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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12

A non-intrusive framework using acoustic signals and deep learning for boiling diagnostics in visual-limited environments

Accurate monitoring of boiling heat transfer is critical for safeguarding high-power systems operating in environments where conventional optical diagnostics are hindered by radiation fields or restricted visual accessibility. This study presents a non-intrusive framework that integrates hydroacoustic sensing with deep learning to infer near-wall boiling characteristics and enable predictive thermal assessment without visual access. In a prototypical subcooled flow-boiling facility representative of the Isotope Production Facility (IPF) at Los Alamos, hydrophones capture boiling-induced acoustic emissions that are transformed into background-removed Short-Time Fourier Transform (STFT) spectrograms. A convolutional neural network (CNN) then regresses heat flux, wall superheat, and key bubble parameters directly from these spectrograms. The CNN achieved predictive accuracy under nominal conditions and demonstrated robustness and generalization under acoustic noise for Signal-to-Noise Ratios (SNRs) down to approximately 0 dB. When integrated into an ANSYS CFX wall-boiling model, the acoustically inferred parameters reproduced boiling curve and critical heat flux (CHF) values consistent with image-based benchmarks. Furthermore, the model retained reliable performance under moderate variations in bulk temperature, flow rate, and hydrophone placement, confirming its generalizability across practical boundary conditions. These results demonstrate the feasibility of hydroacoustic-based deep learning as a viable path toward real-time, radiation-tolerant boiling diagnostics and predictive thermal safety assessment in inaccessible systems such as the IPF.

42 ENGINEERING↗

Laboratory Instrument Software Controlled Spread Spectrum Time Domain Reflectometry for Electrical Cable Testing

This research discusses development of a software-controlled laboratory instrument based spread spectrum time domain reflectometry system (SSTDR). This constitutes one task within PNNL’s Light Water Sustainability Program (LWRS) whose mission includes advancing nondestructive examination (NDE) techniques for off-line and on-line in-situ cable condition monitoring. In 2022, PNNL evaluated SSTDR for detection and characterization of a number of cable anomalies (Glass et al. 2022). The review included comparison of SSTDR to Frequency Domain Reflectometry (FDR) techniques which have enjoyed encouraging feedback and are starting to be used in nuclear power plants for periodic cable condition monitoring of cable systems as part of the plant’s overall cable aging management program. The FDR test introduces a broad-band chirp onto the cable at the cable end then listens for any reflection from a change of impedance along the cable caused by a damaged conductor or insulation, splices, contact with moisture, or other cable anomalies. The signal is captured in the frequency domain then transformed back to the time domain using an inverse Fourier transform (IFT). Based on the velocity of propagation, the impedance response signal is plotted against distance along the cable. Peak locations along the X-axis indicate the distance along the cable where a portion of the signal has been reflected back to the instrument as a result of a cable anomaly. The FDR test is considered the gold standard of reflectometry however it does require the cable to be de-energized to perform the test. The LIVEWIRE commercial SSTDR produces a similar plot to the FDR however all processing is in the time domain. A pseudo-random noise code (PN code) is input onto the cable conductor and the instrument listens for any reflected response from cable anomalies. The SSTDR processes the signal as an autocorrelation comparing the input PN code to any reflected signal detected. The autocorrelation analysis for thermal aging, water and water ingress detection, ground fault and phase-to-phase fault detection at various locations along the cable and with the cable attached and detached from a motor load, and on both energized and un-energized conditions were performed. These results were contrasted to Frequency Domain Reflectometry (FDR) measurements of the un-energized cable. Results were encouraging but indicated more work was warranted – particularly with the SSTDR, it seemed that the insulation damage would likely be better evaluated with multiple bandwidth cable tests particularly including larger bandwidths than were possible with the current commercial instrument. The commercial instrument’s bandwidth was set at 6, 12, 24, and 48MHz but note that SSTDR and FDR definitions of bandwidth trend similarly but are not the same. The FDR response could be more broadly adjusted, and the bandwidth of 100 to 500 MHz produced the best responses. FDR responses to anomalies were clearer than SSTDR responses and indications were that a broader bandwidth SSTDR may lead to improved SSTDR detection capability. This project used a laboratory instrument based SSTDR (primarily using an Arbitrary Waveform Generator (AWG) and a digital oscilloscope plus Python in-house software) that allowed software adjustment of the SSTDR bandwidth, window functions applied to the exciting Pseudo-random Noise (PN) code plus and other aspects of the SSTDR signal processing. Hereafter, this will be referred to as the PNNL SSTDR. Evaluating specific performance of the PNNL SSTDR is left to a separate report. This report documents hardware and software development to produce the SSTDR cable test system.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

