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At least 1,405 records · Page 78
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Exploring fingerprints of ultrafast structural dynamics in molecular solutions with an X-ray laser

We apply ultrashort x-ray laser pulses to track optically excited structural dynamics of [Ir 2 (dimen) 4 ] 2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered x-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir 2 (dimen) 4 ] 2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir 2 (dimen) 4 ] 2+ with a larger Ir–Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. In conclusion, the proposed x-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Generation of Enrichment-Dependent Thermal Neutron Scattering Data

This work details the generation of enrichment-dependent thermal neutron scattering cross sections for several crucial uranium fuel compounds. The evaluations of the thermal scattering law (TSL) and associated cross sections for uranium dioxide (UO 2 ), uranium carbide (UC), and uranium nitride (UN) were performed using standard ab initio lattice dynamics (AILD) methods. The data for uranium metal was produced using a novel hybrid approach of molecular dynamics combined with lattice dynamics methods. 235 U enrichments of 5%, 10% (LEU+), 19.75% (HALEU), 93% (HEU), and 100% were considered, in addition to natural uranium. The enrichment-dependent masses and free atom cross sections were used in the generation of elastic and inelastic thermal neutron scattering cross sections, while the calculation of the phonon density of states (DOS) and resulting TSL considered only the natural isotopic composition of uranium. The use of an identical DOS for all enrichments is expected to have minimal impact on the final data, as the small change in uranium mass should not significantly affect lattice vibrations. The cross sections are shown to exhibit significant dependence on 235 U enrichment. The submission of this data to the National Nuclear Data Center (NNDC) for release in the ENDF/B-VIII.1 database should support the design of advanced reactor concepts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Specific Ion Effects in Lanthanide–Amphiphile Structures at the Air–Water Interface and Their Implications for Selective Separation

The use of surfactants to attract dissolved ions to water surfaces and interfaces is an essential step in both solvent-based and solvent-free separation processes. Here, we have studied the interactions of lanthanide ions in the aqueous subphase with monolayers of dihexadecyl phosphate at air–water interfaces. With heavier lanthanides (atomic number Z ≥ 65) in the subphase, the floating layer can be compressed to an area/molecule of about half the molecular cross section, indicating bilayer formation. X-ray fluorescence and reflectivity data support this conclusion. In the presence of lighter lanthanides (Z < 65), only monolayers are observed. Subphase-concentration-dependent studies using Er 3+ (heavier) and Nd 3+ (lighter) lanthanides show a stepwise progression, with ions attaching to the monolayer only when the solution concentration is >3 × 10 –7 M. Above ~10 –5 M, bilayers form but only in the presence of the heavier lanthanide. Grazing incidence X-ray diffraction shows evidence of lateral ion–ion correlations in the bilayer structure but not in monolayers. Explicit solvent all-atom molecular dynamics simulations confirm the elevated ion–ion correlation in the bilayer system. This bilayer structure isolates heavier lanthanides but not lighter lanthanides from an aqueous solution and is therefore a potential mechanism for the selective separation of heavier lanthanides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ab initio investigation of a hypersonic double cone experiment

This article presents a direct molecular simulation (DMS) of a reactive Mach 8.2 oxygen flow over a double cone geometry. The free stream conditions and article configuration generate a flow with thermal and chemical nonequilibrium, which are common attributes of hypersonic flight. This scenario was first studied experimentally at Calspan University of Buffalo Research Center’s test facility. DMS is a particle method that uses quantum mechanically derived interaction potentials to simulate molecular collisions within a flow field. Since these interaction potentials are the only modeling inputs used in the simulation, all flow features can solely be attributed to the ab initio potential energy surfaces. Hence, providing a comparison of a hypersonic ground test and numerical data anchored to quantum mechanics. The fundamental nature of DMS is leveraged to investigate molecular level mechanisms prevalent in the flow, and comparisons with lower fidelity simulations are presented to highlight the role of these first principles calculations as benchmark solutions.

