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At least 163 records · Page 9

Atomically Dispersed Platinum in Surface and Subsurface Sites on MgO Have Contrasting Catalytic Properties for CO Oxidation

Atomically dispersed metals on metal oxide supports are a rapidly growing class of catalysts. Developing an understanding of where and how the metals are bonded to the supports is challenging because support surfaces are heterogeneous, and most reports lack a detailed consideration of these points. In this work, we report two atomically dispersed CO oxidation catalysts having markedly different metal–support interactions: platinum in the first layer of crystalline MgO powder and platinum in the second layer of this support. Structural models have been determined on the basis of data and computations, including those determined by extended X-ray absorption fine structure and X-ray absorption near edge structure spectroscopies, infrared spectroscopy of adsorbed CO, and scanning transmission electron microscopy. The data demonstrate the transformation of surface to subsurface platinum as the temperature of sample calcination increased. Catalyst performance data demonstrate the lower activity but greater stability of the subsurface platinum than of the surface platinum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distributed Thermal Response Multi-Source Modeling to Evaluate Heterogeneous Subsurface Properties

A thorough assessment of thermal properties in heterogeneous subsurface is necessary in design of low-temperature borehole heat exchangers (BHEs). For this study, a distributed thermal response test (DTRT), which combines distributed temperature sensing (DTS) with a conventional thermal response test (TRT), was conducted in a U-bend geothermal loop installed in an open borehole at the University of Illinois at Urbana-Champaign to estimate thermal properties by analyzing the thermal response of different geologic materials while applying a constant heat input rate. Fiber-optic cables in the DTRT were deployed both inside the U-bend geothermal loop and in the center of the borehole to improve the accuracy of calculated heat-loss rates and borehole temperature profile measurements. To assess the subsurface thermal conductivity during the heating phase of the DTRT, a single-source model and a multi-source model, both based on the infinite line source method, were developed using the borehole temperature data and temperatures inside and along the outside of the loop, separately. The two models returned similar thermal conductivity values. The multi-source modeling has the advantage of predicting the thermal conductivity of heterogeneous geologic materials from borehole temperature profiles during the DTRT heating phase. Additionally, based on the distributed thermal conductivity measured in the borehole, estimates were made for both radial thermal impacts and the rate of heat loss in the BHE.

58 GEOSCIENCES↗

Design and Laboratory Validation of a Capacitive Sensor for Measuring the Recession of Thin-Layered Ablator

Flight vehicles are typically instrumented with subsurface thermocouples to estimate heat transfer at the surface using inverse analysis procedures. If the vehicle has an ablating heat shield, however, temperature time histories from subsurface thermocouples no longer provide enough information to estimate heat flux at the surface. In this situation, the geometry changes and thermal energy leaves the surface in the form of ablation products. The ablation rate is required to estimate heat transfer to the surface. A new concept for a capacitive sensor has been developed to measure ablator depth using the ablator's dielectric effect on a capacitor's fringe region. Relying on the capacitor's fringe region enables the gage to be flush mounted in the vehicle's permanent structure and not intrude into the ablative heat shield applied over the gage. This sensor's design allows nonintrusive measurement of the thickness of dielectric materials, in particular, the recession rates of low-temperature ablators applied in thin (0.020 to 0.060 in. (0.05 to 0.15 mm)) layers. Twenty capacitive gages with 13 different sensing element geometries were designed, fabricated, and tested. A two-dimensional finite-element analysis was performed on several candidate geometries. Calibration procedures using ablator-simulating shims are described. A one-to-one correspondence between system output and dielectric material thickness was observed out to a thickness of 0.055 in. (1.4 mm) for a material with a permittivity about three times that of air or vacuum. A novel method of monitoring the change in sensor capacitance was developed. This technical memorandum suggests further improvements in gage design and fabrication techniques.