An analytic hybrid halo + perturbation theory model for small-scale correlators: baryons, halos, and galaxies

In this work, we update Halo Zeldovich Perturbation Theory (HZPT, [1]), an analytic model for the two-point statistics of dark matter, to describe halo and galaxy clustering, and galaxy-matter cross-correlation on nonlinear scales. The model correcting Zeldovich has an analytic Fourier transform, and therefore is valid in both configuration space and Fourier space. The model is accurate at the 2%-level or less for P_mm (k< 1 h/Mpc), P_hm (k< 1 h/Mpc), P_hh (k< 2 h/Mpc), P gm (k< 1 h/Mpc), P gg (k< 1 h/Mpc), ξ mm (r> 1 Mpc/h), ξ hm (r> 2 Mpc/h), ξ hh (r> 2 Mpc/h), ξ gm (r> 1 Mpc/h), ξ gg (r> 2 Mpc/h), for LRG-like mock galaxies. We show that the HZPT model for matter correlators can account for the effects of a wide range of baryonic feedback models and provide two extended dark matter models which are of 1% (3%) accuracy for k < 10 (8) h/Mpc. We explicitly model the non-perturbative features of halo exclusion for the halo-halo and galaxy-galaxy correlators, as well as the presence of satellites for galaxy-matter and galaxy-galaxy correlation functions. We perform density estimation using N-body simulations and a wide range of HOD galaxy mocks to obtain correlations of model parameters with the cosmological parameters Ω m and σ 8 . HZPT can provide a fast, interpretable, and analytic model for combined-probe analyses of redshift surveys using scales well into the non-linear regime.

79 ASTRONOMY AND ASTROPHYSICS↗

Mechanism and dynamics of fatty acid photodecarboxylase

Photoenzymes are rare biocatalysts driven by absorption of a photon at each catalytic cycle; they inspire development of artificial photoenzymes with valuable activities. Fatty acid photodecarboxylase (FAP) is a natural photoenzyme that has potential applications in the bio-based production of hydrocarbons, yet its mechanism is far from fully understood. RATIONALE To elucidate the mechanism of FAP, we studied the wild-type (WT) enzyme from Chlorella variabilis (CvFAP) and variants with altered active-site residues using a wealth of techniques, including static and time-resolved crystallography and spectroscopy, as well as biochemical and computational approaches. RESULTS A 1.8-Å-resolution CvFAP x-ray crystal structure revealed a dense hydrogen-bonding network positioning the fatty acid carboxyl group in the vicinity of the flavin adenine dinucleotide (FAD) cofactor. Structures solved from free electron laser and low-dose synchrotron x-ray crystal data further highlighted an unusual bent shape of the oxidized flavin chromophore, and showed that the bending angle (14°) did not change upon photon absorption (step 1) or throughout the photocycle. Calculations showed that bending substantially affected the energy levels of the flavin. Structural and spectroscopic analysis of WT and mutant proteins targeting two conserved active-site residues, R451 and C432, demonstrated that both residues were crucial for proper positioning of the substrate and water molecules and for oxidation of the fatty acid carboxylate by 1 FAD* (~300 ps in WT FAP) to form FAD ∙– (step 2). Time-resolved infrared spectroscopy demonstrated that decarboxylation occured quasi-instantaneously upon this forward electron transfer, consistent with barrierless bond cleavage predicted by quantum chemistry calculations and with snapshots obtained by time-resolved crystallography. Transient absorption spectroscopy in H 2 O and D 2 O buffers indicated that back electron transfer from FAD ∙– was coupled to and limited by transfer of an exchangeable proton or hydrogen atom (step 3). Unexpectedly, concomitant with FAD ∙– reoxidation (to a red-shifted form FAD RS ) in 100 ns, most of the CO 2 product was converted, most likely into bicarbonate (as inferred from FTIR spectra of the cryotrapped FAD RS intermediate). Calculations indicated that this catalytic transformation involved an active-site water molecule. Cryo-Fourier transform infrared spectroscopy studies suggested that bicarbonate formation (step 4) was preceded by deprotonation of an arginine residue (step 3). At room temperature, the remaining CO 2 left the protein in 1.5 μs (step 4'). The observation of residual electron density close to C432 in electron density maps derived from time-resolved and cryocrystallography data suggests that this residue may play a role in stabilizing CO 2 and/or bicarbonate. Three routes for alkane formation were identified by quantum chemistry calculations; the one shown in the figure is favored by the ensemble of experimental data. CONCLUSION Finally, we provide a detailed and comprehensive characterization of light-driven hydrocarbon formation by FAP, which uses a remarkably complex mechanism including unique catalytic steps. We anticipate that our results will help to expand the green chemistry toolkit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Embedded Sensing in Additive Manufacturing Metal and Polymer Parts: A Comparative Study of Integration Techniques and Structural Health Monitoring Performance