Science & Technology - Other Topics↗
DOE OSTI2025

Leveraging High-resolution Molecular Composition of Soil Organic Matter to Enhance Carbon Cycling Modeling

Soils store more carbon than the atmosphere and vegetation combined, yet Earth system models still struggle to predict how this vast reservoir will respond to environmental change. A central limitation is that most soil biogeochemical models represent organic matter using bulk conceptual pools or chemically homogeneous fractions, preventing direct use of rapidly expanding molecular-scale datasets. Here we develop and test a new soil decomposition framework that explicitly integrates high-resolution information on organic matter composition. First, we construct a molecularly informed litter decomposition module in which plant inputs are partitioned into five functional compound classes—carbohydrates, proteins, lignin-like aromatics, lipids, and carbonyls—using a molecular mixing model calibrated to solid-state 13 C Nuclear Magnetic Resonance (NMR) spectra. Class-specific kinetics, lignin-dependent physical protection, and substrate-driven microbial carbon use efficiency allow the module to capture metabolic tradeoffs associated with enzyme production and nutrient limitation. We then embed this litter module within a microbially explicit whole-soil model that tracks the transformation of these compound classes through particulate organic matter, dissolved organic matter, mineral-associated organic matter, and microbial biomass. High-resolution Fourier Transform Ion Cyclotron Resonance mass spectrometry (FTICR-MS) data are used to link internal pools to measurable soil organic matter fractions and to constrain key process parameters. Applications at soil-core and ecosystem scales demonstrate that the new model reproduces observed soil respiration dynamics while providing mechanistic attribution of CO 2 fluxes to specific chemical classes and pools. Compared to existing frameworks such as the Community Land Model soil biogeochemistry module and the Millennial model, our approach maintains competitive predictive skill while substantially improving interpretability and opportunities for data–model integration. This work illustrates a viable pathway for leveraging molecular-scale observations to reduce structural uncertainty in soil carbon–climate feedback projections.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Short- to Intermediate-Range Structure, Transport, and Thermophysical Properties of LiF–NaF–ZrF4 Molten Salts

LiF–NaF–ZrF 4 multicomponent molten salts are identified as promising candidates for coolant salts in molten salt reactors and advanced high-temperature reactors. This study focused on low-melting point salt compositions of interest: 38LiF–51NaF–11ZrF 4 , 42LiF–29NaF–29ZrF 4 , and 26LiF–37NaF–37ZrF 4 . Ab-initio molecular dynamics (AIMD) calculations were performed and compared with available experimental data to assess the ability of rigid ion models (RIM) to reproduce short- to intermediate-range structure, transport, and thermophysical properties of the LiF–NaF–ZrF 4 salt mixtures. It is found that as ZrF 4 mol% increases, the average cation–anion coordination number (CN) of monovalent cations (Li + , Na + ) obtained from RIM calculations decreases, while multivalent Zr 4+ CN varied from 15% to 19% in comparison to corresponding AIMD values. In addition, RIM is found to predict the existence of 7, 8, and 9 coordinated fluorozirconate complexes, while AIMD and the available experimental data showed an occurrence of 6, 7, and 8 coordinated complexes in the melt. The intermediate-range structure analysis revealed that while the RIM parameters are able to reproduce a local structure for lower ZrF 4 mol% salts such as in 38LiF–51NaF–11ZrF 4 , an extensive fluorozirconate network formation is observed in RIM simulations for higher ZrF 4 mol% compositions. The network generated by RIM parameters is found to be mainly connected by “corner-sharing” fluorozirconate complexes as opposed to both “edge-sharing” and “corner-sharing” connectively portrayed by AIMD. It is found that a close agreement between AIMD and the RIM salt structure for the 11-mol% ZrF 4 salt resulted in good agreement in the calculated Zr diffusivities and the viscosity values. However, due to the inaccurate short- to intermediate-range structure prediction by RIM for higher ZrF 4 mol% compositions, thermophysical properties such as densities and heat capacity differ by up to 26% and 27%, respectively, upon comparison with AIMD and experimental values. Also, the network-dominated properties such as diffusion coefficients and viscosities differed by up to two and three orders of magnitude, respectively. This study signifies the importance of accurate salt structure generation for an accurate prediction of transport and thermophysical properties of multicomponent molten salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

