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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

The Impact of Freeze‐Thaw History on Soil Carbon Response to Experimental Freeze‐Thaw Cycles

Abstract Freeze‐thaw is a disturbance process in cold regions where permafrost soils are becoming vulnerable to temperature fluctuations above 0°C. Freeze‐thaw alters soil physical and biogeochemical properties with implications for carbon persistence and emissions in Arctic landscapes. We examined whether different freeze‐thaw histories in two soil systems led to contrasting biogeochemical responses under a laboratory‐controlled freeze‐thaw incubation. We investigated controls on carbon composition through Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS) to identify nominal carbon oxidation states and relative abundances of aliphatic‐type carbon molecules in both surface and subsurface soils. Soil cores (∼60 cm‐depth) were sampled from two sites in Alaskan permafrost landscapes with different in situ freeze‐thaw characteristics: Healy (>40 freeze‐thaw cycles annually) and Toolik (<15 freeze‐thaw cycles annually). FT‐ICR‐MS was coupled with in situ temperature data and soil properties (i.e., soil texture, mineralogy) to assess (a) differences in soil organic matter composition associated with previous freeze‐thaw history and (b) sensitivity to experimental freeze‐thaw in the extracted cores. Control (freeze‐only) samples showed greater carbon oxidation in Healy soils compared with Toolik, even in lower mineral horizons where freeze‐thaw history was comparable across both sites. Healy showed the most loss of carbon compounds following experimental freeze‐thaw in the lower mineral depths, including a decrease in aliphatics. Toolik soils responded more slowly to freeze‐thaw as shown by intermediary carbon oxidation distributed across multiple carbon compound classes. Variations in the response of permafrost carbon chemistry to freeze‐thaw is an important factor for predicting changes in soil function as permafrost thaws in high northern latitudes.

Rooney, Erin C.↗
DOE OSTI2014

Three-dimensional texture analysis of contrast enhanced CT images for treatment response assessment in Hodgkin lymphoma: Comparison with F-18-FDG PET

Purpose: To determine the diagnostic performance of three-dimensional (3D) texture analysis (TA) of contrast-enhanced computed tomography (CE-CT) images for treatment response assessment in patients with Hodgkin lymphoma (HL), compared with F-18-fludeoxyglucose (FDG) positron emission tomography/CT. Methods: 3D TA of 48 lymph nodes in 29 patients was performed on venous-phase CE-CT images before and after chemotherapy. All lymph nodes showed pathologically elevated FDG uptake at baseline. A stepwise logistic regression with forward selection was performed to identify classic CT parameters and texture features (TF) that enable the separation of complete response (CR) and persistent disease. Results: The TF fraction of image in runs, calculated for the 45° direction, was able to correctly identify CR with an accuracy of 75%, a sensitivity of 79.3%, and a specificity of 68.4%. Classical CT features achieved an accuracy of 75%, a sensitivity of 86.2%, and a specificity of 57.9%, whereas the combination of TF and CT imaging achieved an accuracy of 83.3%, a sensitivity of 86.2%, and a specificity of 78.9%. Conclusions: 3D TA of CE-CT images is potentially useful to identify nodal residual disease in HL, with a performance comparable to that of classical CT parameters. Best results are achieved when TA and classical CT features are combined.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

REACTION RATES OF {sup 64}Ge(p,γ){sup 65}As AND {sup 65}As(p,γ){sup 66}Se AND THE EXTENT OF NUCLEOSYNTHESIS IN TYPE I X-RAY BURSTS