This study presents a comparative evaluation of post-process sensor integration in additively manufactured (AM) metal and the in-situ process for polymer structures for structural health monitoring (SHM), with an emphasis on embedded sensors. Geometrically identical specimens were fabricated using copper via metal fused filament fabrication (FFF) and PLA via polymer FFF, with piezoelectric transducers (PZTs) inserted into internal cavities to assess the influence of material and placement on sensing fidelity. Mechanical testing under compressive and point loads generated signals that were transformed into time–frequency spectrograms using a Short-Time Fourier Transform (STFT) framework. An engineered RGB representation was developed, combining global amplitude scaling with an amplitude-envelope encoding to enhance contrast and highlight subtle wave features. These spectrograms served as inputs to convolutional neural networks (CNNs) for classification of load conditions and detection of damage-related features. Results showed reliable recognition in both copper and PLA specimens, with CNN classification accuracies exceeding 95%. Embedded PZTs were especially effective in PLA, where signal damping and environmental sensitivity often hinder surface-mounted sensors. This work demonstrates the advantages of embedded sensing in AM structures, particularly when paired with spectrogram-based feature engineering and CNN modeling, advancing real-time SHM for aerospace, energy, and defense applications.

additive manufacturing↗

Thermal Stability and Decomposition Products of P-Doped Ferrihydrite

This work aimed to determine the effect of various amounts of P admixtures in synthetic ferrihydrite on its thermal stability, transformation processes, and the properties of the products, at a broad range of temperatures up to 1000 °C. A detailed study was conducted using a series of synthetic ferrihydrites Fe 5 HO 8 ·4H 2 O doped with phosphates at P/Fe molar ratios of 0.2, 0.5, and 1.0. Ferrihydrite was synthesized by a reaction of Fe 2 (SO 4 ) 3 with 1 M KOH at room temperature in the presence of K 2 HPO 4 at pH 8.2. The products of the synthesis and the products of heating were characterized at various stages of transformation by using differential thermal analysis accompanied with X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy-energy dispersive X-ray spectroscopy. Coprecipitation of P with ferrihydrite results in the formation of P-doped 2-line ferrihydrite. A high P content reduces crystallinity. Phosphate significantly inhibits the thermal transformation processes. The temperature of thermal transformation increases from below 550 to 710–750 °C. Formation of intermediate maghemite and Fe-phosphates, is observed. The product of heating up to 1000 °C contains hematite associated with rodolicoite FePO 4 and grattarolaite Fe 3 PO 7 . Higher P content greatly increases the thermal stability and transformation temperature of rodolicoite as well.

thermal transformations↗

Generalized Cycle Benchmarking Algorithm for Characterizing Midcircuit Measurements

