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At least 1,009 records · Page 56

Integrated Quantum-Classical Protocol for the Realistic Description of Solvated Multinuclear Mixed-Valence Transition-Metal Complexes and Their Solvatochromic Properties

Linear cyanide-bridged polymetallic complexes, which undergo photoinduced metal-to-metal charge transfer, represent prototypical systems for studying long-range electron-transfer reactions and understanding the role played by specific solute–solvent interactions in modulating the excited-state dynamics. Here, to tackle this problem, while achieving a statistically meaningful description of the solvent and of its relaxation, one needs a computational approach capable of handling large polynuclear transition-metal complexes, both in their ground and excited states, as well as the ability to follow their dynamics in several environments up to nanosecond time scales. Here, we present a mixed quantum classical approach, which combines large-scale molecular dynamics (MD) simulations based on an accurate quantum mechanically derived force field (QMD-FF) and self-consistent QMD polarized point charges, with IR and UV–vis spectral calculations to model the solvation dynamics and optical properties of a cyano-bridged trinuclear mixed-valence compound (trans-[(NC) 5 Fe III (μ-CN)Ru II (pyridine) 4 (μ-NC)Fe III (CN) 5 ] 4– ). We demonstrate the reliability of the QMD-FF/MD approach in sampling the solute conformational space and capturing the local solute–solvent interactions by comparing the results with higher-level quantum mechanics/molecular mechanics (QM/MM) MD reference data. The IR spectra calculated along the classical MD trajectories in different solvents correctly predict the red shift of the CN stretching band in the aprotic medium (acetonitrile) and the subtle differences measured in water and methanol, respectively. By explicitly including the solvent molecules around the cyanide ligands and calculating the thermal averaged absorption spectra using time-dependent density functional theory calculations within the Tamm–Dancoff approximation, the experimental solvatochromic shift is quantitatively reproduced going from water to methanol, while it is overestimated for acetonitrile. This discrepancy can likely be traced back to the lack of important dispersion interactions between the solvent cyano groups and the pyridine substituents in our micro solvation model. The proposed protocol is applied to the ground state in water, methanol, and acetonitrile and can be flexibly generalized to study excited-state nonequilibrium solvation dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Drought-induced changes in groundwater-surface water exchange at Lake Mead area

This study focuses on the Lake Mead region in the southwestern United States, a key water reservoir serving over 25 million people and agricultural lands across several states. The area has experienced recurring anthropogenic droughts since the early 2000s. We investigate the hydrological response of the coupled surface-groundwater system to the 2020–2022 drought, one of the most severe on record. To this end, we use Sentinel-1 Interferometric Synthetic Aperture Radar (InSAR) data to quantify vertical land motion caused by the elastic response of the crust to water-mass loss in the lake vicinity. Next, we apply an inverse elastic load modeling framework to quantify water loss. We further assess possible hydraulic connectivity between Lake Mead and adjacent groundwater reservoirs. We detect ground uplift of up to 8 mm/yr near the lake center, likely due to crustal rebound from reduced water-mass loading. We estimated the total water storage loss at 3.03 ± 0.25 km 3 /yr across a 3150 km 2 area surrounding Lake Mead. Groundwater accounts for approximately a third of that, being 0.94 ± 0.32 km 3 /yr. In addition, observed time lags of 6–98 days between lake and groundwater level responses, corresponding to a lateral diffusivity of 3.2–86 m 2 /s, suggest spatially variable connectivity between the lake and aquifers. These findings highlight that drought impacts propagate through the subsurface within interconnected systems, resulting in reduced buffering capacity of groundwater resources following droughts, and emphasizing the need for more integrated surface and groundwater management strategies to enhance resilience under climate and anthropogenic stressors.