The extent of nucleosynthesis in models of type I X-ray bursts (XRBs) and the associated impact on the energy released in these explosive events are sensitive to nuclear masses and reaction rates around the {sup 64}Ge waiting point. Using the well known mass of {sup 64}Ge, the recently measured {sup 65}As mass, and large-scale shell model calculations, we have determined new thermonuclear rates of the {sup 64}Ge(p,γ){sup 65}As and {sup 65}As(p,γ){sup 66}Se reactions with reliable uncertainties. The new reaction rates differ significantly from previously published rates. Using the new data, we analyze the impact of the new rates and the remaining nuclear physics uncertainties on the {sup 64}Ge waiting point in a number of representative one-zone XRB models. We find that in contrast to previous work, when all relevant uncertainties are considered, a strong {sup 64}Ge rp-process waiting point cannot be ruled out. The nuclear physics uncertainties strongly affect XRB model predictions of the synthesis of {sup 64}Zn, the synthesis of nuclei beyond A = 64, the energy generation, and the burst light curve. We also identify key nuclear uncertainties that need to be addressed to determine the role of the {sup 64}Ge waiting point in XRBs. These include the remaining uncertainty in the {sup 65}As mass, the uncertainty of the {sup 66}Se mass, and the remaining uncertainty in the {sup 65}As(p,γ){sup 66}Se reaction rate, which mainly originates from uncertain resonance energies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Impacts of sulfonic acids on fungal manganese oxide production

Microbial manganese (Mn) oxidation plays a critical role in Mn(III/IV) oxide formation in modern day environmental systems. These oxidation processes and resulting biominerals are sensitive to aqueous conditions, such as pH and dissolved constituent concentrations. With Mn and sulfur (S) biogeochemical cycling closely linked in many environmental systems, and dissolved organic sulfur comprising a substantial pool of total sulfur in several environments, the impact of dissolved organic sulfur compounds on Mn redox processes is important to consider. Sulfonic acids, environmentally ubiquitous organosulfur compounds, play substantial roles in S cycling in many natural and contaminated systems. Research to assess the effects of these abundant sulfonic acids on Mn biogeochemical cycling, microbial Mn oxidation processes, and Mn biominerals is needed for understanding and predicting the impact of coupled S and Mn biogeochemical cycles, particularly in environments with dynamic redox gradients or in anthropogenically contaminated systems. Further, with research on microbial and abiotic Mn oxidation processes often using aminosulfonic acids to control pH, understanding the impact of such sulfonic acids on microbial Mn oxidation processes is critical. Several recent studies found that commonly used zwitterionic N substituted aminosulfonic acids, known as Good’s buffers, such as HEPES and MES, can alter abiotic birnessite sheet structures. Here we investigate the impact of two sulfonic acids with broad applications to natural and contaminated sites as well as laboratory settings (HEPES and MES) on fungal Mn oxidation relative to a carbonate buffer and a buffer-free control by three Ascomycete fungi known to oxidize Mn(II): Stagonospora sp. SRC1lsM3a, Paraphaeosphaeria sporulosa AP3s5–JAC2a, and Plectosphaerella cucumerina DS2psM2a2. Structural analyses of the products show that sulfonic acids promote Mn oxidation by P. cucumerina, producing hexagonally symmetric phyllomanganates analogous to hexagonal birnessite or c–disordered H + birnessite [(Ca,Na,K)(Mn 4+ ,Mn 3+ ,$\square$)O 2 nH 2 O], with solid–associated Mn(II) bound to vacancy sites and biomass, while in their absence almost all Mn remains as either aqueous Mn(II) or solid–associated Mn(II) bound to biomass. In contrast, sulfonic acids exert the opposite effect on Mn oxidation by P. sporulosa, with their presence suppressing Mn(II) oxidation to Mn(IV), likely leading to the formation of mycogenic bixbyite (Mn 3+ 2 O 3 ) while the buffer–free control forms a poorly crystalline phyllo- or tectomanganate. Meanwhile, all treatments exert a minimal effect on Mn(II) uptake from solution and Mn oxidation with Stagonospora sp., with all experimental systems and controls forming poorly crystalline, hexagonally symmetric phyllomanganates. The fact that the sulfonic acids here studied exert similar effects on Mn oxidation, but substantially different effects for each fungus, suggests they affect Mn oxidation via mechanistically similar pathways that are likely dependent on interactions with fungal exudates (which vary from species to species) or specific fungal Mn oxidation processes. Interestingly, for all fungi, MES increases Mn(III) in the resulting biominerals, while the carbonate buffer consistently decreases Mn(III). Further, these results clearly demonstrate that sulfonic acids not only alter Mn oxide structures, as has been previously noted in abiotic studies, but can interfere with Mn oxidation reactions themselves, highlighting the incredible sensitivity of both Mn oxide structures and the Mn oxidation process to the aqueous environment.

