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Mixing Pathways in Simple Box Models

Abstract Tracer variance budgets can be used to estimate bulk mixing in a control volume. For example, simple, analytical, bulk formulations of salt mixing, defined here as the destruction of salinity variance, can be found for estuaries with a riverine source of freshwater and a two-layer exchange flow at the mouth using salinity as a representative tracer. For a steady case, the bulk salt mixing M can be calculated as , where S in and S out are the representative salinities in the estuarine exchange flow, and Q R and Q in are the river and landward volume fluxes, respectively. The bulk salt mixing M can be considered as the sum of mixing pathways, where each pathway has a mixing of Q (Δ S ) 2 , where Q is the volume transport and Δ S is the salinity difference across the pathway. For the estuary case, one mixing path is associated with the river inflow, and the other is associated with the inflow of salty, oceanic water. This concept of linking mixing to input–output pathways is extended, in simple box models, from estuaries to scenarios with multiple inputs/outputs, as might be found in a complex estuarine/fjord network, in a region on a continental shelf, or any other control volume with multiple exchanges. This approach allows for the estimation of the relative contributions of each input–output pathway to the total mixing within a control volume.

54 ENVIRONMENTAL SCIENCES↗

High-Quality Factor Microwave Resonators using Rhenium

Coplanar waveguide resonators are a perfect tool to evaluate the losses induced by defects and interfaces in superconducting devices. Even if niobium is the most used superconductor for resonators and qubits, its native oxide at the metal-air (MA) interface limits the device results. Tantalum has recently significantly improved qubit performances due to a thinner and less disordered oxide layer compared to Nb. To further improve the MA interface, we used rhenium, a superconducting material with 1.7 K critical temperature resistant to oxidation: it forms an oxide layer thinner than 1 nm. In this study, we will present a thorough investigation of rhenium CPW resonator measurements with internal quality factors at the single photon level exceeding 2 million. The devices have been fabricated on a sapphire substrate while the processing parameters have been varying and optimized. The measurements have been performed as a function of power and temperature to disentangle different sources of losses, such as two-level systems (TLS) and quasi-particles. A peculiar TLS temperature dependence has been measured and analyzed. In this work, we also vary the participation ratio of the devices to extract the losses introduced by the involved interfaces with higher fidelity and precision. We carried on a deep material characterization effort to link the results to the differences in the fabrication steps, and we will present material characterization measurements performed via AFM, ToF-SIMS, XPS, and TEM.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗

Comparison of Geochemical Reactivity of Marcellus and Caney Shale Based on Effluent Analysis

ABSTRACT: In this comparative study, we analyzed the changes in elemental concentrations of hydraulic fracturing fluids after interaction with the Marcellus and Caney Shale formations. The focus was on assessing the inherent risks and environmental implications associated with flowback waters, including their impact on soil, ground, and drinking water quality, and human health safety. The chemical compositions of effluents were determined through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Mass spectrometry (ICP-MS). The Marcellus Shale, showed concentrations of Cd, averaging 0.380 ppm far exceeding safe water thresholds. Significant levels of As, Se, B, and Pb were detected in both shales, raising concerns about soil and water contamination. Analyzing the effluents from representative samples of sections of the Marcellus (S2 and S7) and Caney (R1 and R2) indicates different geochemical responses over 4 weeks of experiments. This comparison underscores the chemical changes and environmental considerations linked to hydraulic fracturing across shale formations, suggesting the value of tailored monitoring and regulatory measures for each type. 1. INTRODUCTION The Caney and Marcellus shales, differing in geology and geochemistry, represent distinct unconventional reservoirs. The Caney shale, is more ductile, with higher produced water volumes, (Smith et al., 2022) contrasts with the brittle Marcellus shale known for lower brine production but significant data availability. This study aims to elucidate the possible environmental health and safety issues that may arise from the hydraulic fracturing processes. The interaction between fracturing fluids and clays presents a significant challenge. The primary base of these fluids is water, which, when introduced to clay, can induce swelling and constrict flow pathways. This phenomenon is attributed to water molecules infiltrating the layers of clay, particularly in 2:1-type clays, leading to an increased distance between layers. To counteract this, clay stabilizers are employed (Awejori et al., 2021). Despite their effectiveness, these stabilizers are considered temporary solutions. Upon completion of the fracturing process, a concomitant amount of contaminated waters (flow back), with varied content is collected at the surface. From these, we can infer the geochemical reactions and the environmental challenges associated with these waters. Flowback waters can be reinjected or used for other purposes such as irrigation. This requires adequate screening and treatment for safe use.

