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NASA NTRS1992

Experimental determination of the solubility of iridium in silicate melts: Preliminary results

Little is known of the geochemical behavior of iridium. Normally this element is taken to be chalcophile and/or siderophile so that during planetary differentiation processes, e.g., core formation, iridium is extracted from silicate phases into metallic phases. Experimental determination of the metal/silicate partition coefficient of iridium is difficult simply because it is so large. Also there are no data on the solubility behavior of iridium in silicate melts. With information on the solubility of iridium in silicate melts it is possible, in combination with experimental data for Fe-Ir alloys, to calculate the partition coefficient between a metallic phase and a silicate melt.

Borisov, Alexander↗

NASA NTRS1980

Laboratory studies of actinide metal-silicate fractionation

Actinide and Sm partition coefficients between silicate melt and several metallic phases have been measured. Under reducing conditions Si, Th, U and Pu can be reduced to metals from silicate melts and alloyed with a platinum-gold alloy. U and Pu enter a molten Pt-Si alloy with roughly equal affinity but U strongly partitions into the solid Pt. Th behaves qualitatively the same as Pu but is much less readily reduced than U, and Sm appears to remain unreduced. Experiments with Fe metal have shown that the partition coefficients of the actinides between Fe and silicate liquid are extremely low, suggesting a very low actinide concentration in planetary cores. Experiments show that platinum metals can efficiently fractionate actinides and fractionate actinides from lanthanides and this process may be relevant to the condensation behavior of these elements from the solar nebula. Pt-metal grains in Allende Ca-Al-rich inclusions appear to be U-poor, although the sub-class of Zr-bearing Pt metals may have high U contents.

Jones, J. H.↗

DOE OSTI2026

Mechanistic mass transfer in hollow fiber membrane solvent extraction for bio-based isobutanol

Membrane solvent extraction (MSE) has emerged as a promising method for selectively recovering bioproducts from complex aqueous streams. Bio-isobutanol, a next-generation feedstock for biofuel, remains challenging to recover because of its low concentration and the presence of inhibitory substances. This study explores the potential of hollow fiber (HF) MSE for bio-isobutanol recovery and systematically examines the coupled effects of fiber packing, shell-side flow dynamics, and aqueous chemistry on performance. A resistance-in-series model is applied to understand mass transfer in the HF MSE modules, quantify local resistances, and validate overall performance. The results show that increasing the fiber packing provides a larger interfacial area but induces poor flow distribution and channeling, hindering effective isobutanol transport. Meanwhile, increasing the shell-side velocity improves isobutanol recovery due to reductions in the boundary layer thickness. The presence of salts, added to mimic fermentation broth, increases the partition coefficient through salting-out effects, further improving isobutanol flux. A modified correlation for the shell-side mass transfer coefficient (k s,ϕ+v ), integrating geometric and hydrodynamic effects, was developed and validated. The proposed model achieves highly predictive accuracy (r 2 = 0.9808) across a wide range of conditions, outperforming previous models. The findings provide mechanistic insight into the interaction of geometric packing, hydrodynamics, and chemistry in governing mass transfer in HF MSE. Overall, this work demonstrates the potential of HF MSE for efficient bio-isobutanol recovery and also provides practical guidelines on critical factors (packing fraction, partition coefficient, and shell-side velocity), aiding in the design and scaling of MSE systems for resource recovery.

Aqueous chemistry↗

NASA NTRS1992

Experimental determination of U and Th partitioning between clinopyroxene and natural and synthetic basaltic liquid

Experimental measurements of U and the partition coefficients between clinopyroxene and synthetic and natural basaltic liquid are presented. The results demonstrate that crystal-liquid U-Th fractionation is fO2-dependent and that U in terrestrial magmas is not entirely tetravalent. During partial melting, the liquid will have a Th/U ratio less than the clinopyroxene in the source. The observed U-238 - Th-230 disequilibrium in MORB requires that the partial melt should have a U/Th ratio greater than the bulk source and therefore cannot result from clinopyroxene-liquid partitioning. Further, the magnitudes of the measured partition coefficients are too small to generate significant U-Th fractionation in either direction. Assuming that clinopyroxene contains the bulk of the U and Th in the MORB source, the results indicate that U-238 - Th-230 disequilibrium in MORB may not be caused by partial melting at all.