Midcircuit measurements (MCMs) are crucial ingredients in the development of fault-tolerant quantum computation. While there have been rapid experimental progresses in realizing MCMs, a systematic method for characterizing noisy MCMs is still under exploration. In this work, we develop a cycle benchmarking (CB)-type algorithm to characterize noisy MCMs. The key idea is to use a joint Fourier transform on the classical and quantum registers and then estimate parameters in the Fourier space, analogous to Pauli fidelities used in CB-type algorithms for characterizing the Pauli-noise channel of Clifford gates. Furthermore, we develop a theory of the noise learnability of MCMs, which determines what information can be learned about the noise model (in the presence of state preparation and terminating measurement noise) and what cannot, which shows that all learnable information can be learned using our algorithm. As an application, we show how to use the learned information to test the independence between measurement noise and state-preparation noise in an MCM. Finally, we conduct numerical simulations to illustrate the practical applicability of the algorithm. Similar to other CB-type algorithms, we expect the algorithm to provide a useful toolkit that is of experimental interest. Published by the American Physical Society 2025

Zhang, Zhihan (ORCID:0009000862907691)↗

Role of grain boundary crystallography on void growth in FCC metals

The growth of an isolated spherical void at and near a grain boundary or a triple junction is studied by means of full-field crystal plasticity simulations with explicit representation of the void. To examine the fundamental aspects of void/grain boundary interactions in these cases, a three-dimensional large-strain elasto-viscoplastic fast-Fourier transform (LS-EVP-FFT) model with axisymmetric tensile periodic boundary conditions was developed. We employ this model to reveal the role of crystallography (grain orientations, grain boundary misorientation and inclination angle with respect to the largest component of the applied stress) and type of loading on void growth. It was found that grain orientation was the primary crystallographic feature governing void growth in strain-rate controlled simulations. For strains small enough to not significantly alter the local geometry, the overall growth of the void in bicrystal boundaries was not strongly affected by grain boundary inclination angle. The relative amount of void growth experienced within each grain in a bicrystal or tri-crystal was strongly dependent on the grain boundary inclination angle. We found a subset of orientations that exhibit faster void growth in bicrystal boundaries than inside the constituent single crystals. Last, we show that when placed primarily in one grain but near the grain boundary, void growth was similar to void growth when placed at the grain boundary. Furthermore, the growing void remained in the original grain and did not grow into the other grain, regardless of crystallographic character.

36 MATERIALS SCIENCE↗

Mechanistic insights into the colloidal assembly of mesoporous silica using in-operando cross-scale X-ray scattering and spectroscopic measurements

Advancing a mechanistic understanding of the colloidal to solid-phase transformations of silica allows us to tune these meso-scale structures. In this study, we probe the structural transformations associated with the formation of mesoporous silica particles, SBA-15 using in-operando Small Angle X-ray Scattering (SAXS) and Grazing Incidence-Small Angle X-ray Scattering (GI-SAXS). The chemical transformations associated with the hydrolysis and condensation of silica particles is investigated using Attenuated Total Reflection – Fourier Transform Infrared Spectroscopy (ATR-FTIR) measurements. Fast polymerization of Si-O-Si species to form mesoporous silica is noted when SBA-15 is synthesized in the presence of nitrate salts, due to the “salting-in” effect or enhanced solubility of polymers. However, aging the silica particles resulted in plate-like morphologies in the absence of the nitrate salt and spherical morphologies in the presence of nitrate salt. Early onset of nucleation of silica particles in the presence of nitrate salts was captured using GI-SAXS measurements. These studies show that the rational basis for developing new synthesis routes for accelerated kinetics or specific meso-scale structures can be informed by detailed characterization of the evolution in chemistry and meso-scale structure of these materials.

36 MATERIALS SCIENCE↗

Electron-induced chemical transformation of vapor-phase synthesized hybrid resist materials for EUV and beyond EUV lithography

Here, in this study, we utilize an in situ Fourier transform infrared (FTIR) spectroscopy chamber equipped with an electron flood gun to comprehensively investigate the electron-induced chemical transformations in advanced inorganic–organic hybrid resist thin films. The characteristics of the electron gun were assessed, showing a detectable current decrease with increasing Faraday cup bias voltage, confirming that the electron energies impacting the sample were within the expected range. This unique FTIR system was applied to study two hybrid resist thin-film systems, Al–HQ and Zn–HQ, both exhibiting saturation growth characteristics at 150 °C. Results revealed that Al–HQ demonstrated superior electron sensitivity compared to Zn–HQ at energies ≤ 100 eV. Chemical changes observed were consistent with previous findings, underscoring the potential of this methodology to elucidate exposure mechanisms. This research contributes to the fundamental understanding necessary for the development of advanced resist materials for the next-generation nanolithography applications.