Dje, L. B.↗

New Estimates of Ice and Oxygen Fluxes Across the Entire Lid of Lake Vostok From Observations of Englacial Radio Wave Attenuation

Over deep Antarctic subglacial lakes, spatially varying ice thickness and the pressure‐dependent melting point of ice result in distinct areas of melting and freeze‐on at the ice‐water interface, that is, at the lake lid. These ice mass fluxes drive lake circulation and, because basal Antarctic ice contains air clathrate, affect the input of oxygen to the lake, with implications for subglacial life. Inferences of rates of melting and freeze‐on, that is, accretion rates, from radar layer tracking and geodesy are limited in spatial coverage and resolution. Here we develop a new method to estimate accretion rate, and the resulting oxygen input at a lake lid, using airborne radar data over Lake Vostok together with ice‐temperature and chemistry data from the Vostok ice core. Because the lake lid is a coherent reflector of known reflectivity (at our radar frequency), we can infer depth‐averaged radio wave attenuation in the ice, with a spatial resolution of ~1 km along flight lines. Spatial variation in attenuation depends mostly on variation in ice temperature near the lid, which in turn varies strongly with ice mass flux at the lid. We model ice temperature versus depth with ice mass flux as a parameter, thus linking that flux to observed depth‐averaged attenuation. The resulting map of melt and accretion rates independently reproduces features known from earlier studies but now covers the entire lid. We find that freeze‐on is dominant when integrated over the lid, with an ice imbalance of 0.05 to 0.07 cu.km/year, which is robust against uncertainties.

Dale P. Winebrenner↗

SuperLab 2.0 Showcase: Connecting Five Labs to Tackle Grid Complexity and Unlock Unique Grid Asset Potential

SuperLab 2.0 (5-Lab Demo) is a collaborative, national-scale experiment showcasing the coordination of geographically distributed energy assets in real time. The demonstration integrates 25 physical and digital assets, spanning wind, PV, batteries, electrolyzers, DC fast chargers, microgrid controllers, building automation systems, small modular reactor (SMR), control centers, and gas turbines, across five DOE national laboratories-NLR, INL, NETL, LBNL, and SNL. These assets are unified using Energy Sciences Network (ESnet), a low-latency, high-performance U.S. Department of Energy's (DOE) network, and controlled via a centralized energy controller hosted at NLR's ARIES facility. The demonstration validates the ability to stress-test hybrid energy systems under dynamic scenarios to de-risk advanced control strategies for greater resilience and flexibility. SuperLab 2.0 (5-Lab Demo) showcased a major advancement in federated national laboratory collaboration, enabling real-time, cross-laboratory experimentation to coordinate geographically dispersed distributed energy resources (DERs) using various communication protocols and networks. SuperLab 2.0 (5-Lab Demo) built on previous demonstrations conducted between NLR-PNNL and NLR-INL connecting diverse assets including distant protection devices, a SMR simulator, and a high temperature electrolyzer (HTE). Previous demos were based on a single connection between two labs with minimal coordination challenges. The 5-Lab demo with a centralized controller, distributed testbeds across different geographical locations, and use of protocols-based communication represents a scenario closer to real-world grid operations that coordinate resources across a region to meet system needs. This experiment studied how local DER controllers interact with a centralized energy controller during normal and abnormal events to maintain reliability. The SuperLab team across the five labs implemented a notional power system model equivalent of transmission and distribution lines, represented by the data networks interconnecting the labs. Each lab continuously exchanged local parameters (such as P and Q) from its Hardware-In-Loop (CHIL) and Power Hardware-In-Loop (PHIL) assets through centralized energy controller at NLR, enabling real-time interaction and coordination across sites. By leveraging ESnet as the communication backbone, the team successfully operated the distributed assets as a unified power system, with each bus represented by a different laboratory. This setup mirrors how assets interact in real-world power systems across dispersed locations with various protocols and latencies. At each lab site, assets were operated using their own local controllers which were coordinated through an overarching operation and control layer of centralized energy controller, equivalent to how an energy management system (EMS) orchestrates assets across a regional or national grid. SuperLab's federated connectivity utilized a Digital Real-Time Simulators (DRTS)-type gateway to connect Controller Hardware-In-Loop (CHIL) and PHIL assets between labs. To enable this federated connection through ESnet, a deterministic network was established where latency variations were consistent. This consistency allowed the development of digital filters for the power system assets across CHIL and PHIL interfaces to avoid unstable and unreliable grid conditions. This report provides an overview of the cross-laboratory configuration and offers insights into interconnecting geographically distributed research assets to test them as if they were co-located. This experiment represents a step toward linking nine DOE national laboratories, enabling nation-wide simulations that can address utility-driven challenges with grid resilience, flexibility, and modernization.