Latourrette, T. Z.↗

NASA NTRS2006

Aluminum Effect on the Calibration of the Eu Oxybarometer for Nakhlites

Recent studies of Martian meteorites have shown that Martian magma had wide range of oxygen fugacity. In order to estimate the redox state of the Martian crust and mantle, the partitioning coefficient of Eu in the shergottite pyroxene has been extensively studied. Nakhlite, a cumulate clinopyroxenite, is another important group of Martian meteorites. We have studied synthetic compositions (NT, NL, NJ, NJ2 and NJ4) in order to estimate the Nakhla parent melt composition. In our previous work, we calibrated the Eu oxybarometer for nakhlite using the NJ4 composition which we believe is the closest to the Nakhla parent melt. Consequently, we concluded that Nakhla may have crystallized under fairly reducing condition. However, we also found that the partition coefficient is strongly affected by Al contents in melt and in pyroxene. In this abstract we report the correlation between the D values and Al contents in melt and in pyroxene from our Nakhla experimental studies. Also we check the reliability of our previous calibration of Eu oxybarometer, because Rare Earth Elements (REEs) are easily affected by Al content in melt and in pyroxene and Nakhla pyroxene shows unusual patchy Al zoning.

Makishima, J.↗

NASA NTRS1993

Metal-silicate thermochemistry at high temperature - Magma oceans and the 'excess siderophile element' problem of the earth's upper mantle

Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.

Capobianco, Christopher J.↗

DOE OSTI2025

Quantum chemically calculated Abraham parameters for quantifying and predicting polymer hydrophobicity

The leakage and accumulation of plastic in the environment is a significant and growing problem with numerous detrimental impacts and has led to a push toward the design and development of more environmentally benign materials. To this end, we have developed a quantum chemistry-based model for predicting the mobility of polymer materials from molecular structure. Hydrophobicity is used as a surrogate for mobility given that hydrophobic interactions drive much of the partitioning of contaminants in and out of various environmentally relevant compartments. To model polymer hydrophobicity, we adjusted a previously developed Quantum Chemically Calculated Abraham Parameter model to calculate Abraham parameters of small molecules from molecular structure information. The resulting model predicted the octanol-water partition coefficient (K OW ) of polymer repeating units with a root mean square error (RMSE) of 0.48 (log scale). Additionally, the hydrophobicity of high molecular weight polymer materials was captured through solubility parameters and Nile red staining experiments from the literature and predicted with RMSEs of 1.21 (J/cc) 0.5 and 3.42 nm, respectively. Finally, to test the environmental applicability of the model, the relative adsorption capacity of three polymers was predicted and used to unify sorption isotherms across multiple sorbates and polymer sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Adsorption Studies of Dilute Krypton and Xenon from Nitrogen on SBMOF-1 and Activated Charcoal for Applications in Isotope Harvesting

Adsorptive partitioning of dilute krypton (Kr) and xenon (Xe) onto Stony Brook Metal–Organic Framework (SBMOF-1) and activated charcoal (AC) from carrier nitrogen was experimentally measured at temperatures ranging from 195 to 293 K. For this purpose, a closed-loop system for gas adsorption experiments was developed. From the Kr adsorption measurements, the adsorption equilibrium constant for Kr on SBMOF-1 was calculated, yielding a value for the enthalpy of adsorption of −19 ± 1 kJ·mol –1 . The partition coefficients were utilized to estimate the extraction rates of 76 Kr, 77 Kr, and 122 Xe isotopes during isotope harvesting at the Facility for Rare Isotope Beams (FRIB). We conclude that both materials showed promising results for the extraction of noble gases from FRIB effluents using temperature swing adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Predicting Liquid–Liquid Phase Separation of Submicrometer Proxies for Atmospheric Secondary Aerosol

Liquid–liquid phase separation (LLPS) of atmospheric aerosols can significantly impact climate, air quality, and human health. However, their complex composition, small size, and history-dependent properties result in great uncertainty in the modeling of aerosol phase state and atmospheric processes. Herein, using cryogenic transmission electron microscopy (cryo-TEM), we examined model submicron aerosols composed of organic compounds and ammonium sulfate, and established a parameterization for the separation relative humidity (SRH) that accounts for chemical composition, particle size, and equilibration time. We evaluated different variables that describe chemical composition: O/C ratio, partition coefficient, solubility, molar mass, and polarizability. The O/C ratio fits the SRH of micrometer droplets best, and by using a scaling factor to translate the micrometer SRH parameterization to submicron aerosols, we incorporate the effects of size and equilibration time. The measured scaling factor for the submicron mean SRH (30nm – 1μm, 20 min equilibration times) is 0.80, the factor becomes 1 with equilibration time over 1 hour, and is equal to 0, meaning that SRH is absent, when the aerosol dry diameter is smaller than 30 nm. Furthermore, our parameterization will aid in universal SRH modeling, potentially leading to more accurate predictions of aerosol mass, optical properties, hygroscopicity, and heterogeneous chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Machine Learning-Driven Solvent Screening for Biobased 2,3-Butanediol Extraction

