were investigated in spiked food samples. Attribution signatures were identified using a multifaceted approach: Russian VX was synthesized using six synthetic routes and the chemical attribution signatures identified by GC-MS and LC-MS. Three synthetic routes were then down selected and spiked into complex matrices: bottled water, baby food, milk, liquid eggs, and hot dogs. Sampling and extraction methodologies were developed for these materials and used to isolate the attribution signatures and Russian VX from each matrix. Recoveries greater than 60% were achieved for most signatures in all matrices; some signatures provided recoveries greater than 100%, indicating some degradation during sample preparation. A chemometric model was then developed and validated with the concatenated data from GC-MS and LC-MS analyses of the signatures; the classification results of the model were > 75% for all samples. Finally, this work is part three of a three-part series in this issue of the United States-Sweden collaborative efforts towards the understanding of the chemical attribution signatures of Russian VX in crude materials and in food matrices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent hold tank sample results for MCU-17-150-152 (July 2017) and MCU-17-153-155 (August 2017): Quarterly report

A trend summary that includes the last two Solvent Hold Tank (SHT) monthly samples is shown; MCU- 17-150-152 (July SHT) and MCU-17-153-155 (August SHT). Since the last SHT sample sent for analysis was the August sample the chemical state of the solvent is best approximated by the chemical analysis of the August SHT sample (MCU-17-153-155). This report mainly focused on the chemical analysis of the August SHT sample. The analysis data from the July SHT sample are presented in the “trend” plots of this report. Analysis of the August SHT sample (MCU-17-153-155) indicated that the modifier (CS-7SB) was 2% below but the extractant (MaxCalix) concentration was at its nominal recommended level (169,000 mg/L and 46,400 mg/L respectively). The suppressor (TiDG) level has decreased since the last measurement taken while the Modular Caustic-Side Solvent Extraction unit (MCU) was operating in January 2017, but has remained steady in the range of 666 (observed in April) to 715 mg/L (observed in the August 2017 sample) since February 2017, well above the minimum recommended level (479 mg/L), but below the nominal level. The “flat” trends observed in the TiDG, MaxCalix, modifier, and Gamma measurement are consistent with the solvent being idle since January 10, 2017. A strong correlation between density and modifier concentration in the solvent continues to be observed in the SHT samples. This analysis confirms the Isopar™L addition to the solvent in January 2017. This analysis also indicates the solvent did not require further additions. Based on the current monthly sample, the levels of TiDG, Isopar™L, MaxCalix, and modifier are sufficient for continuing operation but are expected to decrease with time if the Modular Caustic-Side Solvent Extraction Unit (MCU) returns to processing radioactive liquid waste. Otherwise, the levels of these components will remain steady. A future Isopar™L trimming addition to the solvent is recommended when MCU resumes processing waste. Two unknown impurities related to the modifier (but not sec-butyl phenol: a modifier degradation product observed before) at the 290 and 110 mg/L levels were observed in the August SHT sample by the Gas - Chromatography-Mass Spectrometry (GC-MS) method. They were observed in a second GC-MS re-run with a new column. Their identification can’t be ascertained at this time. No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). Another impurity observed in the samples was mercury. Based on the August SHT sample, up to 23 ± 5 micrograms of mercury per mL of solvent was detected (the average of the Cold Vapor-Atomic Adsorption [CV-AA] and X-Ray Fluorescence [XRF] methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to either a higher mercury concentration in Salt Batches 8 and 9 (Tank 49H) . The gamma level (~ 2.0E4 dpm/mL) measured in the August SHT samples was one order of magnitude lower than the gamma levels observed in the December 2016 and January 2017 SHT samples. A similar level was observed in the July SHT sample (MCU-SHT-150-152). The gamma level has remained consistently steady since January 10, 2017 when MCU stopped processing radioactive liquid waste. The laboratory will continue to monitor the quality of the solvent in particularly for any new impurities or degradation of the solvent components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

On producing CO 2 from subsurface reservoirs: simulations of liquid-gas phase change caused by decompression