24 POWER TRANSMISSION AND DISTRIBUTION↗

OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) sea spray organic aerosol emissions – implementation in a global climate model and impacts on clouds

Sea spray aerosol is one of the major sources of atmospheric particulate matter globally. It has increasingly been recognized that organic matter derived from ocean biological precursors contributes significantly to the composition of submicron sea spray and may modify sea spray aerosol impacts on clouds and climate. This paper describes the implementation of the OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) parameterization for sea spray organic aerosol emissions in a global Earth system model, the Energy Exascale Earth System Model (E3SM). OCEANFILMS is a physically based model that links sea spray chemistry with ocean biogeochemistry using a Langmuir partitioning approach. We describe the implementation details of OCEANFILMS within E3SM, compare simulated aerosol fields with observations, and investigate impacts on simulated clouds and climate. Four sensitivity cases are tested, in which organic emissions either strictly add to or strictly replace sea salt emissions (in mass and number) and are either fully internally or fully externally mixed with sea salt. The simulation with internally mixed, added organics agrees reasonably well with observed seasonal cycles of organic matter in marine aerosol and has been selected as the default configuration of the E3SM. In this configuration, sea spray organic aerosol contributes an additional source of cloud condensation nuclei, adding up to 30 cm -3 to Southern Ocean boundary-layer cloud condensation nuclei concentrations (supersaturation = 0.1 %). The addition of this new aerosol source strengthens shortwave radiative cooling by clouds by -0.36 W m -2 in the global annual mean and contributes more than -3.5 W m -2 to summertime zonal mean cloud forcing in the Southern Ocean, with maximum zonal mean impacts of about -4 W m -2 around 50–60°S. This is consistent with a previous top-down, satellite-based empirical estimate of the radiative forcing by sea spray organic aerosol over the Southern Ocean. Through its mechanistic approach, OCEANFILMS offers a path towards improved understanding of the feedbacks between ocean biology, sea spray organic matter, and climate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

IRIS Product Recommendations

This report presents the Applied Meteorology Unit's (AMU) evaluation of SIGMET Inc.'s Integrated Radar Information System (IRIS) Product Generator and recommendations for products emphasizing lightning and microburst tools. The IRIS Product Generator processes radar reflectivity data from the Weather Surveillance Radar, model 74C (WSR-74C), located on Patrick Air Force Base. The IRIS System was upgraded from version 6.12 to version 7.05 in late December 1999. A statistical analysis of atmospheric temperature variability over the Cape Canaveral Air Force Station (CCAFS) Weather Station provided guidance for the configuration of radar products that provide information on the mixed-phase (liquid and ice) region of clouds, between 0 C and -20 C. Mixed-phase processes at these temperatures are physically linked to electrification and the genesis of severe weather within convectively generated clouds. Day-to-day variations in the atmospheric temperature profile are of sufficient magnitude to warrant periodic reconfiguration of radar products intended for the interpretation of lightning and microburst potential of convectively generated clouds. The AMU also examined the radar volume-scan strategy to determine the scales of vertical gaps within the altitude range of the 0 C to -20 C isotherms over the Kennedy Space Center (KSC)/CCAFS area. This report present's two objective strategies for designing volume scans and proposes a modified scan strategy that reduces the average vertical gap by 37% as a means for improving radar observations of cloud characteristics in the critical 0 C to -20 C layer. The AMU recommends a total of 18 products, including 11 products that require use of the IRIS programming language and the IRIS User Product Insert feature. Included is a cell trends product and display, modeled after the WSR-88D cell trends display in use by the National Weather Service.