Gregory K Noffz↗

Solution-Processed Temperature-Adaptive Radiative Paint as a Thermal Imaging Sensitizer

Thermography detects mid-infrared radiation from surfaces based on the Stefan-Boltzmann law, mapping surface temperatures and potentially revealing subsurface thermal activity. Recent developments offer an alternative strategy to traditional camera-based improvements: a thermal imaging sensitizer (TIS) coating whose emissivity increases sharply with local temperature, amplifying small thermal variations into high-contrast signals. Existing TIS structures are nanofabricated solid membranes and face significant challenges in fabrication complexity. Here, in this study, we present a solution-processed, liquid form of TIS, termed temperature-adaptive radiative paint (TARP), to address these limitations. TARP offers drastically reduced fabrication costs, scalability to large areas, applicability to curved surfaces, and an extended operating temperature range, while maintaining the function of temperature amplification. Application of TARP enhances small temperature contrast by more than 3 times, substantially improving ambient thermography and enabling broader applications such as detection of structural defects and hot spots in electronic components.

paint↗

The subsurface structure of abraded Al–Zn–Mg–Cu alloy

Surface abrasion has been shown to introduce heavy shear stress and produce a few hundred nanometers thick altered surface layer (ASL) on Al alloys. Such ASLs exhibit microstructural changes at room temperature and different corrosion resistance than the underlying substrate. Here, we report how sample dimensions and temperature affect the deformed subsurface microstructure evolution on an abraded Al–Zn–Mg–Cu alloy using transmission electron microscopy (TEM) and atom probe tomography. The ASL microstructure evolves differently in the bulk sample than in the thin TEM specimen. In the freshly abraded ASL, the original η'/η precipitates and grain boundaries were deformed toward the abrasion direction. After 7-day natural aging of the freshly abraded bulk sample, well-defined subgrains formed locally in the ASL, and unusual Al 2 Cu (θ) and Mg x Zn y phases precipitated at the subgrain boundaries. However, during natural aging of this TEM specimen taken from the abraded and aged bulk samples, much faster changes occurred, including the continued formation of subgrains and θ particles in the entire ASL, and the diffusion of Zn atoms out of Mg x Zn y particles to form a Zn particle. On the other hand, no obvious microstructural changes occurred in the ASL during 3-month natural aging of the TEM specimen immediately taken from the freshly abraded sample. Finally, this work advances the understanding of how Al alloy microstructures respond during and following any shear deformation, and complex and unexpected effects of sample dimensions on the behavior.

36 MATERIALS SCIENCE↗

Skillful Multi‐Month Predictions of Ecosystem Stressors in the Surface and Subsurface Ocean

Abstract Anthropogenic carbon emissions and associated climate change are driving rapid warming, acidification, and deoxygenation in the ocean, which increasingly stress marine ecosystems. On top of long‐term trends, short term variability of marine stressors can have major implications for marine ecosystems and their management. As such, there is a growing need for predictions of marine ecosystem stressors on monthly, seasonal, and multi‐month timescales. Previous studies have demonstrated the ability to make reliable predictions of the surface ocean physical and biogeochemical state months to years in advance, but few studies have investigated forecast skill of multiple stressors simultaneously or assessed the forecast skill below the surface. Here, we use the Community Earth System Model (CESM) Seasonal to Multiyear Large Ensemble (SMYLE) along with novel observation‐based biogeochemical and physical products to quantify the predictive skill of dissolved inorganic carbon (DIC), dissolved oxygen, and temperature in the surface and subsurface ocean. CESM SMYLE demonstrates high physical and biogeochemical predictive skill multiple months in advance in key oceanic regions and frequently outperforms persistence forecasts. We find up to 10 months of skillful forecasts, with particularly high skill in the Northeast Pacific (Gulf of Alaska and California Current Large Marine Ecosystems) for temperature, surface DIC, and subsurface oxygen. Our findings suggest that dynamical marine ecosystem prediction could support actionable advice for decision making.

