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1,057 records · Page 55

Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry that allows these reefs to persist. We investigated seawater carbonate chemistry using discrete samples along the NWHI and ESC from two cruises ~1 year apart (08/26/21 – 09/26/21, 09/09/22 – 10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr?¹, this long-term trend cannot explain the magnitude of ASH change observed between cruises. Temperature-salinity plots similarly indicate no major shifts in intermediate water masses that could account for these changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 – 2019 (excluding 2018) revealed high interannual ASH variability, by as much as >200 m at one site. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience seasonal and interannual shifts between under- and supersaturation. As ocean acidification progresses however, persistent exposure to undersaturated seawater could further threaten these critical deep-sea ecosystems.

coral reefs

Expanding the horizon of bio-naphtha beyond gasoline blend: property characterization and conversion opportunity assessment through technoeconomic and life-cycle analyses

Bio-naphtha, a common by-product of biorefineries, is expected to experience substantial growth in supply due to increasing demands for renewable diesel and synthetic aviation fuel (SAF). However, demand for bio-naphtha itself as a gasoline blendstock is limited because of the electrification of light-duty vehicles. This work investigated valorization opportunities for bio-naphtha from catalytic fast pyrolysis, hydrothermal liquefaction, Fischer–Tropsch synthesis, and hydrotreated esters and fatty acids pathways. These opportunities include producing polymer-grade olefin via steam cracking, SAF via steam cracking followed by olefin oligomerization, and renewable aromatics benzene, toluene, and xylene (BTX) and hydrogen via catalytic reforming. Process models were developed in Aspen Plus V14 and Aspen HYSYS V14 to calculate the mass and energy balances for each conversion step. Technoeconomic assessment and life-cycle analysis were conducted to evaluate the minimum fuel/product selling price, conversion cost, and life-cycle CO2 equivalent (CO2e) emission reduction. Technoeconomic assessment results suggest a minimum fuel/product selling price as low as $1.9/kg of olefins, $6.30/gal of gasoline-equivalent SAF, and $1.2/kg of BTX without any incentives. For all pathways, these prices are dominated by bio-naphtha feedstock costs, which account for at least 76% of the total cost. Compared with petroleum baselines, bio-naphtha-derived SAF, olefins, and BTX can achieve significant CO2e emission reductions from the use of renewable carbon resources. The results of life-cycle analysis and subsequent technoeconomic assessment, incorporating carbon credits, indicate the economic viability of using bio-naphtha for polymer-grade olefin and BTX production, with product costs comparable to market prices.

Xu, Shuang

Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS)

This topical review focuses on the distinct role of carbon support coordination environment of single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview of atomic coordination configurations in SACs, including a discussion of the advanced characterization techniques and simulation used for understanding the active sites. A summary of key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), and carbon dioxide reduction reaction (CO 2 RR). The review then shifts to modulation of the metal atom-carbon coordination environments, focusing on nitrogen and other non-metal coordination through modulation at the first coordination shell and modulation in the second and higher coordination shells. Representative case studies are provided, starting with the classic four-nitrogen-coordinated single metal atom (M$-$N 4 ) based SACs. Bimetallic coordination models including homo-paired and hetero-paired active sites are also discussed, being categorized as emerging approaches. The theme of the discussions is the correlation between synthesis methods for selective doping, the carbon structure–electron configuration changes associated with the doping, the analytical techniques used to ascertain these changes, and the resultant electrocatalysis performance. In conclusion, critical unanswered questions as well as promising underexplored research directions are identified.

36 MATERIALS SCIENCE

Collapse of magnetized white dwarfs as site of heavy-element formation and kilonova signal