Short, David A.↗

Understanding Operando Water Management in Hydroxide‐Exchange‐Membrane Fuel Cells

The water balance in hydroxide-exchange-membrane fuel cells (HEMFCs) is a key challenge for improved performance and durability, intimately linked with the various interfaces and coupled phenomena. For every 4 electrons produced, 4 water molecules are generated in the anode and 2 consumed in the cathode, while electroosmosis transports water across the HEM from the cathode to the anode. Consequently, a concentration gradient drives water back, from anode to cathode. Ineffective water management could lead to cathode dry-out, limiting reaction rate and causing ionomer degradation, or to anode flooding. To address these concerns, it is critical to measure the water transport operando . Herein, a home-built water-flux station is used to measure total water flux during cell operation with different inlet relative humidities and back pressures. Increasing the HEM thickness fourfold decreases the water flux at high current density, and utilizing microporous layers on both the anode and cathode decreases the water flux from the anode to the cathode. However, the most significant variable in changing the water flux was found by increasing the anode back pressure. Furthermore, humidity cycling significantly changed electrochemical performance without affecting the overall water fluxes. These findings can be translated to other devices utilizing an HEM.

AEMFC↗

The Cretaceous-Tertiary Impact Crater and the Cosmic Projectile that Produced it

Evidence gathered to date from topographic data, geophysical data, well logs, and drill-core samples indicates that the buried Chicxulub basin, the source crater for the approximately 65 Ma Cretaceous-Tertiary (K/T) boundary deposits, is approximately 300 km in diameter. A prominent topographic ridge and a ring of gravity anomalies mark the position of the basin rim at approximately 150 km from the center. Wells in this region recovered thick sequences of impact-generated breccias at 200-300 m below present sea level. Inside the rim, which has been severely modified by erosion following impact, the subsurface basin continues to deepen until near the center it is approximately 1 km deep. The best planetary analog for this crater appears to be the 270 km-diameter Mead basin on Venus. Seismic reflection data indicate that the central zone of downward displacement and excavation (the transient crater is approximately 130 km in diameter, consistent with previous studies of gravity anomaly data). Our analysis of projectile characteristics utilizes this information, coupled with conventional scaling relationships, and geochemical constraints on the mass of extraterrestrial material deposited within the K/T boundary layer. Results indicate that the Chicxulub crater would most likely be formed by a long-period comet composed primarily of nonsilicate materials (ice, hydrocarbons, etc.) and subordinate amounts (less than or equal to 50 percent) primitive chondritic material. This collision would have released the energy equivalent to between 4 x 10(exp 8) and 4 x 10(exp 9) megatons of TNT. Studies of terrestrial impact rates suggest that such an event would have a mean production rate of approximately 1.25 x 10(exp -9) y(exp -1). This rate is considerably lower than that of the major mass extinctions over the last 250 million years (approximately 5 x 10(exp -7) y(exp -1). Consequently, while there is substantial circumstantial evidence establishing the cause-effect link between the Chicxulub basin forming event and the K/T biological extinctions, the results of our analysis do not support models of impact as a common or singular causative agent of mass extinctions on Earth.

Sharpton, Virgil L.↗

Wintertime Formaldehyde: Airborne Observations and Source Apportionment Over the Eastern United States

Formaldehyde (HCHO) is generated from direct urban emission sources and secondary production from the photochemical reactions of urban smog. HCHO is linked to tropospheric ozone formation, and contributes to the photochemical reactions of other components of urban smog. In this study pollution plume intercepts during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign were used to investigate and characterize the formation of HCHO in relation to several anthropogenic tracers. Analysis of aircraft intercepts combined with detailed chemical box modeling downwind of several cities suggest that the most important contribution to observed HCHO was primary emission. A box model analysis of a single plume suggested that secondary sources contribute 21±10% of observed HCHO. Ratios of HCHO/CO observed in the northeast U.S., from Ohio to New York, ranging from 0.2-0.6%, are consistent with direct emissions combined with at most modest photochemical production. Analysis of the nocturnal boundary layer and residual layer from repeated vertical profiling over urban influenced areas indicate a direct HCHO emission flux of 1.3 x 10 14 molecules cm -2 h -1 . In a case study in Atlanta, GA, nighttime HCHO exhibited a ratio to CO (0.6 – 1.8%) and was anti-correlated with O 3 . Observations were consistent with mixing between direct HCHO emissions in urban air masses with those influenced by more rapid HCHO photochemical production. The HCHO/CO emissions ratios determined from the measured data are 2.3 - 15 times greater than the NEI 2017 emissions database. The largest observed HCHO/CO was 1.7 – 1.8%, located near co-generating power stations.