Biobased 2,3-butanediol (2,3-BDO) is a valuable biomass-derived chemical due to its versatility in being transformed into a wide variety of products. However, the separation and purification of 2,3-BDO from fermentation broth remain a significant challenge owing to its high boiling point and hydrophilic nature. Herein, we developed a machine learning (ML)-based screening workflow that uses molecular calculations as training data and requires only a small number of experimental measurements for validation to identify alternative solvent candidates for the liquid–liquid extraction (LLE) of 2,3-BDO from aqueous solution. In particular, 130 density functional theory (DFT) calculations with the implicit solvation method not only built a correlation between the computational partition coefficient and the experimental distribution coefficient of 2,3-BDO but also parameterized an Extra-Trees ML model to screen the distribution coefficient for a wider range of 6717 organic solvents. The experimental measurements of only 24 solvents were needed to validate the computational results. A list of 50 prioritized solvents was proposed for 2,3-BDO LLE, and seven additional experimental measurements were conducted to further verify our selected solvents. The impact of the extraction temperature and solvent-to-feed ratio was also investigated for selected solvents in experiments. Furthermore, this work suggested alternative solvents for 2,3-BDO LLE and proposed a versatile workflow that requires fewer experiments and can be applied to a broader range of LLE studies.

Extraction↗

DOE OSTI2024

Liquid–Liquid Equilibrium Prediction in Fast Pyrolysis Bio-Oil Systems: A Framework for Incorporating Bio-Oil Complexity

The study of mixtures of bio-oil, water and organic solvents in different proportions can serve as a cost-effective analysis of its content due to the formation of immiscible phases. This manuscript attempts to replicate experimentally determined partition coefficients (K OW ) of relevant species present in fast pyrolysis bio-oil (FPBO). A commercial flowsheeting simulator with surrogate bio-oil model representation is used. Concurrently, pyrolytic lignins in FPBO (‘pyrolignin’) do not have an agreed-upon structural representation, and the literature is ripe with wide variations of said representations. Thus, during the description of FPBO, this pyrolignin fraction was modeled using 20 possible structures (phenolic dimers to tetramers), with the goal of determining the structures for which the experimental data are best described. Two cases were considered: Case 1 normalized the reported experimental mass balance, while Case 2 included the unreported fraction in the mass balance to the total pyroligin. Please, add here a comment on the prediction of the Water oil equilibrium. The best KOW predictions for levoglucosan (LVG) were obtained when the system was modeled with no pyrolignin, presenting an MRE under 10% for both systems WO and BO. Among the possible structures, D2 (dimer), F1 (trimer) and I1, and I3 (tetramers) presented MRE ≤ 13% for both cases.

09 BIOMASS FUELS↗

DOE OSTI2025

Leveraging Natural Language Processing and Generative Models in Molecular Chemistry: Property Prediction and Novel Compound Generation

The accurate prediction of molecular properties is important for the rational design and the advancement of green chemistry and sustainable materials research. However, the predictive power of traditional computational chemistry methods is limited due to computational restrictions. Here, in this study, we examine an alternative approach to the accurate prediction of properties of organic compounds: natural language processing (NLP)-based molecular embedding. Using viscosity, partition coefficient (log P), and enthalpy of vaporization as test properties through a survey of comprehensive datasets comprising 5695 data points for viscosity, 25 870 data points for log P, and 2296 data points for enthalpy of vaporization. These are important properties for the design of greener, safer, and sustainable chemical processes. Models were trained using NLP methods such as Mol2vec and fine-tuned ChemBERTa, and results were compared with traditional input featurization techniques such as Morgan fingerprints and quantum chemistry derived sigma profiles and DFT features. Among the various machine learning models, Mol2vec demonstrated superior predictive capabilities, achieving the highest correlation coefficient (R 2 = 0.945) and lowest RMSE (0.106 mPa s) for viscosity, as well as high accuracy for log P and enthalpy of vaporization predictions. These findings establish the Mol2vec featurization technique, graph-convolutional neural networks (GCNN), and fine-tuned ChemBERTa model as powerful tools for predictive modeling of organic compounds properties, offering a significant improvement over previously used featurization techniques and opening up strategies for very-high-throughput computational screening. Finally, we integrated ML models with hybrid language-model-based generative adversarial networks (LM-GAN) to generate novel molecular sequences with desirable properties for different research applications. The ability to computationally design solvents with lower viscosity, lower log P, and lower enthalpy of vaporization offers a data-driven route to accelerating the discovery of sustainable alternatives to traditionally toxic solvents.