Environmental Sciences & Ecology↗

Hydrological and Thermal Dynamics of a Supra‐Permafrost Subterranean Estuary

Subterranean estuaries (STEs), where groundwater interacts with seawater, influence surface and subsurface coastal ecology and biogeochemistry. In Arctic-STEs overlying permafrost, groundwater flow and heat transport determine the fate of organic matter. Yet, direct observations of groundwater flow and heat and solute transport processes in Arctic STEs remain limited. This study characterized groundwater flow paths and fluxes and heat transport within an Arctic-STE along Alaska's Beaufort Sea coast during thawing, summer, and freeze-up. Intertidal seabed temperature-depth profiles collected along a 10-m transect captured the active groundwater flow period, from thaw and flow onset in mid-June to freeze-up in late-September. During this period, aquifer geometry evolved non-uniformly due to spatially varying thaw rates across the STE (mean (m) thaw depths–beach: 0.25 to 0.55–0.6 m on 20 June, 25 July, 1 October; seabed: 0.6–0.9 m from 25 July to 1 October). Groundwater and surface water levels, salinity, and subsurface temperature profiles measured over tidal time scales were interpreted alongside groundwater flow-heat transport numerical simulations. Fresh groundwater discharge was sporadic during thawing (m: 0.32 m 3 /day/m), abundant in summer (m: 0.45 m 3 /day/m), and was largely absent during freeze-up. During freeze-up, groundwater flow was driven exclusively by seawater recirculation via tidal pumping (from thawing to summer to freeze-up: 0.00025–0.15–0.5 m3/day/m) and convection. Heat advection dominated near aquatic interfaces (shaping intertidal ice), and conduction controlled vertical temperature gradients in low-flow and unsaturated sediments. These findings will help predict how prolonged summers will alter Arctic-STE cryo-hydrology and biogeochemistry.

54 ENVIRONMENTAL SCIENCES↗

Tidal frequencies and quasiperiodic subsurface water level variations dominate redox dynamics in a salt marsh system

Salt marshes are hotspots of nutrient processing en route to sensitive coastal environments. Whilst our understanding of these systems has improved over the years, we still have limited knowledge of the spatiotemporal variability of critical biogeochemical drivers within salt marshes. Sea-level rise will continue to force change on salt marsh functioning, highlighting the urgency of filling this knowledge gap. Our study was conducted in a central California estuary experiencing extensive marsh drowning and relative sea-level rise, making it a model system for such an investigation. Here we instrumented three marsh positions subjected to different degrees of tidal inundation (6.7%, 8.9%, and 11.2% of the time for the upper, middle, and lower marsh positions, respectively), providing locations with varied biogeochemical characteristics and hydrological interactions at the site. We continuously monitored redox potential (Eh) at depths of 0.1, 0.3, and 0.5 m, subsurface water levels (WL), and temperature at 0.7 m depth at each marsh position. To understand how drivers of subsurface biogeochemical processes fluctuate across tidal cycles, we used wavelet analyses to explain the interactions between Eh and WL. We found that tidal forcing significantly affects key drivers of biogeochemical processes by imparting controls on Eh variability, likely driving subsurface hydro-biogeochemistry of the salt marsh. Wavelet coherence showed that the Eh-WL relationship is nonlinear, and their lead–lag relationship is variable. We found that precipitation events perturb Eh at depth over timescales of hours, even though WL shows relatively minimal change during events. Furthermore, this work highlights the importance of high frequency in situ measurements, such as Eh, to help explain factors that govern subsurface biogeochemistry and hydrological processes in salt marshes.