Formaldehyde↗

Review of Recent Results in Global MHD Modeling: ISTP Project Scientist for Theory and Ground-Based Observations

Global MHD (magnetohydrodynamic) simulations have shown a remarkable ability to describe the global dynamics of geospace. The limitations of the physical approximations underlying MHD would seem to limit the effectiveness of these codes, since kinetic and hybrid effects should manifest themselves by cross-scale coupling from microscales to mesoscales to global scales. However three effects appear to allow the codes to operate much more successfully than one would at first believe. They are:(l) the globally self-consistent nature of the codes with very well defined exterior boundary conditions (the solar wind) which allows the proper intercommunication between magnetospheric regions on MHD scales, (2) the control by global dynamics of the boundary layer locations where micro and meso scale processes operate, and (3) the critical role of numerical diffusion and with a sufficiently high resolution grid, the use of an empirical resistivity term, which if set at a level where the major magnetosphere boundaries properly calibrate against their observed locations, appear to well represent the effects of kinetic and hybrid processes on the global dynamics. The effectiveness of the global MHD codes, which have been developed under the ISTP mission, in describing Wind, Polar and Geotail observations, as well as ground-based observations are described. Particular emphasis is placed upon the Polar imaging data which when combined with ground-based data and global MHD-based synthetic aurora and convection patterns provide a powerful tool in understanding the final link in the solar-terrestrial chain: coupling into the atmosphere and ionosphere.

Curtis, Steven↗

Changes in Tropical Clouds and Atmospheric Circulation Associated with Rapid Adjustment Induced by Increased Atmospheric CO2 – A Multiscale Modeling Framework Study

The radiative heating increase due to increased CO2 concentration is the primary source for the rapid adjustment of atmospheric circulation and clouds. In this study, we investigate the rapid adjustment resulting from doubling of CO2 and its physical mechanism using a multiscale modeling framework (MMF). The MMF includes an advanced higher-order turbulence closure in its cloud-resolving model component and simulates realistic shallow and deep cloud climatology and boundary layer turbulence. The rapid adjustment over the tropics is characterized by 1) reduced ascent and descent strengths over the ocean, 2) increased lower tropospheric stability (LTS) over the subsidence region, 3) shoaling of planetary boundary layers over the ocean, 4) increased deep convection over lands and shift of cloud coverage from the ocean to lands, and 5) reduced sensible (SH) and latent heat (LH) fluxes over the oceanic deep convective regions. Unlike conventional general circulation models and another MMF, a reduction in the global-mean shortwave cloud radiative cooling is not simulated, due to the increase in low clouds at lower altitudes over the ocean, resulting from reduced cloud-top entrainment due to strengthened inversion. Changes in regional circulation play a key role in cloud changes and shift of cloud coverage to lands. Weaker energy transport resulting from water vapor and cloud CO2 masking effects reduces the upward motion and convective clouds in the oceanic regions. The ocean-land transports are linked to the partitioning of surface SH and LH fluxes that increases humidity over lands and enhances deep convection over the tropical lands.