36 MATERIALS SCIENCE↗

Investigation of crossed-twin structure formation in magnesium and magnesium alloys

In this work, the effect of alloying addition on the propensity for twin-twin interactions to transform into crossed-twin structures in magnesium alloys is investigated. A full-field elasto-viscoplastic fast Fourier transform (EVP-FFT) framework combined with a discrete twin model and dislocation density-based hardening law for slip strengths is used to calculate the micromechanical fields in the crystalline matrix around the interacting twins. AZ31 and MgLi alloys are selected along with pure Mg to study the influence of plastic anisotropy in connection with alloying elements. These alloys were selected since their plastic anisotropy measure, which is defined as the ratio between the critical resolved shear stress for pyramidal $\langle$c +a$\rangle$ and basal $\langle$a$\rangle$ slip modes, spanned a wide range. To quantify the role of twin thicknesses, we probe a range of impinging twin thicknesses while fixing the recipient twin thickness. The analysis reveals that: (i) the local driving stress for crossed twin structure formation generated from the interaction of the two twins is lower in a low plastically anisotropic material, like a MgLi alloy, than a high plastically anisotropic material like pure Mg and (ii) the critical impinging twin thickness needed to form the crossed twin structure in pure Mg, AZ31 and MgLi alloys is ~0.5, ~0.75 and ~1.5 times the recipient twin thickness. We propose a relationship between the tendency for crossed twin structure formation and the experimentally observed higher ductility in MgLi alloys compared to pure Mg. Finally, one key implication of the findings is that crossed- twin structure formation can be hindered and the ductility of magnesium alloy thereby improved by properly choosing alloying elements that lower the slip strength for pyramidal $\langle$c + a$\rangle$ slip.

36 MATERIALS SCIENCE↗

Functional Adaptation of LPS-affected Dentoalveolar Fibrous Joints in Rats

We report the functional interplay between cementum of the root and alveolar bone of the socket is tuned by a uniquely positioned 70–80 µm wide fibrous and lubricious ligament in a dentoalveolar joint (DAJ). In this study, structural and biomechanical properties of the DAJ, periodontal ligament space (PDL-space also known as the joint space), alveolar bone of the socket, and cementum of the tooth root that govern the biomechanics of a lipopolysaccharide (LPS)-affected DAJ were mapped both in space and time. The hemi-maxillae from 20 rats (4 control at 6 weeks of age, 4 control and 4 LPS-affected at 12 weeks of age, 4 control and 4 LPS-affected at 16 weeks of age) were investigated using a hybrid technique; micro-X-ray computed tomography (5 µm resolution) in combination with biomechanical testing in situ. Temporal variations in bone and cementum volume fractions were evaluated. Trends in mineral apposition rates (MAR) in additional six Sprague Dawley rats (3 controls, 3 LPS-affected) were revealed by transforming spatial fluorochrome signals to functional growth rates (linearity factor - RW) of bone, dentin, and cementum using a fast Fourier transform on fluorochrome signals from 100-µm hemi-maxillae sections. An overall change in LPS-affected DAJ biomechanics (a 2.5–4.5X increase in tooth displacement and 2X tooth rotation at 6 weeks, no increase in displacement and a 7X increase in rotation at 12 weeks; 27% increase in bone effective strain at 6 weeks and 11% at 12 weeks relative to control) was associated with structural changes in the coronal regions of the DAJ (15% increase in PDL-space from 0 to 6 weeks but only 5% from 6 to 12 weeks compared to control). A significant increase (p < 0.05) in PDL-space between ligated and age-matched control was observed. The bone fraction of ligated at 12 weeks was significantly lower than its age-matched control, and no significant differences (p > 0.05) between groups were observed at 6 weeks. Cementum in the apical regions grew faster but nonlinearly (11% and 20% increase in cementum fraction (CF) at 6 and 12 weeks) compared to control. Alveolar bone revealed site-specific nonlinear growth with an overall increase in MAR (108.5 µm/week to 126.7 µm/week after LPS treatment) compared to dentin (28.3 µm/week in control vs. 26.1 µm/week in LPS-affected) and cementum (126.5 µm/week in control vs. 119.9 µm/week in LPS-affected). A significant increase in CF (p < 0.05) in ligated specimens was observed at 6 weeks of age. Anatomy-specific responses of cementum and bone to the mechano-chemo stimuli, and their collective temporal contribution to observed changes in PDL-space were perpetuated by altered tooth movement. Data highlight the “resilience” of DAJ function through the predominance of nonlinear growth response of cementum, changes in PDL-space, and bone architecture. Despite the significant differences in bone and cementum architectures, data provided insights into the reactionary effects of cementum as a built-in compensatory mechanism to reestablish functional competence of the DAJ. The spatial shifts in architectures of alveolar bone and cementum, and consequently ligament space, highlight adaptations farther away from the site of insult, which also is another novel insight from this study. These adaptations when correlated within the context of joint function (biomechanics) illustrate that they are indeed necessary to sustain DAJ function albeit being pathological.