We present the first end-to-end calculation connecting the accretion-induced collapse (AIC) of a magnetized, rapidly rotating white dwarf to observable kilonova signatures, combining two-dimensional (2D) general-relativistic neutrino-magnetohydrodynamic simulations, followed by radiation hydrodynamics with in-situ nuclear network and 2D Monte Carlo radiative transfer with spatially resolved heating rates. Unlike all previous unmagnetized AIC models – which predicted proton-rich, $^{56}$Ni-dominated ejecta – strong magnetic fields eject ${\approx }\, 0.2\, \mathrm{ M}_\odot$ of neutron-rich material ($\langle Y_e \rangle \sim 0.24$) on dynamical time-scales, before neutrino irradiation can raise the electron fraction, enabling strong r-process nucleosynthesis up to and beyond the third peak. The resulting kilonova is lanthanide-rich ($X_{\rm lan} \approx 8~{{\ \rm per\ cent}}$) and dominated by near-infrared emission. We compute synthetic light curves in the Large Synoptic Survey Telescope and J ames Webb Space Telescope bands and find striking agreement, without parameter tuning, between the observations of AT 2023vfi/GRB 230307A and our broadband light curves for polar viewing angles. These results establish magnetized AIC as a viable channel for heavy r-process element production and a compelling progenitor candidate for long-duration gamma-ray bursts with kilonova signatures.

MHD

Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine-learning interatomic potentials

Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure (δ-phase) during electrochemical cycling. Here, in this computational study, we use charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in LixMn 0.8 Ti 0.1 O 1.9 F 0.1 . Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of nontransition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn 2+ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the δ-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine-learning interatomic potentials for understanding complex oxide materials.

Zhong, Peichen [University of California, Berkeley

Manganese‐Based Spinel Cathodes: A Promising Frontier for Solid‐State Lithium‐Ion Batteries

Recently, all-solid-state lithium-ion batteries (ASSLIBs), which exhibit improved safety and enhanced energy density compared to conventional commercialized lithium-ion batteries (LIBs), thereby have garnered extensive research interest. Among the promising cathode candidates, Mn-based spinel cathodes LiMn 2 O 4 (LMO) and LiNi 0.5 Mn 1.5 O 4 (LNMO), with the unique characteristics of low cost, structural stability, and 3D Li-ion diffusion channels, have demonstrated excellent performance in LIBs and presented great potential in ASSLIBs applications. However, several challenges, including structural degradations, poor interfacial contact, large interfacial resistance, and Mn-dissolution/diffusion during the electrochemical cycling, hinder their practical applications and commercialization in the ASSLIBs. Particularly, the high-voltage LNMO cathodes suffer from the challenge of electrochemical incompatibility with most of the solid-state electrolytes (SSEs). Herein, the spinel structure, the electrochemical behavior, and the structural degradation of the LMO/LNMO are explored. The characteristics and recent progress of the mitigating strategies to the challenges of various SSEs, including polymer-, oxide-, composite-, sulfide-, halide-, and LiPON-based SSEs, are introduced when paired with LMO/LNMO. Finally, the directions for future research to advance Mn-based spinel cathodes and fulfill the requirements of the next-generation ASSLIBs are also discussed.

Dou, Yu [Concordia University, Montreal, QC (Canad

Adsorption of hydroxamic acid ligands for improved extraction of rare earth elements from monazite ores

Efficient separation of rare earth element (REE) ores via froth flotation requires the development of novel ligands with enhanced adsorption capacity and selectivity. To realize these advances, understanding the mechanisms underlying interactions between the ligand and mineral surfaces is essential. This study systematically evaluates the adsorption behavior of alkyl- and aromatic alkyl-substituted hydroxamic acid ligands on monazite surfaces using complementary spectroscopic techniques, including UV–visible (UV–vis) spectroscopy, Raman spectroscopy, infrared spectroscopy, and vibrational sum frequency generation (SFG) spectroscopy, together with the ab initio molecular dynamics (AIMD) simulations. Among the studied ligands, octanohydroxamic acid (OHA) and 4-ethoxy-N,2-dihydroxybenzamide (EDHBA) exhibit high adsorption capacity under basic pH (8–10) by forming multilayers on the surface. OHA has a higher equilibrium adsorption capacity compared to EDHBA, but it forms a less stable multilayer susceptible to disruption in the presence of interfering ions. AIMD results show that OHA adopts a single stable chelating geometry, while EDHBA exhibits multiple binding modes involving distinct interactions with La surface atoms and phosphate-bound oxygens, resulting in more complex adsorption kinetics. The variations in surface binding and intermolecular interactions observed between alkyl and aromatic molecules influence the differences in adsorption kinetics, equilibrium adsorption capacities on the mineral surface, and their flotation performance. This work provides valuable insight into the adsorption mechanism of ligands at mineral interfaces, which is crucial for guiding the design of new ligands with enhanced separation performance.