A Step-by-Step Protocol from METASPACE to Biological Interpretation

Mass spectrometry imaging (MSI) represents an exceptional tool for exploring complex biological systems spatially at the molecular level. However, due to its multidimensional nature and large-scale data output, it presents considerable challenges when it comes to extracting meaningful biological insights. Recent advancements, such as the METASPACE platform, have enabled researchers to efficiently process, annotate, and interpret MSI datasets by leveraging machine learning and cloud-based infrastructure. In this tutorial, we present a detailed and user-friendly R-pipeline designed to help METASPACE users navigate untargeted metabolomic annotations and transform them into practical insights about their biological systems. By combining METASPACE annotations with rapid R-based screening, this workflow not only streamlined the analytical process but also enhanced the understanding of spatial molecular distribution, especially for complex systems. Here, this easy-to-follow approach has the potential for applications in diagnostics, drug discovery, environmental and ecological processes, and more. We envision this pipeline to be particularly useful for newcomers to the field of MSI and

Moreno Pedraza, Abigail↗
DOE OSTI2020

An advanced workflow for single-particle imaging with the limited data at an X-ray free-electron laser

An improved analysis for single-particle imaging (SPI) experiments, using the limited data, is presented here. Results are based on a study of bacteriophage PR772 performed at the Atomic, Molecular and Optical Science instrument at the Linac Coherent Light Source as part of the SPI initiative. Existing methods were modified to cope with the shortcomings of the experimental data: inaccessibility of information from half of the detector and a small fraction of single hits. The general SPI analysis workflow was upgraded with the expectation-maximization based classification of diffraction patterns and mode decomposition on the final virus-structure determination step. The presented processing pipeline allowed us to determine the 3D structure of bacteriophage PR772 without symmetry constraints with a spatial resolution of 6.9 nm. The obtained resolution was limited by the scattering intensity during the experiment and the relatively small number of single hits.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS2000

A Consolidated Block Grant Proposal to Carry Out the Analysis of Data from the ISO Satellite

This block grant covers the activities of three research groups at STScI: search for cold molecular hydrogen in the galaxy; dust characterization in circumstellar shells around evolved massive stars; and the relationship between dust absorption and emission in galaxies. We proposed to group the efforts and resources available to several approved ISO projects in order to more efficiently deal with the data reduction and analysis. We give a brief description of primary objectives and scope of each project, along with the final status of the project as of the expiration date of the grant. Owing to many delays on the part of the ISO Project, the calibrated data was received very late, which resulted in significant delays in deriving the results. In addition, for one of the components of this project, the ISO data was finally determined to be of too low a quality to be useful.

Allen, Ron↗
DOE OSTI2022

Investigation of Molecular Diffusion at Block Copolymer Thin Films Using Maximum Entropy Method-Based Fluorescence Correlation Spectroscopy and Single Molecule Tracking

Fluorescence correlation spectroscopy (FCS) has been widely used to investigate molecular diffusion behavior in various samples. The use of the maximum entropy method (MEM) for FCS data analysis provides a unique means to determine multiple distinct diffusion coefficients without a priori assumption of their number. Comparison of the MEM-based FCS method (MEM-FCS) with another method will reveal its utility and advantage as an analytical tool to investigate diffusion dynamics. Herein, we measured diffusion of fluorescent probes doped into nanostructured thin films using MEM-FCS, and validated the results with single molecule tracking (SMT) data. The efficacy of the MEM code employed was first demonstrated by analyzing simulated FCS data for systems incorporating one and two diffusion modes with broadly distributed diffusion coefficients. The MEM analysis accurately afforded the number of distinct diffusion modes and their mean diffusion coefficients. These results contrasted with those obtained by fitting the simulated data to conventional two-component and anomalous diffusion models, which yielded inaccurate estimates of the diffusion coefficients. Subsequently, the MEM analysis was applied to FCS data acquired from hydrophilic dye molecules incorporated into microphase-separated polystyrene-block-poly(ethylene oxide) (PS-b-PEO) thin films characterized under a water-saturated nitrogen atmosphere. The MEM analysis revealed distinct fast and slow diffusion components attributable to molecules diffusing on the film surface and inside the film, respectively. SMT studies of the same materials yielded trajectories for mobile molecules that appear to follow the curved PEO microdomains. Diffusion coefficients obtained from the SMT data were consistent with those obtained for the slow diffusion component detected by MEM-FCS. Furthermore, these results highlight the utility of MEM-FCS and SMT for gaining complementary information on molecular diffusion processes in heterogeneous material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