58 GEOSCIENCES↗

Cloud area determination from AVIRIS data using water vapor channels near 1 micron

Fractional cloud area is derived from spectral images collected by the Airborne Visible-IR Imaging Spectrometer (AVIRIS). The derivation is made by ratioing radiances near the 0.94- and the 1.14-microns water vapor band centers against those in the intermediate atmospheric window regions. The derivation makes use of the facts that (1) the reflectances of most ground targets vary approximately linearly with wavelength in the 0.94- and the 1.14-micron water vapor band absorption regions, and (2) the peak absorptions of the water vapor band over cloudy areas are smaller than those over nearby clear surface areas because of the rapidly decreasing atmospheric water vapor concentration with height. The band ratioing technique effectively discriminates among clouds and surface areas having similar reflectance values.

Gao, Bo-Gai↗

Validation of standardized data formats and tools for ground-level particle-based gamma-ray observatories

Context. Ground-based γ-ray astronomy is still a rather young field of research, with strong historical connections to particle physics. This is why most observations are conducted by experiments with proprietary data and analysis software, as is usual in the particle physics field. However, in recent years, this paradigm has been slowly shifting toward the development and use of open-source data formats and tools, driven by upcoming observatories such as the Cherenkov Telescope Array (CTA). In this context, a community-driven, shared data format (the gamma-astro-data-format, or GADF) and analysis tools such as Gammapy and ctools have been developed. So far, these efforts have been led by the Imaging Atmospheric Cherenkov Telescope community, leaving out other types of ground-based γ-ray instruments. Aims. We aim to show that the data from ground particle arrays, such as the High-Altitude Water Cherenkov (HAWC) observatory, are also compatible with the GADF and can thus be fully analyzed using the related tools, in this case, Gammapy. Methods. We reproduced several published HAWC results using Gammapy and data products compliant with GADF standard. We also illustrate the capabilities of the shared format and tools by producing a joint fit of the Crab spectrum including data from six different γ-ray experiments. Results. We find excellent agreement with the reference results, a powerful confirmation of both the published results and the tools involved. Conclusions. The data from particle detector arrays such as the HAWC observatory can be adapted to the GADF and thus analyzed with Gammapy. A common data format and shared analysis tools allow multi-instrument joint analysis and effective data sharing. To emphasize this, a sample of Crab nebula event lists is made public with this paper. Because of the complementary nature of pointing and wide-field instruments, this synergy will be distinctly beneficial for the joint scientific exploitation of future observatories such as the Southern Wide-field Gamma-ray Observatory and CTA.

79 ASTRONOMY AND ASTROPHYSICS↗

Remote sensing of Mississippi River characteristics

A data collection program initiated by the Vicksburg District, to develop a workable knowledge of the principles relating to the transport of water and sediment to gain a better understanding of the Mississippi River characteristics is introduced. Aerial photographs and thermal infrared imagery were collected over two test reaches at low and high water stages. Qualitative interpretation of the data relates to the river characteristics such as flow patterns, relative velocities, sediment concentration distribution, water-depth effects, and effects of man made structures. Ground truth information is correlated with the remotely sensed data.

Ruff, J. F.↗

Prototype active scanner for nighttime oil spill mapping and classification

A prototype, active, aerial scanner system was constructed for nighttime water pollution detection and nighttime multispectral imaging of the ground. An arc lamp was used to produce the transmitted light and four detector channels provided a multispectral measurement capability. The feasibility of the design concept was demonstrated by laboratory and flight tests of the prototype system.

Sandness, G. A.↗

Classification of simulated and actual NOAA-6 AVHRR data for hydrologic land-surface feature definition

An examination of the possibilities of using Landsat data to simulate NOAA-6 Advanced Very High Resolution Radiometer (AVHRR) data on two channels, as well as using actual NOAA-6 imagery, for large-scale hydrological studies is presented. A running average was obtained of 18 consecutive pixels of 1 km resolution taken by the Landsat scanners were scaled up to 8-bit data and investigated for different gray levels. AVHRR data comprising five channels of 10-bit, band-interleaved information covering 10 deg latitude were analyzed and a suitable pixel grid was chosen for comparison with the Landsat data in a supervised classification format, an unsupervised mode, and with ground truth. Landcover delineation was explored by removing snow, water, and cloud features from the cluster analysis, and resulted in less than 10% difference. Low resolution large-scale data was determined useful for characterizing some landcover features if weekly and/or monthly updates are maintained.