Zhou, Muchu [ORNL] (ORCID:0000000182650215)

Spacecraft Fire Safety Predictions using Verified Saffire Model

A model developed using Fire Dynamics Simulator (FDS) that aimed to determine the effect of a fire in a spacecraft was validated by data collected during the Saffire campaign. The model used inlet and outlet temperatures and CO 2 concentrations of the Saffire payload where fire spread was taking place to determine the amount of heat and combustion products that made it into Northrop Grumman’s Cygnus vehicle. The model was then validated using six remote sensors in various places in the vehicle, as well as a far field device (FFD) in the open zenith section that was representative of average vehicle values. The current work focuses on using the model to predict fire safety scenarios. One simulation aimed to determine the fate of HCl, which sticks to surfaces. The model prediction showed that the HCl was removed from the atmosphere rapidly. This compared well against the FFD data in the Saffire VI campaign event where a bottle of 5% HCl was released into the vehicle. An additional simulation where the Environmental Control and Life Support System (ECLSS) was shut off once the FFD reached 5 ppm of HCl showed that HCl stayed in the atmosphere considerably longer. Continuing the simulation with the ECLSS activated and after temperatures returned to their initial conditions, resulted in a rapid removal of HCL similar to that observed in the original HCl release scenario model. Finally, a simulation that used the heat release rate from a lithium-ion battery test to determine the effect it would have on a spacecraft was performed. This simulation used a heat addition rate that is considerably higher than what was determined from the burning of solid fuels in the Saffire campaign and hence produced a non-trivial temperature increase in more locations within the vehicle.

Fire Safety

Joint scheduling of energy, fast and primary frequency response reserves in integrated transmission–distribution networks

Inverter-based distributed energy resources (DERs) connected to distribution networks (DNs) can provide fast frequency support, but their reserve deliverability depends on feeder constraints and differs from synchronous primary frequency response (PFR). Existing transmission–distribution coordination studies usually treat reserve generically or neglect feeder-level feasibility, while frequency-security scheduling studies rarely represent distribution feeders explicitly. This paper develops a bi-level day-ahead scheduling framework for integrated transmission–distribution networks that jointly clears energy, transmission-side PFR, and distribution-side fast frequency response (FFR) under exogenous hourly inertia and largest-loss inputs from an external unit commitment (UC) schedule. The transmission problem is modeled with DC-optimal power flow (OPF) and closed-form second-order cone (SOC) frequency-security constraints, whereas each DN is represented by a reserve-aware branch-flow AC-OPF so that scheduled fast reserves remain deliverable during activation. The bi-level problem is reformulated through Karush–Kuhn–Tucker (KKT) conditions into a mixed-integer SOC program, and a penalty term is used to tighten the distribution-network relaxation. In the reduced test system, lower exogenous inertia increased the required primary response from 179.64 MW to 191.08 MW, distribution-side fast response reduced total frequency-response procurement by up to 4.9%, and neglecting distribution constraints overstated the combined distribution-side energy and reserve award by up to 18%. In the expanded study, the largest case was solved in 2.02 s with a 0.00% optimality gap. Time-domain simulations kept the frequency nadir above 59.0 Hz in all tested hours. These results demonstrate the value of fast-response modeling and distribution-feasible reserve delivery in coordinated market clearing.

Noh, Seung-Gil

Precise Modeling of a Complex Solenoidal Magnetic Field Using a Combination of Analytic Functions and a PINN