WHONDRS Summer 2019 Sampling Campaign: Global River Corridor Sediment FTICR-MS, Dissolved Organic Carbon, Aerobic Respiration, Elemental Composition, Grain Size, Total Nitrogen and Organic Carbon Content, Bacterial Abundance, and Stable Isotopes (v10)

The WHONDRS Summer 2019 Sampling (S19S) Campaign collected samples in 97 globally distributed river corridor systems between July and September 2019. Surficial streambed sediments were collected at three locations within each site (upstream, midstream, and downstream). Surface water was collected at the downstream site. This dataset includes a portion of the data types produced from the sediment samples and does not include any results from the surface water. Surface water data can be found at https://data.ess-dive.lbl.gov/view/doi:10.15485/1603775. The S19S campaign was designed with the science community to ask questions associated with links among core/transient metabolomes, microbial metabolism, biogeochemical function, and physical properties of watershed and river corridor systems. This data package was originally published in December 2020. It was updated in April 2021 (v2; modified files), May 2022 (v3; new and modified files), November 2022 (v4; new and modified files), January 2023 (v5 and v6; new and modified files), February 2023 (v7; new and modified files), August 2023 (v8; new and modified files), July 2025 (v9; new and modified files), and June 2026 (v10; new and modified files). Version 10 includes major restructuring of the files and their formats. See the change history in the readme for details. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset contains (1) readme, (2) data dictionary, (3) file level metadata, (4) sampling protocol, (5) a data checks report, (6) field metadata, (7) international generic sample number (IGSN) mapping file, (8) joint genome institute (JGI) mapping file, (9) a folder of site photos, and (10) a folder of sample data. The sample data folder contains (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) and FTICR methods; (2) respiration rates and normalized respiration rates calculated from laboratory sediment incubations, (3) X-ray fluorescence (XRF) elemental composition, (4) grain size distribution from the < 2 millimeter fraction of sediment, (5) total organic carbon and total nitrogen content, (6) bacterial abundance flow cytometry data, (7) sediment stable isotopes (C and N), (8) laboratory methods, (9) water and sediment mass and volume used in incubations, (10) a folder with code, inputs, and plots for the respiration rates, (11) a folder containing XRF data, (12) a folder containing unaligned, peak-picked high resolution characterization of dissolved organic matter from sediment via 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory), (12) and a folder containing processed FTICR-MS data. All files are .msa, .txt, .spx, .xml, .csv, .pdf, .txt, .jpg, or .jpeg.

13C↗
DOE OSTI2021

High-resolution CARMA Observation of Molecular Gas in the North America and Pelican Nebulae