Xu, Kuan-Man↗

Linking Remotely Sensed Aerosol Types to Their Chemical Composition

Aerosol types measured during the Ship-Aircraft Bio-Optical Research (SABOR) experiment are related to GEOS-Chem model chemical composition. The application for this procedure to link model chemical components to aerosol type is desirable for understanding aerosol evolution over time. The Mahalanobis distance (DM) statistic is used to cluster model groupings of five chemical components (organic carbon, black carbon, sea salt, dust and sulfate) in a way analogous to the methods used by Burton et al. [2012] and Russell et al. [2014]. First, model-to-measurement evaluation is performed by collocating vertically resolved aerosol extinction from SABOR High Spectral Resolution LiDAR (HSRL) to the GEOS-Chem nested high-resolution data. Comparisons of modeled-to-measured aerosol extinction are shown to be within 35% +/- 14%. Second, the model chemical components are calculation into five variables to calculate the DM and cluster means and covariances for each HSRL-retrieved aerosol type. The layer variables from the model are aerosol optical depth (AOD) ratios of (i) sea salt and (ii) dust to total AOD, mass ratios of (iii) total carbon (i.e. sum of organic and black carbon) to the sum of total carbon and sulfate (iv) organic carbon to black carbon, and (v) the natural log of the aerosol-to-molecular extinction ratio. Third, the layer variables and at most five out of twenty SABOR flights are used to form the pre-specified clusters for calculating DM and to assign an aerosol type. After determining the pre-specified clusters, model aerosol types are produced for the entire vertically resolved GEOS-Chem nested domain over the United States and the model chemical component distributions relating to each type are recorded. Resulting aerosol types are Dust/Dusty Mix, Maritime, Smoke, Urban and Fresh Smoke (separated into 'dark' and 'light' by a threshold of the organic to black carbon ratio). Model-calculated DM not belonging to a specific type (i.e. not meeting a threshold probability) is termed an outlier and those DM values that can belong to multiple types (i.e. showing weak probability of belonging to a specific cluster) are termed as Overlap. MODIS active fires are overlaid on the model domain to qualitatively evaluate the model-predicted Smoke aerosol types.

Aerosol Types↗

Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO 4 and Th–ReO 4 Frameworks and Solutions

Technetium-99, a β-emitter produced from 235 U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO 4 – ) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An–TcO 4 – bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO 4 – , nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO 4 – /Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Furthermore, nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO 4 – , the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO 4 – . Density functional theory calculations on ReO 4 – /TcO 4 – isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th–TcO 4 – persists in solution, while Th–ReO 4 – bonding is less apparent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thiol post-translational modifications modulate allosteric regulation of the OpcA–G6PDH complex through conformational gate control

In cyanobacteria, the redox-sensitive protein OpcA acts as a metabolic switch for G6PDH, enabling rapid adjustment of reducing power generation from glycogen catabolism and thereby precisely regulating carbon flux between anabolic and catabolic pathways. Although redox-sensitive cysteines in OpcA are known to regulate G6PDH, the mechanisms by which redox post-translational modifications (PTMs) on OpcA control G6PDH structure and activity remain unclear. Here, we combine computational modeling with experimental redox proteomics in Synechococcus elongatus PCC 7942 to dissect this mechanism. Experimentally, redox proteome analysis revealed differential redox PTM patterns, particularly on cysteines within the G6PDH-binding site of OpcA. These environmentally sensitive PTM changes at the interface suggest that thiol modifications in this region form a key regulatory node. More broadly, redox proteomics identified site-specific cysteine modifications under light/dark transitions and circadian cycling, linking distinct redox regimes to discrete PTM states. We employed PTM-Psi simulations to show that thiol PTMs near the OpcA–G6PDH interface are critical for allosteric regulation of G6PDH. The thiol PTMs on OpcA affect a putative gate region in G6PDH for substrate ingress and product egress as well as key hydrogen-bond networks within the active site. We infer that PTMs on OpcA tune the conformational landscapes of individual G6PDH subunits toward functionally relevant configurations according to environmental gradients, biasing the enzyme toward catalytically favorable states. Together, our results reveal a molecular mechanism in which thiol PTMs on OpcA modulate G6PDH structure and function through PTM-induced reorganization of conformational dynamics and allosteric communication. These findings demonstrate that PTM-level regulation provides a critical control layer from genotypes to phenotypes that enables cyanobacteria to rapidly adapt to environmental fluctuations through precise metabolic fine-tuning.