We demonstrate an iterative approach to modeling a sparsely measured magnetic field in a large-bore solenoid. This approach uses a hybrid of traditional and machine learning techniques. The traditional technique is a linear least-squares fit using a series solution to Laplace's equation, while the machine learning technique involves the training of a physics-informed neural network (PINN) on the least-squares fit residuals. We use a newly defined activation function "DELTAsnake," a modification to the snake activation function proposed by Ziyin et al. that allows for stronger curvature and non-monotonicity. The combined model approximately obeys Maxwell's equations to a level sufficient for producing high quality physics simulations and analysis. Our approach is applied to a highly realistic calculation of the expected magnetic field in the Mu2e experiment's Detector Solenoid which includes a simple model for the expected statistical measurement uncertainties. Using ten toy measurement simulations, we demonstrate the capabilities of our model in comparison to the least-squares method alone; the least-squares method alone results in a reduced chi-squared statistic of ${2.15 \pm 0.01}$, while our approach improves the reduced chi-square to ${1.034 \pm 0.005}$. Furthermore, for an average toy simulation, we show that the range of the RMS of the three field component residuals reduces from ${0.07-0.37}$ Gauss to ${0.05-0.07}$ Gauss. We find that this novel method is robust against a realistic systematic uncertainty deriving from Hall probe calibration bias and can be used to significantly reduce the number of measurements required to achieve an accurate model.

Kampa, Cole [Caltech] (ORCID:0000000192972920)

Constraints on Nuclear Symmetry Energy Parameters

A review is made of constraints on the nuclear symmetry energy parameters arising from nuclear binding energy measurements, theoretical chiral effective field predictions of neutron matter properties, the unitary gas conjecture, and measurements of neutron skin thicknesses and dipole polarizabilities. While most studies have been confined to the parameters 𝑆 𝑉 and L, the important roles played by, and constraints on 𝐾 sym , or, equivalently, the neutron matter incompressibility 𝐾 𝑁 , are discussed. Strong correlations among 𝑆 𝑉 ,𝐿, and 𝐾 𝑁 are found from both nuclear binding energies and neutron matter theory. However, these correlations somewhat differ in the two cases, and those from neutron matter theory have smaller uncertainties. To 68% confidence, it is found from neutron matter theory that 𝑆 𝑉 = 32.0 ± 1.1 MeV, 𝐿 = 51.9 ± 7.9 MeV and 𝐾 𝑁 = 152.2 ± 38.1 MeV. Theoretical predictions for neutron skin thickness and dipole polarizability measurements of the neutron-rich nuclei 48 Ca, 120 Sn, and 208 Pb are compared to recent experimental measurements, most notably the CREX and PREX neutron skin experiments from Jefferson Laboratory. By themselves, PREX I+II measurements of 208 Pb and CREX measurement of 48 Ca suggest 𝐿 = 121 ± 47 MeV and 𝐿 = −5 ± 40 MeV, respectively, to 68% confidence. However, we show that nuclear interactions optimally satisfying both measurements imply 𝐿 = 53 ± 13 MeV, nearly the range suggested by either nuclear mass measurements or neutron matter theory, and is also consistent with nuclear dipole polarizability measurements. This small parameter range implies 𝑅 1.4 = 11.6 ± 1.0 km and Λ 1.4 = 228$^{+148}_{−90}$, which are consistent with NICER X-ray and LIGO/Virgo gravitational wave observations of neutron stars.

neutron skins

Composite Lithium Metal Structure to Mitigate Pulverization and Enable Long‐Life Batteries

In lithium metal batteries, non‐uniform stripping of lithium results in pit formation, which promotes subsequent non‐uniform, dendritic deposition. This viscous cycle leads to pulverization of lithium which promotes cell shorting or capacity degradation, symptoms further exaggerated by high electrode areal loading and lean electrolytes. Here, to address this challenge, a composite lithium metal anode is engineered that contains uniformly distributed, nanometer‐sized carbon particles. This composite lithium is shown to strip more uniformly since the growth of non‐uniform pits is intercepted by the carbon particles. This mechanism is corroborated by a continuum electrochemical model. Subsequent lithium deposition on carbon particles is also found to be more uniform than on the surface with irregular pits. Notably, the pulverization rate of composite lithium is 26 times slower than that of commercial lithium. Moreover, in a Li‐S battery with sulfurized polyacrylonitrile cathode, the use of the composite anode extends the cycle life by three times when the areal capacity is 8 mAh cm −2 . The approach of using an engineered lithium composite structure to address challenges during both stripping and plating can inform future designs of lithium metal anodes for high areal capacity operations.

high areal capacity

ClassNMSW- a real-time classification approach for non-recycled municipal solid waste using hyperspectral imaging