58 GEOSCIENCES↗
DOE OSTI2016

Assessment of mitochondrial dysfunction-related, drug-induced hepatotoxicity in primary rat hepatocytes

Evidence that mitochondrial dysfunction plays a central role in drug-induced liver injury is rapidly accumulating. In contrast to physiological conditions, in which almost all adenosine triphosphate (ATP) in hepatocytes is generated in mitochondria via aerobic respiration, the high glucose content and limited oxygen supply of conventional culture systems force primary hepatocytes to generate most ATP via cytosolic glycolysis. Thus, such anaerobically poised cells are resistant to xenobiotics that impair mitochondrial function, and are not suitable to identify drugs with mitochondrial liabilities. In this study, primary rat hepatocytes were cultured in galactose-based medium, instead of the conventional glucose-based medium, and in hyperoxia to improve the reliance of energy generation on aerobic respiration. Activation of mitochondria was verified by diminished cellular lactate release and increased oxygen consumption. These conditions improved sensitivity to the mitochondrial complex I inhibitor rotenone. Since oxidative stress is also a general cause of mitochondrial impairment, cells were exposed to test compounds in the presence of transferrin to increase the generation of reactive oxygen species via increased uptake of iron. Finally, 14 compounds with reported mitochondrial liabilities were tested to validate this new drug-induced mitochondrial toxicity assay. Overall, the culture of primary rat hepatocytes in galactose, hyperoxia and transferrin is a useful model for the identification of mitochondrial dysfunction-related drug-induced hepatotoxicity. - Highlights: • Drug-induced mitochondrial toxicity was evaluated using primary rat hepatocytes. • Galactose and hyperoxia could activate OXPHOS in primary rat hepatocytes. • Cells with enhanced OXPHOS exhibit improved sensitivity to mitochondrial toxins. • Transferrin potentiate mitochondrial toxicity via increased ROS production.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Revisiting superconductivity in the extended one-band Hubbard model: Pairing via spin and charge fluctuations

The leading superconducting instabilities of the two-dimensional extended repulsive one-band Hubbard model within spin-fluctuation pairing theory depend sensitively on electron density, band, and interaction parameters. We map out the phase diagrams within a random-phase-approximation spin- and charge-fluctuation approach, and find that while B 1g (d x 2 –y 2 ) and B 2g (d xy ) pairing dominates in the absence of repulsive longer-range Coulomb interactions V NN , the latter induces pairing in other symmetry channels, including, e.g., A 2g (g-wave), nodal A 1g (extended s-wave), or nodal E u (p-wave) spin-triplet superconductivity. At the lowest temperatures, transition boundaries in the phase diagrams between symmetry-distinct spin-singlet orders generate complex time-reversal symmetry broken superpositions. By contrast, we find that boundaries between singlet and triplet regions are characterized by first-order transitions. Finally, motivated by recent photoemission experiments, we have determined the influence of an additional explicitly attractive nearest-neighbor interaction, V NN < 0, on the superconducting gap structure. Furthermore, depending on the electronic filling, such an attraction boosts E u (p-wave) spin-triplet or B 1g (d x 2 –y 2 ) spin-singlet ordering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Kiloparsec-scale dust disks in high-redshift luminous submillimeter galaxies