Allosteric regulation↗

Understanding the Space Weathering of Mercury Through Laboratory Experiments

Introduction: Airless surfaces across the solar system are continually modified by energetic particles from solar wind and micrometeoroid bombardment [1,2]. This process is known as space weathering, and it alters the chemical, microstructural, and optical properties of surface regoliths on airless bodies, including Mercury. On the Moon and S-type asteroids, the reflectance spectral signatures of space weathering include reddening (increasing reflectance with increasing wavelength), darkening (lowering of reflectance), and the attenuation of characteristic absorption bands [2]. Such spectral changes are driven by the production of Fe-bearing nanoparticles(npFe) through both solar wind irradiation and micrometeoroid bombardment. While our understanding of space weathering for the Moon and near-Earth S-types asteroids is advanced, insight into how these processes operate on other planetary bodies is limited. In particular, Mercury experiences a uniquely intense space weathering environment than planetary counterparts at 1 AU, including a moreintense solar wind flux and higher velocity micrometeoroid impacts [4]. Additionally, Mercury has a surface composition unique in the inner solar system, including regions of the surface with very low albedo known as the low reflectance material (LRM), which is enriched in carbon, likely graphite, up to 4wt.% [5].In addition, the concentration of Fe across Mercury’s surface islow (<2 wt.%) compared to the Moonor S-type asteroids asteroids[6]. Our understanding of the effects of space weathering on C-rich and Fe-poor phases is limited. Since Fe plays a critical role inthe development of space weathering characteristicson other airless surfaces(e.g., npFe), its limited availability may significantly affect the development of space weathering features in Mercury surface materials. We can simulate space weathering processes in the laboratory to explore their effects on the microstructural, chemical, and spectral characteristics of Mercury surface materials[7]. Here we used pulsed laser irradiation to simulate the short duration, high-temperature events associated with micrometeoroid impacts. We performed coordinated analyses including reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these mercurian analog samples. Methods: For these experiments, we usedforsteritic olivine with varying FeOcontents, a mineral phase proposed to be abundant on the surface of Mercury. We mixed each sample with graphite to simulate LRM regions of the surface. Wesynthesized the olivinesamplesat 1-bar at NASA’s Johnson Space Centerand prepared pressed powder pellets for laser irradiation [8].We prepared three samples, each with a base layer of olivineto maintain structural integrity and topped witha surface layer containing the graphite-olivine mixture: 1) Sample SC-001 San Carlos olivine(Fo90.91),2)Sample F-S-002 with0.05 wt.% FeO olivine, and 3) F-T-004 with 0.53 wt.% FeO olivine. Each sample was mixed with 5 wt.% powdered graphite and had grain sizes ranging from 45to 125μm. We irradiated each sample usinga pulsed Nd-YAG laser, (l=1064 nm, ~6 ns pulse duration, energy of 48 mJ/pulse) while undervacuumat Northern Arizona University. The laser was rastered1x and then 5x over the surfaceof each sample to simulate progressive space weathering. We collected in situreflectance spectra from the samples after each laser pulse witha Nicolet IS50 Fourier-Transform Infrared spectrometer (lfrom 0.65-2.5 μm). We used an FEI Nova NanoSEM200scanning electron microscope (SEM) and a Hitachi TM4000 Plus benchtop SEM at Purdue University to image the surface morphology and topography of the samples. We extracted thin sections for analysis in the transmission electron microscope(TEM)using the FEI Helios NanoLab 660 focused ion beam (FIB) SEM at the University of Arizona.We performed analysis of the microstructural and chemical characteristics of the samples using the 200 keV JEOL 2500 scanning TEM at Johnson Space Center. Reflectance Spectroscopy Results:Reflectance spectra for each sample are shown in Fig. 1.SC-001:The spectrum of the unirradiated sample exhibits a weak 1.0 μm absorption feature, associated with Fe2+in the olivine,and low overall reflectance (Fig. 1a). Thereflectance and the depth of the absorption band increases after 1x laser raster but are at their lowest after 5x laser rasters.F-T-004:The unirradiated sample has a blue-sloped spectrum with low reflectance without identifiable absorption features (Fig. 1b). With progressive laser irradiation, the sample reflectance increases and becomes strongly red-sloped.F-S-002:The unirradiated sample exhibits a dark, blue-slopedspectrum. The brightness of the sample increases significantly from <0.2average reflectance over >0.8 reflectance in the most irradiated sampleand thespectral slope also becomesslightly reddened (Fig. 1c). Microstructural and Chemical Analysis: Two primary alteration textures were observed in the samples exposed to simulated space weathering: 1) fluffy C-rich,and 2) vesiculated melt. The fluffy C-rich texture is composed oflow-densitydeposits distributed across the surface of the sample(Fig. 2A). Analysis of a FIB section extracted from a low-density C-rich region in sample SC-001 reveals multiple globule-type deposits, discrete from stacked graphite, likely produced via melting from the laser irradiation [9].The vesiculated melt textureis smooth and uniformly distributed across isolated regions of the sample surface. The vesicles measure up to 100s of nmin diameter. Analysis of a FIB section from this texture was extracted from sample F-T-004 reveals a layer of amorphous melt material, close to 100 nm thick and uniform across the FIB section (Fig. 2B). Isolated regions of this melt layer contain small nanoparticles, <5 nm in diameter. Chemical analysis through energy dispersive X-ray spectroscopy reveals the composition of this layer is enriched in Si and depleted in Mg and O compared to the underlying sample. Implications for Space Weathering on Mercury: Previous experiments simulating space weathering of Mercury have showndarkening and reddening of spectra[7,10].However, our use of low-Fe materials and graphite to create a sample set more analogous to the mercurian surface. Our results indicate that sample composition plays a significant and important role in the space weathering of Mercury. In particular, our spectral data demonstrates a strong correlation between spectral slope, Fe content, and simulated space weathering. While the variation in FeO content between samples F-S-002 and F-T-004 is <0.6 wt.%, the spectra deviate from flat to strongly red-sloped(F-T-004). This reddeningmay be linked to the presence of very small nanoparticles observed in the melt textures extracted from sample F-T-004. For the SC-001 sample, the fluffy C-rich textures may be developed by the amalgamation of small graphite particles into these unique morphologies. Such observations indicate that space weathering on Mercury may result in both familiar and new microstructural and chemical characteristics. References: [1]Hapke B. (2001) J. Geophys. Res.-Planet.,106,10039–10073. [2]Pieters C.M. and Noble S.K. (2016) J. Geophys. Res-Planet., 121, 1865–1884. [3] Lucey P.G., and Riner, M.A. (2011) Icarus,212, 451-462.[4]CintalaM.J.(1992)J. Geophys. Res.-Planet.,97,947–973.[5]Klima R.L.et al.(2018)Geophys.Res.Letters, 45, 2945–2953. [6]Nittler L.R., et al. (2011) Science 333, 1847-1850.[7]Sasaki S. and Kurahashi E. (2004) Space weathering on Mercury, Adv.Space Res., 33, 2152-2155.[8] Vander KaadenK.E., et al. (2018) LPSCXLIX, Abstract 1230. [9] McGlaun M.L. et al. (2019) LPSCL, Abstract 2019. [10] TrangD.et al. (2018)LPSCXLIX,Abstract2083