Real-time classification of non-recycled municipal solid waste (NMSW) is essential for efficient valorization. This study introduces ClassNMSW, a comprehensive framework for classifying 22 NMSW subclasses under industrial constraints by using hyperspectral imaging (HSI). A primary innovation of this work is the development of a variance-controlled spectral extraction algorithm. Unlike traditional methods that rely on simple averaging, this approach systematically investigates the extent of pixel extraction to minimize the loss of critical chemical information while maximizing data reduction thus ensuring high spectral fidelity with low computational cost. The approach developed in this work integrates automated, computer-vision-based background removal, eliminating the need for the manual thresholding common in current literature. To resolve ambiguities among chemically similar subclasses, a tiered classification and multi-camera fusion strategy (NIR17 and NIR22) is implemented. Results demonstrate that ClassNMSW achieves an object-wise weighted accuracy of 98.70% for single-sensor configurations and 100% under sensor fusion. A novel rolling-window strategy satisfies desired end-to-end latency of <2 s, satisfying the strict deterministic requirements of high-speed industrial sorting environments. The ClassNMSW framework provides a scalable foundation for advancing circularity and resource recovery in large-scale waste valorization operations.

99 - GENERAL AND MISCELLANEOUS

Dielectric Spectroscopy Cable NDE for Unequal Aging Over Different Lengths

This Pacific Northwest National Laboratory milestone report assesses the effect of unequal aging over different lengths of cable on dielectric spectroscopy (DS) bulk impedance measurements from the cable end. DS measurements can indicate the remaining useful life of cables; however, most benchmark tests are based on accelerated aging of the entire cable. If only a portion of the cable is exposed to a harsh environment (as is frequently the case), the DS measurement will indicate a significantly less-aged cable than if the entire cable were exposed to a uniform environmental stress. The DS measurement is primarily related to the intrinsic insulation material relative permittivity—typically between 1.5 and 3.0. Insulation aging increases permittivity and, correspondingly, the cable’s overall capacitance measured from the cable end. To judge the health of the overall cable system, operators are primarily interested in the condition of the most severely aged section since that is where a failure is most likely to occur. This can be expressed as the dimensionless relative permittivity of the severely aged section divided by the permittivity of a pristine cable. This relative permittivity is an intrinsic material parameter independent of cable length and can serve as a quantitative indication of the insulation condition. If the relative percentages of cable exposed to a harsh and benign environment are known, the DS measurement of the entire cable length, including both pristine and aged sections, can be compensated to predict the relative permittivity (relative to pristine permittivity) of the most severly aged segment. A test was performed on three 50 ft (16 m) cables with 10%, 50%, and 90% of the cable inside a thermal aging oven. Predictably, the aging effect on the DS response was greatest in the 90% sample, followed by the 50% sample, and then the 10% sample. The more interesting result is the ratio of the aged insulation permittivity to the pristine insulation permittivity. Based on prior work, an end-of-life cable has a value of approximately 1.35. If the relative percentages of pristine and severely aged cable lengths are known, and the total cable-length capacitance of the initial pristine cable and the combined pristine plus aged cable are known, the relative aged permittivity (ratio of aged section permittivity / pristine section permittivity) can be estimated. The relative cable lengths exposed to a harsh environment may be known or estimated based on plant layout drawings or cable reflectometry tests that can locate the oven entry and exit points. The compensation was verified using a lumped-parameter model to predict the aged-segment permittivity e2/e1, where e2 is the aged-segment permittivity and e1 is the pristine-segment permittivity. For all three percentages of aged cable lengths, the ratio was quite similar, as would be expected since all cable segments were exposed to the same aging environment. This ratio of aged permittivity to pristine permittivity can be compared to other damage indicating tests, including elongation at break, to assess cable condition.

