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At least 613 records · Page 34

Longitudinal Patterns in Nitrate Revealed Through Drone‐Based Measurements in an Agriculturally Influenced Midwestern U.S. River

Nitrate concentrations in streams and rivers in the Midwestern United States are often elevated, reflecting the predominance of agriculture in the surrounding landscape. Recent advances in technology, including surface water drones and more precise sensors, provide opportunities to investigate nitrate dynamics with high spatial and temporal resolution. We deployed an aquatic drone, the AquaBOT, in a sixth-order, agriculturally influenced river to examine longitudinal patterns in water quality. Our goal was to measure the spatial and temporal heterogeneity in nitrate and nitrate removal processes and determine the influence of tributary inputs on main stem chemistry. We navigated the drone along a 12-km reach of the Des Moines River (Iowa, USA) nine times between June 2021 and August 2022. Across the deployments, mean nitrate concentration was positively related to discharge and was nearly two orders of magnitude higher in spring than summer. We observed contrasting patterns in main stem nitrate, which decreased downstream during some runs (e.g., 3.1–2.7 mg N L −1 in June 2021), demonstrating net nitrate uptake along the reach, and remained constant on other dates. Similarly, tributaries to the Des Moines had a varied influence on riverine nitrate. Tributaries either increased or decreased main stem nitrate concentrations depending on the tributary and the date. Nitrate removal rates were spatially and temporally variable but showed some consistency at the subreach (2 km) scale, with two subreaches often showing elevated rates of nitrate removal across dates. In conclusion, our study reveals nuanced heterogeneity in nitrate dynamics of the Des Moines River despite the homogeneity of agricultural land cover in the watershed.

54 ENVIRONMENTAL SCIENCES↗

Tuning the Coordination Environment of Rh Single Atoms on Highly Dispersed Reducible Oxides for Enhanced Reverse Water-Gas Shift Performance

Controlling the dynamic mobility of catalyst surface active sites and their interactions with the surrounding environment is critical in generating active surfaces that directly influence the catalytic activity and selectivity. Here, we report a strategy for tailoring the dispersion and electronic environment of single atom Rh catalysts by decorating the alumina support with highly dispersed (HD) cerium and molybdenum oxides. The resulting catalysts exhibit markedly different behavior in the Reverse Water Gas Shift (RWGS) reaction. In particular, Rh/MoOx(HD)/Al2O3 maintains atomically dispersed Rh even at elevated temperatures (up to 400 °C), achieving CO selectivity of up to 100% and resists sintering via the formation of a newly developed structure featuring Rh single atoms embedded in MoOx clusters. In situ spectroscopy and microscopy analyses confirm the stabilization of Rh and the dynamic evolution of Rh–Mo coordination under reaction conditions. Our findings highlight the power of support modification in steering active site structure and activity, offering a pathway toward enhanced and tunable single atom catalysts for CO2 valorization.

CO selectivity↗

Crossover as Determinant for Safety and Performance Tradeoffs in Proton Exchange Membrane Water Electrolyzers

Hydrogen (H2) crossover is a pressing challenge constraining safe and efficient operation of proton exchange membrane water electrolyzers (PEMWEs) especially amongst strides to employ thinner membranes, which enables improved energy efficiency, and elevated cathode pressures, that reduces the energy burden on downstream compressors. Here, we develop a microstructure-aware multicomponent reactive-transport framework that resolves dissolved and gaseous H2 transport pathways and mechanistically links electrode architecture to crossover related safety and performance. We show that operability is co-governed by the cathode catalyst layer (CCL) and the anode porous transport layer (APTL) which sets the H2 crossover flux and the egress capacity respectively. Elevated Pt/C ratio in the CCL suppresses crossover flux by up to 23% while a higher APTL porosity lowers H2 in O2 fraction by 0.6% in the anode effluent. We condense the findings into (cathode pressure-current density) maps overlaid with safety limits and performance targets and ultimately define two safety-performance unified metrics to gauge the size and quality of the operating window. Given the push towards higher pressure and deeper turndown for renewable integration, this study provides mechanistic design guidance to prevent crossover-induced safety risks while preserving the desired performance.