We present high-resolution (0.″16) 870 μm Atacama Large Millimeter/submillimeter Array (ALMA) imaging of 16 luminous (L{sub IR}∼4×10{sup 12} L{sub ⊙}) submillimeter galaxies (SMGs) from the ALESS survey of the Extended Chandra Deep Field South. This dust imaging traces the dust-obscured star formation in these z∼2.5 galaxies on ∼1.3 kpc scales. The emission has a median effective radius of R {sub e} = 0.″24 ± 0.″02, corresponding to a typical physical size of R{sub e}= 1.8 ± 0.2 kpc. We derive a median Sérsic index of n = 0.9 ± 0.2, implying that the dust emission is remarkably disk-like at the current resolution and sensitivity. We use different weighting schemes with the visibilities to search for clumps on 0.″12 (∼1.0 kpc) scales, but we find no significant evidence for clumping in the majority of cases. Indeed, we demonstrate using simulations that the observed morphologies are generally consistent with smooth exponential disks, suggesting that caution should be exercised when identifying candidate clumps in even moderate signal-to-noise ratio interferometric data. We compare our maps to comparable-resolution Hubble Space Telescope H{sub 160}-band images, finding that the stellar morphologies appear significantly more extended and disturbed, and suggesting that major mergers may be responsible for driving the formation of the compact dust disks we observe. The stark contrast between the obscured and unobscured morphologies may also have implications for SED fitting routines that assume the dust is co-located with the optical/near-IR continuum emission. Finally, we discuss the potential of the current bursts of star formation to transform the observed galaxy sizes and light profiles, showing that the z∼0 descendants of these SMGs are expected to have stellar masses, effective radii, and gas surface densities consistent with the most compact massive (M{sub ∗} ∼ 1–2 × 10{sup 11} M{sub ⊙}) early-type galaxies observed locally.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1995

Estimation of penetration of forest canopies by Interferometric SAR measurements

In contrast to traditional Synthetic Aperture Radar (SAR), an Interferometric SAR (INSAR) yields two additional measurements: the phase difference and the correlation between the two interferometric channels. The phase difference has been used to estimate topographic height. For homogeneous surfaces, the correlation depends on the system signal-to-noise (SNR) ratio, the interferometer parameters, and the local slope. In the presence of volume scattering, such as that encountered in vegetation canopies, the correlation between the two channels is also dependent on the degree of penetration of the radiation into the scattering medium. In this paper, we propose a method for removing system and slope effects in order to obtain the decorrelation due to penetration alone. The sensitivities and accuracy of the proposed method are determined by Monte Carlo experiments, and we show that the proposed technique has sufficient sensitivity to provide penetration measurements for airborne SAR systems. Next, we provide a theoretical model to estimate the degree of penetration in a way which is independent of the details of the scattering medium. We also present a model for the correlation from non-homogeneous layers. We assess the sensitivity of the proposed inversion technique to these inhomogeneous situations. Finally, we present a comparison of the interferometric results against in situ data obtained by an airborne laser profilometer which provides a direct measurement of tree height and an estimate of the vegetation density profile in the forested areas around Mt. Adams, WA.

Rodriguez, Ernesto↗
NASA NTRS2009

Finding ExoEarths: The Problem of Exozodical Dust

Dust coming from asteroids and comets will strongly affect direct imaging and characterization of terrestrial planets in the Habitable Zones of nearby stars. Such dust in the Solar System is called the zodiacal dust. Higher levels of similar dust are seen around many nearby stars, confined in disks called debris disks. Future high-contrast images of an Earth-like exoplanet (or "exoEarth") will very likely be background-limited by light scattered of both local Solar System zodiacal dust and circumstellar dust in the extrasolar system (exozodiacal dust). Clumps in the exozodiacal dust, which are expected in planet-hosting systems,, may also be a source of confusion. Here we discuss the problems associated with direct observations of an Earth-like planet in the presence of unknown levels of exozodiacal dust. Basic formulae showing the effect of zodiacal and exozodiacal dust on exoEarth direct imaging will be presented, and performance estimates for some future mission concepts summarized. Current detection limits for debris dust and future prospects for sensitive exozodiacal dust observations will also be discussed. Finally, we highlight a few additional problems relating to exozodiacal dust that have yet to be solved.