ARENA Test Bed

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok [Yale Univ., New Haven, CT (United

Evidence for the Interaction of the IRS 16 Wind With the Ionized and Molecular Gas at the Galactic Center

We present a number of high-resolution radio images showing evidence for the dynamical interaction of the outflow arising from the IRS 16 complex with the ionized gas associated with the Northern Arm of Sgr A West, and with the northwestern segment of the circumnuclear molecular disk which engulfs the inner few parsecs of the Galactic center. These interactions offer an opportunity to explain some important aspects of the complex morphology of ionized and molecular gas at the Galactic center. In particular we suggest that the wind disturbs the dynamics of the Northern Arm within 0.1 pc of the center, is responsible for the waviness of the arm at larger distances and is collimated by Sgr A West and the circumnuclear disk. The waviness is discussed in terms of the Rayleigh-Taylor instability induced by the ram pressure of the wind incident on the surface of the Northern Arm. Another consequence of this interaction is the strong mid IR polarization of the Northern Arm in the vicinity of the IRS 16 complex which is explained as a result of the ram pressure of the wind compressing the gas and the magnetic field. The IRS 16 complex must therefore lie close to the Northern Arm. On a large scale we argue that the wind has swept up the diffuse material in the inner parsec of the Galactic center and that the interaction with the inner part of the northwestern part of the circumnuclear ring is responsible for the H 2 v = 1-0 emission and the ionized streamers. Lastly, we discuss the possibility that the outflow from IRS 16 could be responsible for eating away the inner edge of the circumnuclear disk and provide friction needed for the infall of the material in the arms of Sgr A West.

IRS 16

A Survey of Lunar Rock Types and Comparison of the Crusts of Earth and Moon

The principal known types of lunar rocks are briefly reviewed, and their chemical relationships discussed. In the suite of low-KREEP highland rocks, Fe/(Fe + Mg) in the normative mafic minerals increases and the albite content of normative plagioclase decreases as the total amount of normative plagioclase increases, the opposite of the trend predicted by the Bowen reaction principle. Lunar highland samples analyzed are uniformly distributed in this sequence, in which normative plagioclase contents range from ~ 40 percent to ~ 100 percent. The distribution of compositions of rocks from terrestrial layered mafic intrusives is substantially different: here the analyses fall in several discrete clusters (anorthositic rocks, norites, granophyres and ferrogabbros, ultramafics), and the chemical trends noted above are not reproduced. It is suggested that the observed trends in lunar highland rocks could be produced by crystal fractionation in a deep global surface magma system if (1) plagioclase tended to float, upon crystallization, and (2) the magma was kept agitated and well mixed (probably by thermal convection) until crystallization was far advanced and relatively little residual liquid was left. When such a system was finally immobilized, the Fe-, Na-rich residual liquid would produce Fe-rich mafic minerals in the upper levels of the system, but could not much alter the composition of abundant calcic plagioclase. Conversely, the same liquid would produce sodic plagioclase deep in the sequence, but could not much alter the composition of abundant magnesian mafic minerals. After the crustal system solidified, but before extensive cooling had developed a thick, strong lithosphere, mantle convection was able to draw portions of the lunar anorthositic crust down into the mantle in a manner analogous to the present-day behavior of the terrestrial mantle and crust. At depth, the crustal material was heated; KREEP-rich norite was extracted by partial melting and erupted at the surface as a lava, analogous to terrestrial andesite eruptions.

John A Wood

Pinning ångström-size solid ionic channels for rare-earth element separation

High-purity rare-earth elements are essential for modern technologies, yet current solvent extraction processes are energy-intensive and environmentally harmful because of inadequate selectivity and ligand toxicity. Although combining size exclusion and binding affinity can improve lanthanide separation, the role of long-range confinement remains underexplored. Here we report lanthanide separation in aqueous systems using extremely confined manganese oxide solid ionic channels with optimized layer spacing. Different lanthanides induce distinct solid-state phase transformations in manganese oxide, creating a strong driving force for separation. Two lanthanide groups, differing by ~1.4 Å in spacing, were identified and confirmed to be stable by density functional theory. The narrower confinement of heavier Group II lanthanides improves cross-group separation by increasing the dehydration barrier for lighter Group I lanthanides without inducing strong binding. Here, we further developed a strategy to pin the confinement dimensions and enhance same-group separation, increasing enrichment factors for La–Nd and La–Pr pairs from 1.6 ± 0.1 and 1.5 ± 0.1 to 5.4 ± 0.1 and 4.2 ± 0.1, respectively.

Chemical engineering