Electrolysis↗

QA/QC-ed Groundwater Level Time Series in PLM-1 and PLM-6 Monitoring Wells, East River, Colorado (2016-2022)

This data set contains QA/QC-ed (Quality Assurance and Quality Control) water level data for the PLM1 and PLM6 wells. PLM1 and PLM6 are location identifiers used by the Watershed Function SFA project for two groundwater monitoring wells along an elevation gradient located along the lower montane life zone of a hillslope near the Pumphouse location at the East River Watershed, Colorado, USA. These wells are used to monitor subsurface water and carbon inventories and fluxes, and to determine the seasonally dependent flow of groundwater under the PLM hillslope. The downslope flow of groundwater in combination with data on groundwater chemistry (see related references) can be used to estimate rates of solute export from the hillslope to the floodplain and river. QA/QC analysis of measured groundwater levels in monitoring wells PLM-1 and PLM-6 included identification and flagging of duplicated values of timestamps, gap filling of missing timestamps and water levels, removal of abnormal/bad and outliers of measured water levels. The QA/QC analysis also tested the application of different QA/QC methods and the development of regular (5-minute, 1-hour, and 1-day) time series datasets, which can serve as a benchmark for testing other QA/QC techniques, and will be applicable for ecohydrological modeling. The package includes a Readme file, one R code file used to perform QA/QC, a series of 8 data csv files (six QA/QC-ed regular time series datasets of varying intervals (5-min, 1-hr, 1-day) and two files with QA/QC flagging of original data), and three files for the reporting format adoption of this dataset (InstallationMethods, file level metadata (flmd), and data dictionary (dd) files).QA/QC-ed data herein were derived from the original/raw data publication available at Williams et al., 2020 (DOI: 10.15485/1818367). For more information about running R code file (10.15485_1866836_QAQC_PLM1_PLM6.R) to reproduce QA/QC output files, see README (QAQC_PLM_readme.docx). This dataset replaces the previously published raw data time series, and is the final groundwater data product for the PLM wells in the East River. Complete metadata information on the PLM1 and PLM6 wells are available in a related dataset on ESS-DIVE: Varadharajan C, et al (2022). https://doi.org/10.15485/1660962. These data products are part of the Watershed Function Scientific Focus Area collection effort to further scientific understanding of biogeochemical dynamics from genome to watershed scales. 2022/09/09 Update: Converted data files using ESS-DIVE’s Hydrological Monitoring Reporting Format. With the adoption of this reporting format, the addition of three new files (v1_20220909_flmd.csv, V1_20220909_dd.csv, and InstallationMethods.csv) were added. The file-level metadata file (v1_20220909_flmd.csv) contains information specific to the files contained within the dataset. The data dictionary file (v1_20220909_dd.csv) contains definitions of column headers and other terms across the dataset. The installation methods file (InstallationMethods.csv) contains a description of methods associated with installation and deployment at PLM1 and PLM6 wells. Additionally, eight data files were re-formatted to follow the reporting format guidance (er_plm1_waterlevel_2016-2020.csv, er_plm1_waterlevel_1-hour_2016-2020.csv, er_plm1_waterlevel_daily_2016-2020.csv, QA_PLM1_Flagging.csv, er_plm6_waterlevel_2016-2020.csv, er_plm6_waterlevel_1-hour_2016-2020.csv, er_plm6_waterlevel_daily_2016-2020.csv, QA_PLM6_Flagging.csv). The major changes to the data files include the addition of header_rows above the data containing metadata about the particular well, units, and sensor description. 2023/01/18 Update: Dataset updated to include additional QA/QC-ed water level data up until 2022-10-12 for ER-PLM1 and 2022-10-13 for ER-PLM6. Reporting format specific files (v2_20230118_flmd.csv, v2_20230118_dd.csv, v2_20230118_InstallationMethods.csv) were updated to reflect the additional data. R code file (QAQC_PLM1_PLM6.R) was added to replace the previously uploaded HTML files to enable execution of the associated code. R code file (QAQC_PLM1_PLM6.R) and ReadMe file (QAQC_PLM_readme.docx) were revised to clarify where original data was retrieved from and to remove local file paths.