Ormsby, J. P.↗

Planetary atmospheres

Observations and theoretical models of planetary atmospheres published during the period 1983-1986 are reviewed, including Vega and Voyager data and results from ground-based remote sensing. Consideration is given to water-vapor and sulfur-compound distributions, electrical phenomena, and dynamics in the Venus atmosphere; dust storms, water cycles, and water and ice erosion on Mars; the compositions, temperature profiles, and dynamics of the Jovian and Saturnian atmospheres; chemical processes and zonal winds on Titan; and the radiation budgets and chemical compositions of the outer planets.

Leovy, Conway↗

Regelation and ice segregation

Macroscopic processes can have an important effect on the state of regolith water. The two primary mechanisms responsible for the formation of segregated ice on Earth, thermally induced regelation and hydraulic fracturing, are reviewed while their potential importance on Mars is examined. While regelation is the dominant terrestrial process, it requires a warmer and wetter environment than currently exists on Mars. In this respect, the conditions required for hydraulic fracturing are less demanding. In assessing its potential importance on Mars, it is noted that hydraulic fracturing can produce a localized zone of high pressure water that could readily disrupt an overburden of frozen ground. Such a process, it is concluded, may have triggered the release of groundwater that led to the formation of the major outflow channels.

Miller, Robert D.↗

Life support and internal thermal control system design for the Space Station Freedom

A Review of the Space Station Freedom Environmental Control and Life Support System (ECLSS) as well as the Internal Thermal Control System (ITCS) design, including recent changes resulting from an activity to restructure the program, is provided. The development state of the original Space Station Freedom ECLSS through the restructured configuration is considered and the selection of regenerative subsystems for oxygen and water reclamation is addressed. A survey of the present ground development and verification program is given.

Humphries, R.↗

Potential health risks from postulated accidents involving the Pu-238 RTG on the Ulysses solar exploration mission

Potential radiation impacts from launch of the Ulysses solar exploration experiment were evaluated using eight postulated accident scenarios. Lifetime individual dose estimates rarely exceeded 1 mrem. Most of the potential health effects would come from inhalation exposures immediately after an accident, rather than from ingestion of contaminated food or water, or from inhalation of resuspended plutonium from contaminated ground. For local Florida accidents (that is, during the first minute after launch), an average source term accident was estimated to cause a total added cancer risk of up to 0.2 deaths. For accidents at later time after launch, a worldwide cancer risk of up to three cases was calculated (with a four in a million probability). Upper bound estimates were calculated to be about 10 times higher.

Goldman, Marvin↗

Factors controlling dimethylsulfide emission from salt marshes

The factors that control the emission of methylated gases from salt marshes are being studied. Research focusses on dimethylsulfide (DMS) formation and the mechanism of DMS and CH4 emission to the atmosphere. The approach is to consider the plants as valves regulating the emission of methylated gases to the atmosphere with the goal of developing appropriate methods for emission measurement. In the case of CH4, the sediment is the source and transport to the atmosphere occurs primarily through the internal gas spaces in the plants. The source of DMS appears to be dimethyl sulfoniopropionate (DMSP) which may play a role in osmoregulation in plant tissues. Concentrations of DMSP in leaves are typically several-fold higher than in roots and rhizomes. Even so, the large below ground biomass of this plant means that 2/3 of the DMSP in the ecosystem is below ground on the aerial basis. Upon introduction to sediment water, DMSP rapidly decomposes to DMS and acrylic acid. The solubility of a gas (its equilibrium vapor pressure) is a fundamental aspect of gas exchange kinetics. The first comprehensive study was conducted of DMS solubility in freshwater and seawater. Data suggest that the Setchenow relation holds for H at intermediate salinities collected. These data support the concept that the concentration of DMS in the atmosphere is far from equilibrium with seawater.