60 APPLIED LIFE SCIENCES↗

Nonlinear spectral analysis of ion acoustic solitons arising from a streaming charged object using the numerical inverse scattering transform

Observations of nonlinear coherent plasma phenomena in spacecraft and terrestrial experiments often rely on visual identification of solitary modes because nonlinear coherent modes are broadband in a Fourier transform based analysis. We implement an alternative spectral decomposition known as the inverse scattering transform and demonstrate its ability to successfully isolate nonlinear modes on the homogeneous and forced Korteweg–De Vries equation which models these nonlinear modes. We also demonstrate for the first time that this decomposition is useful when forcing is applied. This is because the stable modes generated by localized forcing are similar to the homogeneous solutions where the inverse scattering transform is a rigorous decomposition. This spectral technique is then applied to simulations of ion acoustic waves generated by a 10 mm spherical debris object interacting with the ionospheric plasma orbiting at 2000 km altitude. The algorithm is found to successfully detect the resultant solitons. This demonstrates the feasibility of using this spectral technique as a real time analysis tool for screening spacecraft data for nonlinear solitary modes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Inverse problem in the large momentum effective theory framework

One proposal to compute parton distributions from first principles is the large momentum effective theory (LaMET), which requires the Fourier transform of matrix elements computed nonperturbatively. Lattice quantum chromodynamics (QCD) provides calculations of these matrix elements over a finite range of Fourier harmonics that are often noisy or unreliable in the largest computed harmonics. It has been suggested that enforcing an exponential decay of the missing harmonics helps alleviate this issue. Using nonperturbative data, we show that the uncertainty introduced by this inverse problem in a realistic setup remains significant without very restrictive assumptions, and that the importance of the exact asymptotic behavior is minimal for values of 𝑥 where the framework is currently applicable. We show that the crux of the inverse problem lies in harmonics of the order of 𝜆 = 𝑧⁢𝑃 𝑧 ∼ 5–15, where the signal in the lattice data is often barely existent in current studies, and the asymptotic behavior is not firmly established. We stress the need for more sophisticated techniques to account for this inverse problem, whether in the LaMET or related frameworks like the short-distance factorization. We also address a misconception that, with available lattice methods, the LaMET framework allows a “direct” computation of the 𝑥-dependence, whereas the alternative short-distance factorization only gives access to moments or fits of the 𝑥-dependence.