M S Thompson↗

Combustion of solid fuel slabs with gaseous oxygen in a hybrid motor analog

Using a high-pressure, two-dimensional hybrid motor, an experimental investigation was conducted on fundamental processes involved in hybrid rocket combustion. HTPB (Hydroxyl-terminated- Polybutadiene) fuel cross linked with diisocyanate was burned with GOX under various operating conditions. Large amplitude pressure oscillations were encountered in earlier test runs. After identifying the source of instability and decoupling the GOX feed line system and combustion chamber, the pressure oscillations were drastically reduced from +/- 20% of the localized mean pressure to an acceptable range of +/- 1.5%. Embedded fine-wire thermocouples indicated that the surface temperature of the burning fuel was around 1000 K depending upon axial locations and operating conditions. Also, except near the leading-edge region, the subsurface thermal wave profiles in the upstream locations arc thicker than those in the downstream locations since the solid-fuel regression rate, in general, increases with distance along the fuel slab. The recovered solid fuel slabs in the laminar portion of the boundary layer exhibited smooth surfaces, indicating the existence of a liquid melt layer on the burning fuel surface in the upstream region. After the transition section, which displayed distinct transverse striations, the surface roughness pattern became quite random and very pronounced in the downstream turbulent boundary-layer region. Both real time X-ray radiography and ultrasonic pulse-echo techniques were used to determine the instantaneous web thicknesses and instantaneous solid-fuel regression rates over certain portions of the fuel slabs. Globally averaged and axially dependent but time-averaged regression rates were also obtained and presented. Several tests were conducted using, simultaneously, one translucent fuel slab and one fuel slab processed with carbon black powder. The addition of carbon black did not affect the measured regression rates or surface temperatures in comparison to the translucent fuel slabs.

Chiaverini, Martin J.↗