In this paper, we present the first results from a CARMA high-resolution {sup 12}CO(1-0), {sup 13}CO(1-0), and C{sup 18}O(1-0) molecular line survey of the North America and Pelican (NAP) Nebulae. CARMA observations have been combined with single-dish data from the Purple Mountain 13.7 m telescope, to add short spacings and to produce high-dynamic-range images. We find that the molecular gas is predominantly shaped by the W80 H ii bubble, driven by an O star. Several bright rims noted in the observation are probably remnant molecular clouds, heated and stripped by the massive star. Matching these rims in molecular lines and optical images, we construct a model of the three-dimensional structure of the NAP complex. Two groups of molecular clumps/filaments are on the near side of the bubble: one is being pushed toward us, whereas the other is moving toward the bubble. Another group is on the far side of the bubble, and moving away. The young stellar objects in the Gulf region reside in three different clusters, each hosted by a cloud from one of the three molecular clump groups. Although all gas content in the NAP is impacted by feedback from the central O star, some regions show no signs of star formation, while other areas clearly exhibit star formation activity. Additional molecular gas being carved by feedback includes cometary structures in the Pelican Head region, and the boomerang features at the boundary of the Gulf region. The results show that the NAP complex is an ideal place for the study of feedback effects on star formation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

AlphaFold -assisted structure determination of a bacterial protein of unknown function using X-ray and electron crystallography

Macromolecular crystallography generally requires the recovery of missing phase information from diffraction data to reconstruct an electron-density map of the crystallized molecule. Most recent structures have been solved using molecular replacement as a phasing method, requiring an a priori structure that is closely related to the target protein to serve as a search model; when no such search model exists, molecular replacement is not possible. New advances in computational machine-learning methods, however, have resulted in major advances in protein structure predictions from sequence information. Methods that generate predicted structural models of sufficient accuracy provide a powerful approach to molecular replacement. Taking advantage of these advances, AlphaFold predictions were applied to enable structure determination of a bacterial protein of unknown function (UniProtKB Q63NT7, NCBI locus BPSS0212) based on diffraction data that had evaded phasing attempts using MIR and anomalous scattering methods. Using both X-ray and micro-electron (microED) diffraction data, it was possible to solve the structure of the main fragment of the protein using a predicted model of that domain as a starting point. The use of predicted structural models importantly expands the promise of electron diffraction, where structure determination relies critically on molecular replacement.

molecular replacement↗
NASA NTRS2008

Huygens Gas Chromatograph Mass Spectrometer Results from Titan

The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of N-14/N-15, C-12/C-13, and D/H, mole fractions of radiogenic argon (Ar-40)and primordial argon Ar-36), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be below the detection limit of the instrument or absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products include the instrument response to surface outgassing of C2N2, C2H6, acetylene (C2H2),and carbon dioxide (CO2). More recent results include the detection of benzene (C6H6) and height profiles of molecular hydrogen (H2). Numerous other trace species evaporating from the surface were also identified using the GCMS data.

Niemann, Hasso↗
DOE OSTI2023

X‐ray characterization of three possible edible oleogelators: Experiment and theory

Abstract Three oleogelator molecules (Triacontane (TC), Stearic acid (SA), and Behenyl Lignocerate (BL)) were studied individually, in pairs, or all together to make an oleogel using triolein as the oil. WAXS, SAXS and USAXS were used to elucidate the solid structures from angstroms to a few micrometers. A two‐dimensional mapping of atomic positions for each molecule was carried out to understand the crystalline multilayer structures formed. We assumed that the molecules were rigidly extended and that they underwent no significant (hindered) rotations so that the free energy is determined by the Lennard‐Jones interactions of closely packed multilayers. TC molecules were predicted to form a tilt angle of , yielding a SAXS line at Å ─1 , in acceptable agreement with the measured . For SA crystals (predicted) yielding a SAXS line at compared to (observed). No mixed crystals were observed for any pair of molecules or when all three were used. USAXS data showed that SA forms large nanocrystals compared to TC and BL. All three combinations of molecular pairs showed basic scatterers smaller or similar to those of individual molecules. The theory presented here, together with the experimental results, showed why no mixed crystals are formed from two or all three molecules. Data from the USAXS region suggested that, when using all three molecules, a more compact fractal structure was obtained, compared with those if one or two of the molecules were used.