Dutrieux, Hervé [Aix-Marseille Université, Marseil↗

kokkos-fft: A shared-memory FFT for the Kokkos ecosystem

kokkos-fft provides a unified, performance-portable interface for Fast Fourier Transforms (FFTs) within the Kokkos ecosystem (C. Trott et al., 2021). It seamlessly integrates with leading local FFT libraries including FFTW, cuFFT, rocFFT, and oneMKL. Designed for simplicity and efficiency, kokkos-fft offers a user experience akin to numpy.fft for in-place and out-of-place transforms, while leveraging the raw speed of vendor-optimized libraries. A demonstration solving 2D Hasegawa-Wakatani turbulence with the Fourier spectral method illustrates how kokkos-fft can deliver significant speedups over Python-based alternatives without drastically increasing code complexity, empowering researchers to perform high-performance FFTs simply and effectively.

97 MATHEMATICS AND COMPUTING↗

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↗

The transformation of lepidocrocite (γ-FeOOH) with Fe($\tiny{II}$) (aq) in slightly acidic media: intermediate pathways and biomimetic behavior

Lepidocrocite (LP) is commonly found in natural or anthropogenic environments and oxidized alloy steel waste storage containers. Despite its importance, the end products formed and its mineral transformation pathways, including intermediate steps and underlying mechanisms under Fe(II) (aq) catalysis still need to be clarified due to decades of dispersed research. Here, in this work, we investigated LP's catalytic transformation with 10 mM and 0.2 mM Fe(II) (aq) at their natural solution pH's via bulk (X-ray Diffraction/XRD, Raman and Attenuated Total Reflectance Fourier Transform Infrared/ATR-FTIR) and micro/nano-scale (semi in situ Transmission Electron Microscopy/TEM) analysis. In general, we observed that goethite (GT) and LP were the main end products. However, a series of two major distinct intermediate events that were initiated by a dissolution type of reaction along with an “induction period” (lack of dissolution) on LP occurred. Fascinatingly, two of the intermediate steps along its mineral transformation presented novel types of non-classical mechanisms of crystallization via some type of guided oriented particle attachment. Furthermore, one of these intermediate steps is biomimetic in appearance, similar to what is observed during bacterial particle attachment. However, it uses inorganic nano-wire antennas that have a sensory-like function as observed with bacterial fimbriae and/or flagellum through an electron transparent film (similar to a bio-film matrix). Finally, this work leads us to comprehend the evolution of some well documented crystal morphologies for GT commonly observed in natural and anthropogenic settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mineralogical transformations in polymetallic nodules and the change of Ni, Cu and Co crystal-chemistry upon burial in sediments

Polymetallic nodules from the Clarion and Clipperton Zone of the equatorial Pacific Ocean were studied using X-ray diffraction, X-ray absorption, Fourier-transformed infrared spectroscopy and transmission electron microscopy. Here, this study includes nodules found at the sediment surface as well as subsurface (14–16 cm sediment depth) and deeply buried (530–985 cm sediment depth) nodules. The surface and subsurface nodules are currently under oxic conditions whereas the deeply buried nodules are under suboxic conditions. Surface nodules consist mainly of turbostratic phyllomanganates (7 Å and 10 Å vernadite and Fe-vernadite); todorokite is a minor phase, if present at all. In contrast, subsurface and especially deeply buried nodules predominantly consist of todorokite, which increases in abundance with depth in the sediment. Thus, upon burial of nodules within the shallow sediment, phyllomanganates transform to todorokite, probably through the combined action of time and change in the ambient chemical conditions. Nodules from deeper sediment depth (>500 cm) consist primarily of todorokite and additionally show signs of dissolution. The transformation of phyllomanganates to todorokite and their further dissolution upon nodule burial under suboxic conditions induces modifications in the crystal-chemistry of Ni, Co, and Cu. In surface nodules, Ni and Co are incorporated in the octahedral sheets of phyllomanganates, whereas Cu mainly is located at the edges of those phyllomanganate sheets. In buried nodules Cu and to a lesser extent Ni are incorporated in todorokite by forming outer-sphere complexes within the tunnels. However, Ni is predominantly incorporated within the octahedra of the newly formed todorokite structure. Co is also enriched in the octahedra of todorokite as a result of dissolution of hydrogenetic vernadite and re-incorporation in the more stable Mn-phase formed during the diagenetic transformation. Co enrichment under suboxic conditions after burial within the sediments is noteworthy since Co in surface nodules is characteristic for oxic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