Roberge, Aki↗
DOE OSTI2025

Chromium versus Aluminum: Impact of Nickel Alloy Composition and Interfacial Kinetics on High-Temperature Passivating Oxide Formation

High-temperature corrosion resistance depends critically on the formation of a passivating surface oxide, which is highly sensitive to alloy composition and structure. Such details often elude experimental investigation, and simplified analytical models fail to provide a truly chemical view of passivating oxide evolution. Here, we explicitly compare the fundamental chemistry of Cr and Al as prototypical passivating elements in Ni alloys by directly simulating competing reaction and diffusion processes within the oxide film using kinetic Monte Carlo and density functional theory. We find that the origin and expression of passivating behavior during early-stage thermal oxidation are qualitatively different between the two alloy systems. Ni–Cr alloys feature a sudden onset of passivation associated with a sharp phase transition upon Cr enrichment that directly couples oxidation kinetics to phase transformation behavior. In contrast, Ni–Al alloys display more continuous oxide phase variation with Al enrichment, ultimately resulting in a lower composition threshold for passivation and a thinner passivating layer. In addition, we elucidate the nonobvious role of metal exchange within the alloy near the oxide boundary, which fundamentally alters film composition and passivating behavior. Furthermore, our results have key implications for engineering improved corrosion-resistant alloys, both in terms of compositional variation and processing.

Alloys↗
DOE OSTI2019

Requirements and sensitivity analysis for temporally- and spatially-resolved thermometry using neutron resonance spectroscopy

Neutron resonance spectroscopy (NRS) has been used extensively to make temperature measurements that are accurate, absolute, and nonperturbative within the interior of material samples under extreme conditions applied quasistatically. Yet NRS has seldom been used in dynamic experiments. There is a compelling incentive to do so because of the significant shortcomings of alternative techniques. An important barrier to adopting dynamic NRS thermometry is the difficulty in fielding it with conventional spallation neutron sources. To enable time-dependent and spatially resolved temperature measurements in dynamic environments, more compact neutron sources that can be used at user facilities in conjunction with other diagnostic probes (such as x-ray light sources) are required. Such sources may be available using ultrafast high-intensity optical lasers. We evaluate such possibilities by determining the sensitivities of the temperature estimate on neutron-beam and diagnostic parameters. Based on that evaluation, requirements are set on a pulsed neutron-source and diagnostics to make a meaningful dynamic temperature measurement. Dynamic thermometry measurements are examined in this context when driven by two alternative fast-neutron sources: the Los Alamos Neutron Scattering Center (LANSCE) proton accelerator driving isotropic spallation neutrons as a baseline and a laser-plasma ion accelerator driving a neutron beam from deuterium breakup. Strategies to close the gap between the required and demonstrated performance of laser-based fast-neutron sources are presented. A short-pulse high-intensity laser with state-of-the-art pulse contrast and an energy of a few hundred Joules would drive a compact neutron source suitable for NRS thermometry that could transform the dynamic study of materials.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Cryogenic single-molecule fluorescence annotations for electron tomography reveal in situ organization of key proteins in Caulobacter

Superresolution fluorescence microscopy and cryogenic electron tomography (CET) are powerful imaging methods for exploring the subcellular organization of biomolecules. Superresolution fluorescence microscopy based on covalent labeling highlights specific proteins and has sufficient sensitivity to observe single fluorescent molecules, but the reconstructions lack detailed cellular context. CET has molecular-scale resolution but lacks specific and nonperturbative intracellular labeling techniques. Here, we describe an imaging scheme that correlates cryogenic single-molecule fluorescence localizations with CET reconstructions. Our approach achieves single-molecule localizations with an average lateral precision of 9 nm, and a relative registration error between the set of localizations and CET reconstruction of ∼30 nm. We illustrate the workflow by annotating the positions of three proteins in the bacterium Caulobacter crescentus : McpA, PopZ, and SpmX. McpA, which forms a part of the chemoreceptor array, acts as a validation structure by being visible under both imaging modalities. In contrast, PopZ and SpmX cannot be directly identified in CET. While not directly discernable, PopZ fills a region at the cell poles that is devoid of electron-dense ribosomes. We annotate the position of PopZ with single-molecule localizations and confirm its position within the ribosome excluded region. We further use the locations of PopZ to provide context for localizations of SpmX, a low-copy integral membrane protein sequestered by PopZ as part of a signaling pathway that leads to an asymmetric cell division. Our correlative approach reveals that SpmX localizes along one side of the cell pole and its extent closely matches that of the PopZ region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2009