54 ENVIRONMENTAL SCIENCES↗

Sub-Diurnal Methane Variations on Mars Driven by Barometric Pumping and Planetary Boundary Layer Evolution

In recent years, the Tunable Laser Spectrometer within the Sample Analysis at Mars (TLS-SAM) instrument on board the Mars Science Laboratory (MSL) Curiosity rover has detected methane variations in the atmosphere at Gale crater. Methane concentrations appear to fluctuate seasonally as well as sub-diurnally, which is difficult to reconcile with an as-yet-unknown transport mechanism delivering the gas from underground to the atmosphere. To potentially explain the fluctuations, we consider barometrically induced transport of methane from an underground source to the surface, modulated by temperature-dependent adsorption. The subsurface fractured-rock seepage model is coupled to a simplified 1-D atmospheric mixing model to provide insights on the pattern of atmospheric methane concentrations in response to transient surface methane emissions, as well as to predict sub-diurnal variation in methane abundance for the northern summer period, which is a candidate time frame for a MSL Curiosity sampling campaign. Our analysis suggests that there is a lower limit to the subsurface fracture density that can produce the observed methane patterns, below which the atmospheric methane variations would be out of phase with the observations. The best-performing model scenarios indicate a significant, short-lived methane pulse just prior to sunrise, the detection of which by TLS-SAM would be a potential indicator of the contribution of barometric pumping to Mars' atmospheric methane variations.

54 ENVIRONMENTAL SCIENCES↗

Temporal variations in regional models of the Sargasso Sea from GEOS-3 altimetry

The paper considers temporal variations in regional models of the Sargasso sea from GEOS-3 telemetry. The methods of regional models and the analysis of overlapping passes are utilized, and short-wave maxima and minima in the regional surface models are examined for correlations with surface and remote sensed infrared temperature data supplemented with subsurface expendable bathythermograph data (XBT). The analysis of overlapping passes provide a better picture of instanteneous sea surface height (SSH) variability through wavelengths greater than 30 km. Correlation studies with cyclonic and anticyclonic ocean eddies from infrared imagery and XBT data indicate satisfactory agreement with equivalent SSH features 98% of the time if the time varying factors are allowed for.

Mather, R. S.↗

Laser/Heterodyne Measurement of Temperature and Salinity

Proposed visible-light laser/heterodyne receiver would remotely measure temperature and salinity of subsurface water. Operation is based on acoustic/optical scattering of light by sound waves. Application of this concept is foreseen in current research on energy conversion from ocean currents produced by thermal gradients and on future marine remote-sensing program.

Jobson, D. J.↗

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗

Drilling, Coring and Sampling Using Piezoelectric Actuated Mechanisms: From the USDC to a Piezo-Rotary-Hammer Drill

NASA exploration missions are increasingly including sampling tasks but with the growth in engineering experience (particularly, Phoenix Scout and MSL) it is now very much recognized that planetary drilling poses many challenges. The difficulties grow significantly with the hardness of sampled material, the depth of drilling and the harshness of the environmental conditions. To address the requirements for samplers that could be operated at the conditions of the various bodies in the solar system, a number of piezoelectric actuated drills and corers were developed by the Advanced Technologies Group of JPL. The basic configuration that was conceived in 1998 is known as the Ultrasonic/Sonic Driller/Corer (USDC), and it operates as a percussive mechanism. This drill requires as low preload as 10N (important for operation at low gravity) allowing to operate with as low-mass device as 400g, use an average power as low as 2- 3W and drill rocks as hard as basalt. A key feature of this drilling mechanism is the use of a free-mass to convert the ultrasonic vibrations generated by piezoelectric stack to sonic impacts on the bit. Using the versatile capabilities f the USDC led to the development of many configurations and device sizes. Significant improvement of the penetration rate was achieved by augmenting the hammering action by rotation and use of a fluted bit to remove cuttings. To reach meters deep in ice a wireline drill was developed called the Ultrasonic/Sonic Gopher and it was demonstrated in 2005 to penetrate about 2-m deep at Antarctica. Jointly with Honeybee Robotics, this mechanism is currently being modified to incorporate rotation and inchworm operation forming Auto-Gopher to reach meters deep in rocks. To take advantage of the ability of piezoelectric actuators to operate over a wide temperatures range, piezoelectric actuated drills were developed and demonstrated to operate at as cold as -200oC and as hot as 500oC. In this paper, the developed mechanisms will be reviewed and discussed including the configurations, capabilities, and challenges.