ChemBERTa↗

NASA NTRS1986

Partitioning of K, U, and Th between sulfide and silicate liquids - Implications for radioactive heating of planetary cores

Experimental partitioning studies are reported of K, U, and Th between silicate and FeFeS liquids designed to test the proposal that actinide partitioning into sulfide liquids is more important then K partitioning in the radioactive heating of planetary cores. For a basaltic liquid at 1450 C and 1.5 GPa, U partitioning into FeFeS liquids is five times greater than K partitioning. A typical value for the liquid partition coefficient for U from a granitic silicate liquid at one atmosphere at 1150 C and low fO2 is about 0.02; the coefficient for Th is similar. At low fO2 and higher temperature, experiments with basaltic liquids produce strong Ca and U partitioning into the sulfide liquid with U coefficient greater than one. The Th coefficient is less strongly affected.

Murrell, M. T.↗

NASA NTRS2011

Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

Usui, T.↗

NASA NTRS2010

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

Shofner, G. A.↗

NASA NTRS2015

Re-Evaluation of HSE DATA in Light of High P-T Partitioning Data: Late Chondritic Addition to Inner Solar System Bodies Not Always Required for HSE

Studies of terrestrial peridotite and martian and achondritic meteorites have led to the conclusion that addition of chondritic material to growing planets or planetesimals, after core formation, occurred on Earth, Moon, Mars, asteroid 4 Vesta, and the parent body of the angritic meteorites. One study even proposed that this was a common process in the final stages of growth. These conclusions are based al-most entirely on the 8 highly siderophile elements (HSE; Re, Au, Pt, Pd, Rh, Ru, Ir, Os), which have been used to argue for late accretion of chondritic material to the Earth after core formation was complete. This idea was originally proposed because the D(metal/silicate) values for the HSE are very high (greater than 10,000), yet their concentration in the terrestrial mantle is too high to be consistent with such high Ds. The HSE in the terrestrial mantle also are present in chondritic relative abundances and hence require similar Ds if this was the result of core-mantle equilibration. The conclusion that late chondritic additions are required for all five of these bodies is based on the chondritic relative abundances of the HSE, as well as their elevated concentrations in the samples. An easy solution is to call upon addition of chondritic material to the mantle of each body, just after core formation; however, in practice this means similar additions of chondritic materials to each body just after core formation which ranges from approximately 4-5 Ma after T(sub 0) for 4 Vesta and the angrites, to 10-25 Ma for Mars, to 35 to 60 Ma for Moon and perhaps the Earth. Since the work of there has been a realization that high PT conditions can lower the partition coefficients of many siderophile elements, indicating that high PT conditions (magma ocean stage) can potentially explain elevated siderophile element abundances. However, detailed high PT partitioning data have been lacking for many of the HSE to evaluate whether such ideas are viable for all four bodies. Re-cent partitioning studies have covered P, T, fO2, and compositional ranges that allow values to be predicted at conditions relevant to these five inner solar system bodies. Because the D(HSE) metal/silicate are lowered substantially at higher PT conditions and natural com-positions (FeNi metallic liquids and peridotites) it is natural to re-examine the role of core formation on the HSE patterns in a variety of inner solar system bodies. Here I will discuss other processes (including high PT core formation for Mars, Moon and Earth) that can produce the observed HSE patterns, and demonstrate that there are viable hypotheses other than the "one size fits all" hypothesis of late chondritic additions.

Righter, K.↗

NASA NTRS1994

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Beckett, J. R.↗

NASA NTRS2005

Influence of Silicate Melt Composition on Metal/Silicate Partitioning of W, Ge, Ga and Ni

The depletion of the siderophile elements in the Earth's upper mantle relative to the chondritic meteorites is a geochemical imprint of core segregation. Therefore, metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle. The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. Several recent studies have shown the importance of silicate melt composition on the partitioning of siderophile elements between silicate and metallic liquids. It has been demonstrated that many elements display increased solubility in less polymerized (mafic) melts. However, the importance of silicate melt composition was believed to be minor compared to the influence of oxygen fugacity until studies showed that melt composition is an important factor at high pressures and temperatures. It was found that melt composition is also important for partitioning of high valency siderophile elements. Atmospheric experiments were conducted, varying only silicate melt composition, to assess the importance of silicate melt composition for the partitioning of W, Co and Ga and found that the valence of the dissolving species plays an important role in determining the effect of composition on solubility. In this study, we extend the data set to higher pressures and investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid.

Singletary, S. J.↗