Carbon dioxide (CO 2 ) extraction from deep reservoirs is currently important in CO 2 enhanced oil recovery (EOR) and may become more important in the future if interim CO 2 storage becomes common. In late 2014, we were involved in a production test of liquid CO 2 from the Middle Duperow dolostone at Kevin Dome, Montana. The test resulted in lowering the temperature at the well bottom to ~2 °C, and showed that the well and reservoir had very low CO 2 productivity. We have used the CO 2 modeling capabilities of the TOUGH codes to simulate the test and to show that liquid CO 2 in the reservoir changes to gas phase as the pressure is lowered in the well during production testing. The associated phase change and decompression combine to drastically lower the bottom-hole temperature, creating the potential for water ice or CO 2 hydrate to form. By hypothesizing a relatively high-permeability damage zone near the well surrounded by lower permeability reservoir rock, we can match the observed pressure, temperature, and production rate. Moving from the Kevin Dome test to the question of CO 2 extraction from deep reservoirs in general, we carried out a parametric study to investigate the effects of reservoir depth and transmissivity on CO 2 production rate for a prototypical reservoir. Simulations show that depth and high transmissivity favor productivity. Complex phase changes within the ranges of P-T encountered in typical CO 2 production wells affect production rates. The results of our parametric study may be useful for the preliminary feasibility assessment of CCO 2 extraction from deep reservoirs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A flavone derivative from Sesbania sesban leaves and its cytotoxicity against murine leukemia P-388 cells

Sesbania sesban, locally named as Jayanti, is one of Indonesia plants belonging to Fabaceae family. This species is traditionally used by Indonesian people to cure digestive disorders, fever, or headache. Jayanti can grow well in tropical to subtropical region, such as in Asia and Africa. Based on literature, qualitative analysis of the methanol extract of leaves of S. sesban showed that it contained flavonoids, alkaloids, saponins and glycosides. In addition, the activity assay of extracts of different tissues of this species showed antitumor, antimalarial, and antidiabetic activityies (leaves and seed extracts), antioxidants (flower extract), and analgesic (wood extract). Though the extracts of S. sesban parts showed interesting activities, chemical study of those extracts have not been widely reported. Therefore, the objective of this research was to isolate the secondary metabolites from methanol extract of leaves of S. sesban and to determine their cytotoxicity against murine leukemia P-388 cells. One compound has been obtained and identified as 3-hydroxy-4',7-dimethoxyflavone (1), a new isolated compound from nature. This compound was obtained through separation of methanol extract using various chromatographic techniques, such as vacuum liquid chromatography and radial chromatography. The structure elucidation of isolated compound was based on 1D NMR ({sup 1}H-NMR and {sup 13}C-NMR) and 2D NMR (HMBC). The cytotoxicity of methanol extract and compound 1 against murine leukemia P-388 cells examined through MTT assay showed IC{sub 50} value of 60.04 μg/mL and 5.40 μg/mL, respectively.

60 APPLIED LIFE SCIENCES↗

Machine-learning-assisted insight into spin ice Dy 2 Ti 2 O 7

Complex behavior poses challenges in extracting models from experiment. An example is spin liquid formation in frustrated magnets like Dy 2 Ti 2 O 7 . Understanding has been hindered by issues including disorder, glass formation, and interpretation of scattering data. Here, we use an automated capability to extract model Hamiltonians from data, and to identify different magnetic regimes. This involves training an autoencoder to learn a compressed representation of three-dimensional diffuse scattering, over a wide range of spin Hamiltonians. The autoencoder finds optimal matches according to scattering and heat capacity data and provides confidence intervals. Validation tests indicate that our optimal Hamiltonian accurately predicts temperature and field dependence of both magnetic structure and magnetization, as well as glass formation and irreversibility in Dy 2 Ti 2 O 7 . The autoencoder can also categorize different magnetic behaviors and eliminate background noise and artifacts in raw data. Our methodology is readily applicable to other materials and types of scattering problems.

36 MATERIALS SCIENCE↗

Using Digital Radiography To Image Liquid Nitrogen in Voids

Digital radiography by use of (1) a field-portable x-ray tube that emits low-energy x rays and (2) an electronic imaging x-ray detector has been found to be an effective technique for detecting liquid nitrogen inside voids in thermal-insulation panels. The technique was conceived as a means of investigating cryopumping (including cryoingestion) as a potential cause of loss of thermal insulation foam from space-shuttle external fuel tanks. The technique could just as well be used to investigate cryopumping and cryoingestion in other settings. In images formed by use of low-energy x-rays, one can clearly distinguish between voids filled with liquid nitrogen and those filled with gaseous nitrogen or other gases. Conventional film radiography is of some value, but yields only non-real-time still images that do not show time dependences of levels of liquids in voids. In contrast, the present digital radiographic technique yields a succession of images in real time at a rate of about 10 frames per second. The digitized images can be saved for subsequent analysis to extract data on time dependencies of levels of liquids and, hence, of flow paths and rates of filling and draining. The succession of images also amounts to a real-time motion picture that can be used as a guide to adjustment of test conditions.