Mid-Infrared Reflectance Imaging of Thermal-Barrier Coatings

An apparatus for mid-infrared reflectance imaging has been developed as means of inspecting for subsurface damage in thermal-barrier coatings (TBCs). The apparatus is designed, more specifically, for imaging the progression of buried delamination cracks in plasma-sprayed yttria-stabilized zirconia coatings on turbine-engine components. Progression of TBC delamination occurs by the formation of buried cracks that grow and then link together to produce eventual TBC spallation. The mid-infrared reflectance imaging system described here makes it possible to see delamination progression that is invisible to the unaided eye, and therefore give sufficiently advanced warning before delamination progression adversely affects engine performance and safety. The apparatus (see figure) includes a commercial mid-infrared camera that contains a liquid-nitrogen-cooled focal plane indium antimonide photodetector array, and imaging is restricted by a narrow bandpass centered at wavelength of 4 microns. This narrow wavelength range centered at 4 microns was chosen because (1) it enables avoidance of interfering absorptions by atmospheric OH and CO2 at 3 and 4.25 microns, respectively; and (2) the coating material exhibits maximum transparency in this wavelength range. Delamination contrast is produced in the midinfrared reflectance images because the introduction of cracks into the TBC creates an internal TBC/air-gap interface with a high diffuse reflectivity of 0.81, resulting in substantially higher reflectance of mid-infrared radiation in regions that contain buried delamination cracks. The camera is positioned a short distance (.12 cm) from the specimen. The mid-infrared illumination is generated by a 50-watt silicon carbide source positioned to the side of the mid-infrared camera, and the illumination is collimated and reflected onto the specimen by a 6.35-cm-diameter off-axis paraboloidal mirror. Because the collected images are of a steady-state reflected intensity (in contrast to the transient thermal response observed in infrared thermography), collection times can be lengthened to whatever extent needed to achieve desired signal-to-noise ratios. Each image is digitized, and the resulting data are processed in several steps to obtain a true mid-infrared reflectance image. The raw image includes thermal radiation emitted by the specimen in addition to the desired reflected radiation. The thermal-radiation contribution is eliminated by subtracting the image obtained with the illumination off from the image obtained with the illumination on. A flat-field correction is then made to remove the effects of non-uniformities in the illumination level and pixel-to-pixel variations in sensitivity. This correction is performed by normalizing to an image of a standard object that has a known reflectance at a wavelength of 4 microns. After correction, each pixel value is proportional to the reflectance (at a wavelength of 4-microns) at the corresponding location on the specimen. Mid-infrared reflectance imaging of specimens that were thermally cyc led for different numbers of cycles was performed and demonstrated t hat mid-infrared reflectance imaging was able to monitor the gradual delamination progression that occurs with continued thermal cycling . Reproducible values were obtained for the reflectance associated w ith an attached and fully delaminated TBC, so that intermediate refle ctance values could be interpreted to successfully predict the numbe r of thermal cycles to failure.

Edlridge, Jeffrey I.↗
DOE OSTI2019

Dependence of interface energetics and kinetics on catalyst loading in a photoelectrochemical system

Solar hydrogen production by the photoelectrochemical method promises a means to store solar energy. While it is generally understood that the process is highly sensitive to the nature of the interface between the semiconductor and the electrolyte, a detailed understanding of this interface is still missing. For instance, few prior studies have established a clear relationship between the interface energetics and the catalyst loading amount. Here we aim to study this relationship on a prototypical Si-based photoelectrochemical system. Two types of interfaces were examined, one with GaN nanowires as a protection layer and one without. It was found that when GaN was present, higher Pt loading (> 0.1 μg/cm 2 ) led to not only better water reduction (and, hence, hydrogen evolution) kinetics but also more favorable interface energetics for greater photovoltages. In the absence of the protection layer, by stark contrast, increased Pt loading exhibited no measurable influence on the interface energetics, and the main difference was observed only in the hydrogen evolution kinetics. Furthermore, the study sheds new light on the importance of interface engineering for further improvement of photoelectrochemical systems, especially concerning the role of catalysts and protection layers.