Chemistry↗
DOE OSTI2024

Molecular Dynamical and Quantum Mechanical Exploration of the Site-Specific Dynamics of Cy3 Dimers Internally Linked to dsDNA

Performing spectroscopic measurements on biomolecules labeled with fluorescent probes is a powerful approach to locating the molecular behavior and dynamics of large systems at specific sites within their local environments. The indocarbocyanine dye Cy3 has emerged as one of the most commonly used chromophores. The incorporation of Cy3 dimers into DNA enhances experimental resolution owing to the spectral characteristics influenced by the geometric orientation of excitonically coupled monomeric units. Various theoretical models and simulations have been utilized to aid in the interpretation of the experimental spectra. In this study, we employ all-atom molecular dynamics simulations to study the structural dynamics of Cy3 dimers internally linked to the dsDNA backbone. We used quantum mechanical calculations to derive insights from both the linear absorption spectra and the circular dichroism data. Furthermore, we explore potential limitations within a commonly used force field for cyanine dyes. The molecular dynamics simulations suggest the presence of four possible Cy3 dimeric populations. The spectral simulations on the four populations show one of them to agree better with the experimental signatures, suggesting it to be the dominant population. Furthermore, the relative orientation of Cy3 in this population compares very well with previous predictions from the Holstein–Frenkel Hamiltonian model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

Since the first detailed compositional analysis of dissolved organic matter (DOM) in 1995, high resolution mass spectrometry (HRMS) has become a vital tool for DOM characterization. While the upward trend in HRMS for molecular level analysis of DOM continues, so do the challenges of data comparison and interpretation between laboratories operating instruments of differing performance and user operating conditions. It is therefore essential that the community establishes whether data and trends can be compared robustly between research groups. To this end, 4 identically prepared DOM samples were each studied by 16 laboratories, representing 17 commercially-purchased instruments located across 8 countries, using positive- and negative-mode electrospray ionization (ESI) HRMS analysis. Despite the widely reported sensitivity of ESI experiments to sample matrix, preparation, ion source operation and instrument tuning parameters, the instruments used in this study showed relatively low variability between results for the same samples, particularly H/C and AI metrics. The variation in O/C and m/z metrics was relatively higher, although z-score graphs and %BCD demonstrated that the relative difference in general chemical composition between samples was the same for each instrument included in the study. As such, these metrics can be used for fingerprinting of DOM samples and as a benchmark for quality control in participating laboratories, with future strides in environmental science building upon these efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Quantification of the REE 3+ aqua ions and chloride species in aqueous fluids by in situ Raman spectroscopy using perturbations of the water band

Acidic NaCl-rich aqueous fluids play a crucial role in forming hydrothermal rare earth elements (REE) mineral deposits. Aqueous REE mobility is mostly controlled by the stabilities of REE 3+ and REE chloride species. Our current knowledge of REE speciation is based on solubility data, thermodynamic models and in situ spectroscopic measurements, sometimes coupled with molecular simulations. Here, in this study, we investigate Nd and Yb speciation in pH2 Cl-bearing solutions at 25 °C and 0.1 MPa with variable Cl/REE ratios using Raman Spectroscopy in solutions with 0.1 to 0.6 mol/kg NdCl 3 or YbCl 3 and 0.2 to 3.2 mol/kg NaCl. Due to the challenges in resolving the REE-Cl band, we developed a new method using the water vibrational mode and multivariate curve resolution (MCR) analysis. The Raman spectra for the vibrational band of water (2700 to 3900 cm –1 ) were collected at 25 °C and fitted by three Gaussian sub-peaks, then quantified using MCR analysis to de-convolute the water band into bulk H 2 O and the perturbations caused by of Cl – , REE 3+ , and REE chloride species. REE speciation based on the perturbations of the water band indicates that REE 3+ aqua ions dominate acidic solutions at 25 °C, but up to ~20 mol% YbCl 2+ forms at high YbCl 3 concentrations. The new method is promising for quantifying in situ speciation of the REE 3+ aqua ions and REE chloride species in aqueous fluids while providing information on the hydration of ions. This method improves our molecular level understanding of REE aqueous species stability and their role in REE mobilization during fluid-rock interaction.

58 GEOSCIENCES↗