Cox, Dwight↗

Solid and Liquid Waste Drying Bag

Method and system for processing waste from human activities, including solids, liquids and vapors. A fluid-impermeable bag, lined with a liquid-impermeable but vapor-permeable membrane, defining an inner bag, is provided. A vacuum force is provided to extract vapors so that the waste is moved toward a selected region in the inner bag, extracted vapors, including the waste vapors and vaporized portions of the waste liquids are transported across the membrane, and most or all of the solids remain within the liner. Extracted vapors are filtered, and sanitized components thereof are isolated and optionally stored. The solids remaining within the liner are optionally dried and isolated for ultimate disposal.

Litwiller, Eric↗

Theory of hydrophobicity: transient cavities in molecular liquids

Observation of the size distribution of transient cavities in computer simulations of water, n-hexane, and n-dodecane under benchtop conditions shows that the sizes of cavities are more sharply defined in liquid water but the most-probable-size cavities are about the same size in each of these liquids. The calculated solvent atomic density in contact with these cavities shows that water applies more force per unit area of cavity surface than do the hydrocarbon liquids. This contact density, or "squeezing" force, reaches a maximum near cavity diameters of 2.4 angstroms. The results for liquid water are compared to the predictions of simple theories and, in addition, to results for a reference simple liquid. The numerical data for water at a range of temperatures are analyzed to extract a surface free energy contribution to the work of formation of atomic-size cavities. Comparison with the liquid-vapor interfacial tensions of the model liquids studied here indicates that the surface free energies extracted for atomic-size cavities cannot be accurately identified with the macroscopic surface tensions of the systems.

NASA Center ARC↗

[3H]Indole-3-acetyl-myo-inositol hydrolysis by extracts of Zea mays L. vegetative tissue

[3H]Indole-3-acetyl-myo-inositol was hydrolyzed by buffered extracts of acetone powders prepared from 4 day shoots of dark grown Zea mays L. seedlings. The hydrolytic activity was proportional to the amount of extract added and was linear for up to 6 hours at 37 degrees C. Boiled or alcohol denatured extracts were inactive. Analysis of reaction mixtures by high performance liquid chromatography demonstrated that not all isomers of indole-3-acetyl-myo-inositol were hydrolyzed at the same rate. Buffered extracts of acetone powders were prepared from coleoptiles and mesocotyls. The rates of hydrolysis observed with coleoptile extracts were greater than those observed with mesocotyl extracts. Active extracts also catalyzed the hydrolysis of esterase substrates such as alpha-naphthyl acetate and the methyl esters of indoleacetic acid and naphthyleneacetic acid. Attempts to purify the indole-3-acetyl-myo-inositol hydrolyzing activity by chromatographic procedures resulted in only slight purification with large losses of activity. Chromatography over hydroxylapatite allowed separation of two enzymically active fractions, one of which catalyzed the hydrolysis of both indole-3-acetyl-myo-inositol and esterase substrates. With the other enzymic hydrolysis of esterase substrates was readily demonstrated, but no hydrolysis of indole-3-acetyl-myo-inositol was ever detected.

NASA Program Space Biology↗

Direct analysis of organic priority pollutants by IMS

Many routine methods for monitoring of trace amounts of atmospheric organic pollutants consist of several steps. Typical steps are: (1) collection of the air sample; (2) trapping of organics from the sample; (3) extraction of the trapped organics; and (4) identification of the organics in the extract by GC (gas chromatography), HPLC (High Performance Liquid Chromatography), or MS (Mass Spectrometry). These methods are often cumbersome and time consuming. A simple and fast method for monitoring atmospheric organics using an IMS (Ion Mobility Spectrometer) is proposed. This method has a short sampling time and does not require extraction of the organics since the sample is placed directly in the IMS. The purpose of this study was to determine the responses in the IMS to organic 'priority pollutants'. Priority pollutants including representative polycyclic aromatic hydrocarbons (PAHs), phthalates, phenols, chlorinated pesticides, and polychlorinated biphenyls (PCB's) were analyzed in both the positive and negative detection mode at ambient atmospheric pressure. Detection mode and amount detected are presented.