Dacey, John W. H.↗

Microwave backscattering and emission model for grass canopies

Microwave radar and radiometer measurements of grasslands indicate a substantial reduction in sensor sensitivity to soil moisture in the presence of a thatch layer. When this layer is wet it masks changes in the underlying soil, making the canopy appear warm in the case of passive sensors (radiometer) and decreasing backscatter in the active case (scatterometer). A model for a grass canopy with thatch will be presented in this paper to explain this behavior and to compare with observations. The canopy model consists of three layers: grass, thatch, and the underlying soil. The grass blades are modeled by elongated elliptical discs and the thatch is modeled as a collection of disk shaped water droplets (i.e., the dry matter is neglected). The ground is homogeneous and flat. The distorted Born approximation is used to compute the radar cross section of this three layer canopy and the emissivity is computed from the radar cross section using the Peake formulation for the passive problem. Results are computed at L-band (1.4 GHz) and C-band (4.75 GHz) using canopy parameters (i.e., plant geometry, soil moisture, plant moisture, etc.) representative of Konza Prairie grasslands. The results are compared to C-band scatterometer measurements and L-band radiometer measurements at these grasslands.

TRT-THEORETICAL↗

Aqueous Cleaning and Validation for Space Shuttle Propulsion Hardware at the White Sands Test Facility

The NASA White Sands Test Facility (WSTF) has developed an entirely aqueous final cleaning and verification process to replace the current chlorofluorocarbon (CFC) 113 based process. This process has been accepted for final cleaning and cleanliness verification of WSTF ground support equipment. The aqueous process relies on ultrapure water at 50 C (323 K) and ultrasonic agitation for removal of organic compounds and particulate. The cleanliness is verified bv determining the total organic carbon (TOC) content and filtration with particulate counting. The effectiveness of the aqueous methods for detecting hydrocarbon contamination and particulate was compared to the accepted CFC 113 sampling procedures. Testing with known contaminants, such as hydraulic fluid and cutting and lubricating oils, to establish a correlation between aqueous TOC and CFC 113 nonvolatile residue (NVR) was performed. Particulate sampling on cleaned batches of hardware that were randomly separated and sampled by the two methods was performed. This paper presents the approach and results, and discusses the issues in establishing the equivalence of aqueous sampling to CFC 113 sampling, while describing the approach for implementing aqueous techniques on Space Shuttle Propulsion hardware.

Hornung, Steven D.↗

Generation of Level 3 SMMR and SSM/I Brightness Temperatures for the Period 1978-1999

The NOAA/NASA Pathfinder Program was initially designed to assure that certain key remote sensing data sets of particular significance to global change research were scientifically validated, consistently processed and made readily available to the research community at minimal cost. Through this Program the National Snow and Ice Data Center (NSIDC), University of Colorado has successfully processed, archived and distributed the Scanning Multichannel Microwave Radiometer (SMMR) and Special Sensor Microwave/Imager (SSM/I) Level 3 (EASE-Grid format) Pathfinder data sets for the period 1978 to 1999. These data are routinely distributed to approximately 150 researchers through various media including CD-ROM, 8 mm tape, ftp and the EOS Information Management System (IMS). At NSIDC these data are currently being applied in the development and validation of algorithms to derive snow water equivalent (NASA NAG5-6636), the mapping of frozen ground and the detection of the onset of melt over ice sheets, sea ice and snow cover. The EASE-Grid format, developed at NSIDC in conjunction with the SMMR-SSM/I Pathfinder project has also been applied to Advanced Very High Resolution Radiometer (AVHRR) and TOVS Pathfinder data, as well as ancillary data such as digital elevation, land cover classification and several in situ data sets. EASE-Grid will also be used for all land products derived from the NASA EOS AMSR-E instrument.