14 SOLAR ENERGY↗
DOE OSTI2025

A Computational Framework to design 3D stiffness gradient acoustic metamaterials for impedance matching

Acoustic waves play a crucial role in various applications, including medical imaging, non-destructive testing, and sonar systems. One of the significant challenges in these applications is impedance matching, which is essential for minimizing reflections and maximizing the transfer of acoustic energy between different media. Acoustic metamaterials offer a promising solution to this challenge. In addition to impedance control, gradient stiffness can enhance structural efficiency and enable spatial control of wave propagation, making it a valuable feature in acoustic metamaterial design. In this pa- per, we present our developed computational method to design 3D stiffness gradient acoustic metamaterials for impedance matching. The key steps in our approach include generating initial designs using a periodic covariance function to provide unit cells that are both periodic on the boundaries and randomly formed inside the unit cell. Furthermore, we integrated manufacturing constraints into the design process, ensuring that the structures are interconnected for fabrication. We propose two computational optimization algorithms: GenUnit, based on a non-dominated sorting genetic algorithm (NSGA-II), and MLMatch, which leverages differentiable machine learning. The two approaches are not separate contributions but complementary com- ponents of a unified framework. GenUnit requires no training data and directly interfaces with physics-based simulations, making it highly accurate but slower for large-scale exploration. In contrast, MLMatch is data-hungry during training but, once trained, enables near-instantaneous inference and broad design-space coverage. Together, they form a hybrid strategy: ML- Match rapidly explores the global design space, and GenUnit provides local refinement with high-fidelity accuracy. This balance between training cost, inference time, and precision is the motivation for including both methods in the same study. We applied this dual-algorithm framework to generate two metallic-based metamaterial designs that match the acoustic impedance of water while exhibiting a controlled gradient in stiffness (from stiff to soft). The stiffness gradient is particularly advantageous in applications where one side of the structure must interface with soft or sensitive surfaces, such as human tissue or delicate components. Here, this work paves the way for improved materials in various acoustic applications, particularly in ultrasound devices, by providing better impedance.

Metamaterial↗
DOE OSTI2023

Comparing the Effect of Anthropogenically Amplified Halogen Natural Emissions on Tropospheric Ozone Chemistry Between Pre-Industrial and Present-Day

Reactive halogens (X + XO, X = I, Br or Cl) catalytically destroy a fraction of tropospheric ozone under present-day (PD) conditions, however, their distribution and potential impact on tropospheric ozone under pre-industrial (PI) conditions remain largely unexplored. This study uses the Community Atmosphere Model with Chemistry (CAM-Chem) to investigate the effect of anthropogenically amplified natural emissions of halogenated species and their subsequent chemistry on tropospheric ozone under PI and PD atmospheric conditions. Model results show that the global tropospheric ozone depletion due to natural halogens is slightly more sensitive in PI than PD, with percentage changes in tropospheric ozone burden (TOB) of -14.1 ± 0.6% for PI and -12.9 ± 0.6% for PD. Individually, the role of iodine and chlorine in ozone depletion is equivalent in both periods (ΔTOB I : ~-7% and ΔTOB Cl : ~-2.5%), while bromine plays a larger role in PI (ΔTOB Br : -5.5 ± 0.6%) versus PD (ΔTOB Br : -4.3 ± 0.7%). The increase in anthropogenic ozone precursor emissions from PI to PD has amplified the natural emission of inorganic halogens and led to a shift in the partitioning of inorganic halogens from reactive to reservoir species. Consequently, halogen-driven ozone depletion from the surface to the free troposphere is larger in PI than PD. In contrast, in the upper troposphere, the ozone depletion is larger in PD influenced mainly by stratospheric intrusion of reactive halogens from long-lived species. This study highlights the importance of including a complete chemical coupling of natural halogens and atmospheric pollutants in chemistry-climate models to adequately assess their effects on tropospheric ozone in a changing climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Effects of Experimental Warming and Elevated CO 2 on CO 2 and CH 4 Fluxes in an Ombrotrophic Black-Spruce. Final Report