ultrasonic/Sonic Driller/ Corer (USDC)↗

Mars - Subsurface properties from observed longitudinal variation of the 3.5-mm brightness temperature

Extensive 3.5-mm measurements are reported which show a variation in the brightness temperature of Mars, with the Central Meridian Longitude that is generally in phase with the variation at 2.8 cm and is opposite in sign from the variations at 20 microns. It is pointed out that the phase result is not unexpected, since 3.5 mm is longer than the wavelength at which the phase behavior is expected to change. The result that the 3.5-mm rotation curve amplitude is larger than the amplitudes at both 20 microns and 2.8 cm, however, is unexpected. This result, it is noted, can be explained as a consequence of subsurface scattering from rocks smaller than 1.5 cm in radius. A correlation of subsurface scatterers with the location of the high-thermal inertial regions would be consistent with the hypothesis that rock abundance predominates in determining the thermal inertia.

Epstein, E. E.↗

Corundum Discovered by SuperCam and the Perseverance Rover at Jezero Crater, Mars

Minerals provide clues to the type of geologic environments in which they form. The primary types of minerals that have been identified on Mars indicate a history dominated by volcanism followed by interaction with water. However, other minerals are sometimes found. Here we present results from the SuperCam instrument on the Perseverance rover in which the mineral corundum (α-Al2O3) has been identified using a technique called time-resolved luminescence spectroscopy. Corundum has a unique light-emitting (luminescence) feature based on two well-known peaks as well as the time it takes for this light to fade after being excited by a laser, which is referred to as the lifetime. Corundum forms in specific environments that are enriched in aluminum and depleted in silicon and have been subjected to high temperature and pressure. Such places include deep subsurface magmas or shallower locations that have been exposed to high temperature through tectonic processes or meteorite impacts. Given their small size, association with a mineral called plagioclase, and location on the heavily impacted crater rim, we propose that these corundum minerals formed through impact processes.

58 GEOSCIENCES↗

Planetary observations at a wavelength of 1.32 mm

Observations at a wavelength of 1.32 mm have been made of the Jovian planets, Ceres, the satellites Callisto and Ganymede, and the HII region DR 21. The observed brightness temperatures are presented. Those of the Jovian planets agree with the values expected from model atmosphere calculations, except that of Jupiter, which is lower than expected. Ceres and the satellites do not have atmospheres so their emission arised in their subsurface layers. The observed brightness temperatures are intermediate between those measured at infrared and centimeter wavelengths.

Ulich, B. L.↗

Electrically Conducting, Ca-Rich Brines, Rather Than Water, Expected in the Martian Subsurface

If Mars ever possessed a salty liquid hydrosphere, which later partly evaporated and froze down, then any aqueous fluids left near the surface could have evolved to become dense eutectic brines. Eutectic brines, by definition, are the last to freeze and the first to melt. If CaC12-rich, such brines can remain liquid until temperatures below 220 K, close to the average surface temperature of Mars. In the Martian subsurface, in intimate contact with the Ca-rich basaltic regolith, NaC1-rich early brines should have reacted to become Ca-rich. Fractional crystallization (freezing) and partial melting would also drive brines toward CaC12-rich compositions. In other words, eutectic brine compositions could be present in the shallow subsurface of Mars, for the same reasons that eutectic magma compositions are common on Earth. Don Juan Pond, Antarctica, a CaC12-rich eutectic brine, provides a possible terrestrial analog, particularly because it is fed from a basaltic aquifer. Owing to their relative density and fluid nature, brines in the Martian regolith should eventually become sandwiched between ice above and salts beneath. A thawing brine sandwich provides one explanation (among many) for the young gullies recently attributed to seepage of liquid water on Mars. Whether or not brine seepage explains the gullies phenomenon, dense, CaC12-rich brines are to be expected in the deep subsurface of Mars, although they might be somewhat diluted (temperatures permitting) and of variable salt composition. In any case, they should be good conductors of electricity.

Burt, D. M.↗