Partington, Kim↗

Elevation Change of the Southern Greenland Ice Sheet from Satellite Radar Altimeter Data

Long-term changes in the thickness of the polar ice sheets are important indicators of climate change. Understanding the contributions to the global water mass balance from the accumulation or ablation of grounded ice in Greenland and Antarctica is considered crucial for determining the source of the about 2 mm/yr sea-level rise in the last century. Though the Antarctic ice sheet is much larger than its northern counterpart, the Greenland ice sheet is more likely to undergo dramatic changes in response to a warming trend. This can be attributed to the warmer Greenland climate, as well as a potential for amplification of a global warming trend in the polar regions of the Northern Hemisphere. In collaboration with Drs. Curt Davis and Craig Kluever of the University of Missouri, we are using data from satellite radar altimeters to measure changes in the elevation of the Southern Greenland ice sheet from 1978 to the present. Difficulties with systematic altimeter measurement errors, particularly in intersatellite comparisons, beset earlier studies of the Greenland ice sheet thickness. We use altimeter data collected contemporaneously over the global ocean to establish a reference for correcting ice-sheet data. In addition, the waveform data from the ice-sheet radar returns are reprocessed to better determine the range from the satellite to the ice surface. At JPL, we are focusing our efforts principally on the reduction of orbit errors and range biases in the measurement systems on the various altimeter missions. Our approach emphasizes global characterization and reduction of the long-period orbit errors and range biases using altimeter data from NASA's Ocean Pathfinder program. Along-track sea-height residuals are sequentially filtered and backwards smoothed, and the radial orbit errors are modeled as sinusoids with a wavelength equal to one revolution of the satellite. The amplitudes of the sinusoids are treated as exponentially-correlated noise processes with a time-constant of six days. Measurement errors (e.g., altimeter range bias) are simultaneously recovered as constant parameters. The corrections derived from the global ocean analysis are then applied over the Greenland ice sheet. The orbit error and measurement bias corrections for different missions are developed in a single framework to enable robust linkage of ice-sheet measurements from 1978 to the present. In 1998, we completed our re-evaluation of the 1978 Seasat and 1985-1989 Geosat Exact Repeat Mission data. The estimates of ice thickness over Southern Greenland (south of 72N and above 2000 m) from 1978 to 1988 show large regional variations (+/-18 cm/yr), but yield an overall rate of +1.5 +/- 0.5 cm/yr (one standard error). Accounting for systematic errors, the estimate may not be significantly different from the null growth rate. The average elevation change from 1978 to 1988 is too small to assess whether the Greenland ice sheet is undergoing a long-term change.

Haines, Bruce J.↗

Maya Forest Water Resources I: Using NASA Earth Observations to Map Forested Inundation in the Maya Forest

As climate change increases the severity and frequency of extreme weather events in the tropics, it is vital for the safety of local communities and the health of ecosystems to monitor seasonal inundation. Forested inundation affects the ability of forested wetlands to provide ecosystem services, such as flood mitigation, water filtration, carbon storage, and erosion mitigation. While ground-based monitoring has traditionally been used to map inundation extent, those methods are costly and time-intensive. The NASA DEVELOP team focused on seasonal inundation throughout 2008 in the Maya Forest, when changes in inundation were drastic. To monitor seasonal inundation, our team used in situ field data and Earth observations from Landsat 7 Enhanced Thematic Mapper (ETM+), Advanced Land Observing Satellite (ALOS) Phased Array type L-band Synthetic Aperture Radar (PALSAR) 1, Shuttle Radar Topography Mission (SRTM), and products from the Ice, Cloud, and Land Elevation Satellite (ICESat). The team applied a Random Forest algorithm to Landsat 7 imagery, generating an object-level land cover classification with an overall accuracy of 72.1% and forest class with 100% recall and 78% precision. The team applied L-band backscatter thresholds from existing literature to forest-masked ALOS imagery and refined the thresholds in an iterative process using field data and hydrology models to delineate seasonal inundation extent. These publicly available data products help end users from Belize’s Land Information Center (LIC) and Forest Department, Guatemala’s Center for Monitoring and Evaluation (CEMEC), and Mexico’s El Colegio de la Frontera Sur (ECOSUR) to inform land management and protect community infrastructure.

Madelyn Savan↗