High latitude peatlands and permafrost soils contain nearly half of the soil carbon pool on Earth. The potential for large soil C stocks in peatlands and permafrost to become a positive feedback to climate change by increasing net emissions of CO₂ and CH₄ to the atmosphere is a subject of grave concern. This research was conducted at the Spruce and Peatland Responses Under Changing Environments (herein SPRUCE) experimental facility, located in the USDA’s Marcell Experimental Forest in northern Minnesota. The site is dominated by Picea mariana [herein black spruce], ericaceous shrubs and Sphagnum spp. Ten 12m-diameter open top chambers expose portions of the 8.1-ha S1 bog to warming up to +9°C in 2.25°C increments at ambient and elevated CO₂ (eCO₂, 900ppm). The Finzi lab group began manual measurements of CO₂ and CH₄ fluxes and their C-isotopic compositions in 2014. With funding from the DOE-TES program automated measurements of these species began in 2015. With a one-year no cost extension we were able to make measurements through the 2018 growing season. Across the study period we find that experimental warming of the peatland significantly increases the flux of CO₂ and CH₄ to the atmosphere. The highest temperature treatments had the highest fluxes. As peatlands have complex topography and water table dynamics, many of these results were contingent upon the topographic location in which the measurements were made. In the raised portions of the peatland divorced from the water table, fluxes of CO₂ were high and fluxes of CH₄ were low. By contrast, in the lower portions of the peatland surface, which is at or very near the water table, fluxes of CH₄ were substantially higher. A significant fraction of the total annual CH₄ flux was derived from episodic ebullitive fluxes. The occurrence and size of these ebullitive fluxes also increased with temperature. Experimental fumigation of the black spruce peatland with elevated concentrations of atmospheric CO₂ [herein eCO₂] also had significant effects on emissions of greenhouse gasses. In general these effects were far more subtle than the effects of rising temperature. This indicates that temperature change more than atmospheric chemistry changes are affect the belowground cycle of C in the peatland. Overall, this study shows that boreal peatlands are highly sensitive to changes in temperature. The warmer it becomes the more C will be lost from the peatland to the atmosphere. This appears to create a positive feedback loop that is likely to enhance the concentration of greenhouse gases in the atmosphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

K2 ROTATION PERIODS FOR LOW-MASS HYADS AND THE IMPLICATIONS FOR GYROCHRONOLOGY

As the closest open cluster to the Sun, the Hyades is an important benchmark for many stellar properties, but its members are also scattered widely over the sky. Previous studies of stellar rotation in the Hyades relied on targeted observations of single stars or data from shallower all-sky variability surveys. The re-purposed Kepler mission, K2 , is the first opportunity to measure rotation periods ( P {sub rot}) for many Hyads simultaneously while also being sensitive to fully convective M dwarf members. We analyze K2 data for 65 Hyads and present P {sub rot} values for 48. Thirty-seven of these are new measurements, including the first P {sub rot} measurements for fully convective Hyads. For 9 of the 11 stars with P {sub rot} in the literature and this work, the measurements are consistent; we attribute the two discrepant cases to spot evolution. Nearly all stars with masses ≲0.3 M {sub ⊙} are rapidly rotating, indicating a change in rotation properties at the boundary to full convection. When confirmed and candidate binaries are removed from the mass–period plane, only three rapid rotators with masses ≳0.3 M {sub ⊙} remain. This is in contrast to previous results showing that the single-valued mass–period sequence for ≈600 Myr old stars ends at ≈0.65 M {sub ⊙} when binaries are included. We also find that models of rotational evolution predict faster rotation than is actually observed at ≈600 Myr for stars ≲0.9 M {sub ⊙}. The dearth of single rapid rotators more massive than ≈0.3 M {sub ⊙} indicates that magnetic braking is more efficient than previously thought, and that age–rotation studies must account for multiplicity.

79 ASTRONOMY AND ASTROPHYSICS↗