Giam, C. S.↗

Fault Detection in the Solvent Extraction Process with Non-traditional Sensors

Solvent extraction is used to separate metals or other complexes into two different immiscible liquids and is an essential component of the PUREX Process. Improvements to the solvent extraction process can directly contribute to an organization’s ability to ensure the purity and recovery of special nuclear materials from spent nuclear fuel. Such improvements can benefit nuclear reprocessing efforts, increase fuel reutilization, and limit the concentration of actinides in nuclear waste repositories.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

110th Anniversary: High-Molecular-Weight Chitin and Cellulose Hydrogels from Biomass in Ionic Liquids without Chemical Crosslinking

In this work, cellulose, chitin, and composite 3D hydrogels and membranes were fabricated without any chemical modification from high-molecular-weight chitin and cellulose-rich material (CRM) extracted from shrimp shell or pine wood, respectively, using the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2 mim][OAc]). The hydrogels were prepared by redissolution of the extracted biopolymers in the same IL, or in a one-pot process directly from a solution of the biomass after extraction, followed by molding/gelation (“3D gels”) or casting (membranes), and then washing. For comparison, the preparation of gels was attempted using commercial microcrystalline cellulose or chitin. From all of the sources, the regenerated CRM or chitin required significantly lower load. Hydrogels were also converted to aerogels via transformation to alcogels and then Sc-CO 2 drying, giving materials of low density, high porosity, favorable compressibility, high water uptake, and moderate antioxidant activity. Air-dried membranes were dense, of high tensile strength, and exhibited high water-vapor transmission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Pore Fluid Chemistry on Fine-Grained Sediment Fabric and Compressibility

Fines, defined here as grains or particles, less than 75µm in diameter, exist nearly ubiquitously in natural sediment, even those classified as coarse. Macroscopic sediment properties, such as compressibility, which relates applied effective stress to the resulting sediment deformation, depend on the fabric of fines. Unlike coarse grains, fines have sizes and masses small enough to be more strongly influenced by electrical interparticle forces than by gravity. These electrical forces acting through pore fluids are influenced by pore-fluid chemistry changes. Macroscopic property dependence on pore-fluid chemistry must be accounted for in sediment studies involving subsurface flow and sediment stability analyses, as well as in engineered flow situations such as groundwater pollutant remediation, hydrocarbon migration or other energy resource extraction applications. This study demonstrates how the liquid-limit-based electrical sensitivity index can be used to predict sediment compressibility changes due to pore-fluid chemistry changes. Laboratory tests of electrical sensitivity, sedimentation and compressibility illustrate mechanisms linking micro- and macro-scale processes for selected pure, endmember fines. In conclusion, a specific application considered here is methane extraction via depressurization of gas hydrate-bearing sediment, which causes a dramatic pore-water salinity drop concurrent with sediment being compressed by the imposed effective stress increase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deposit formation in liquid fuels. I - Effect of coal-derived Lewis bases on storage stability of Jet A turbine fuel

The development of reasonably precise techniques for the measurement of storage stability of jet aviation fuel is described. Lewis bases, extracted by ligand-exchange from a coal-derived liquid, are shown to adversely affect storage stability (as determined by an accelerated storage test) when added to Jet A turbine fuel. JFTOT results suggesting slight decreases in thermal stability of fuel 'spiked' (i.e., contaminated with a measured quantity of reagent) with extract are reported. Addition to Jet A turbine fuel of individual heterocyclic nitrogen compounds is shown to produce comparable decreases in storage stability.

Dahlin, K. E.↗

Chemical changes in thirdhand smoke associated with remediation using an ozone generator

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m 3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h -1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O 3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Periodic boundary conditions for arbitrary deformations in molecular dynamics simulations

A generalization of the Lees-Edwards periodic boundary conditions (gLE-PBC) for molecular dynamics (MD) simulations is developed to allow for arbitrary deformations to be applied to the domain. The gLE-PBC domain remains a rectangular cuboid regardless of the applied deformation in contrast with the Lagrangian-rhomboid periodic boundary conditions (LR-PBC) where the domain deforms according to the applied deformation. Furthermore, the kinematics of gLE-PBC are validated against pure shear. The gLE-PBC method for interacting systems is then validated against the LR-PBC method and analytical solutions for a solid under isotropic compression, one-dimensional shearing, three-dimensional extension and shearing and for a liquid under Couette flow. Bulk physical properties extracted from the gLE-PBC simulations agree well with values calculated from equilibrium MD simulations. Three dimensional shearing and a deformation with a full velocity gradient matrix are also simulated, showing the range of problems gLE-PBC can explore.

74 ATOMIC AND MOLECULAR PHYSICS↗

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination of X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