54 ENVIRONMENTAL SCIENCES↗

Identifying snowfall elevation patterns by assimilating satellite-based snow depth retrievals

Precipitation in mountain regions is highly variable and poorly measured, posing important challenges to water resource management. Traditional methods to estimate precipitation include in-situ gauges, Doppler weather radars, satellite radars and radiometers, numerical modeling and reanalysis products. Each of these methods is unable to adequately capture complex orographic precipitation. Here, we propose a novel approach to characterize orographic snowfall over mountain regions. We use a particle batch smoother to leverage satellite information from Sentinel-1 derived snow depth retrievals and to correct various gridded precipitation products. This novel approach is tested using a simple snow model for an alpine basin located in Trentino Alto Adige, Italy. Here, we quantify the precipitation biases across the basin and found that the assimilation method (i) corrects for snowfall biases and uncertainties, (ii) leads to cumulative snowfall elevation patterns that are consistent across precipitation products, and (iii) results in overall improved basin-wide snow variables (snow depth and snow cover area) and basin streamflow estimates.

54 ENVIRONMENTAL SCIENCES↗

Comparison of fiber-optic distributed temperature sensing and high-sensitivity sensor spatial surveying of stream temperature

Measuring surface water temperature spatial variability is needed to estimate the interaction between surface water and groundwater, evaluate fish habitat and thermal inertia, and to estimate streamflow frequency and duration. Fiber optic distributed temperature sensing (FO-DTS) has been used in rivers and lakes, providing high-resolution and sensitive temperature monitoring over large temporal and spatial scales. However, in streams with cobbly or bedrock-lined streambeds and variable bathymetry, use of FO-DTS to measure temperature close to the surface water and groundwater interface can be challenging if even feasible. FO-DTS can also be costly, involve difficult installations, and require an advanced understanding of the technology, calibration, and data processing. In this study, we compared FO-DTS stream temperature survey results to an alternative temperature survey method employing a towed transect of high-resolution temperature loggers spaced at 1-m and transported in the stream along the study reach, to measure the spatial distribution of stream-water temperature in East Fork Poplar Creek near Oak Ridge, Tennessee, USA. We assessed the applicability and limitations of the two methods, and quantitatively compared in-situ temperature survey results measured simultaneously with each method. Regression results showed strong temporal and spatial correlation between the two methods. Differences were only elevated near the stream banks in areas that were coincident with correlation slope deviations from unity, which was attributed to shallower water and lower data density. Kriging standard errors were also low at channel center with minor increases near the stream banks. Furthermore, the results suggested that the array of the individual temperature sensors can provide a practical alternative to FO-DTS for thermal characterization of surface water, providing slightly lower spatial and temporal resolution, but with higher accuracy of temperature measurement, with greater simplicity, and with a broader range of conditions where it may be applied.

54 ENVIRONMENTAL SCIENCES↗

Variational encoder geostatistical analysis (VEGAS) with an application to large scale riverine bathymetry

Estimation of riverbed profiles, also known as bathymetry, plays a vital role in many applications, such as safe and efficient inland navigation, prediction of bank erosion, land subsidence, and flood risk management. The high cost and complex logistics of direct bathymetry surveys, i.e, depth imaging, have encouraged the use of indirect measurements such as surface flow velocities. However, estimating high-resolution bathymetry from indirect measurements is an inverse problem that can be computationally challenging. Here, we propose a reduced-order model (ROM) based approach that utilizes a variational autoencoder (VAE), a type of deep neural network with a narrow layer in the middle, to compress bathymetry and flow velocity information and accelerate bathymetry inverse problems from flow velocity measurements. In our application, the shallow-water equations (SWE) with appropriate boundary conditions (BCs), e.g., the discharge and/or the free surface elevation, constitute the forward problem, to predict flow velocity. Then, ROMs of the SWEs are constructed on a nonlinear manifold of low dimensionality through a variational encoder and the bathymetry inversion problem is derived on the low-dimensional latent space in a Hierarchical Bayesian setting. Further, the reformulation allows variational inference with a small number (e.g., $\mathscr{O}$ (100) of ROM runs and efficient uncertainty quantification. We have tested our inversion approach on a one-mile reach of the Savannah River, GA, USA. Once the neural network is trained (offline stage), the proposed technique can perform the inversion operation orders of magnitude faster than traditional inversion methods that are commonly based on linear projections, such as principal component analysis (PCA), or the principal component geostatistical approach (PCGA). Furthermore, tests show that the algorithm can estimate the bathymetry with good accuracy even with sparse flow velocity measurements.

54 ENVIRONMENTAL SCIENCES↗

Mapping snow depth and volume at the alpine watershed scale from aerial imagery using Structure from Motion

Time series mapping of snow volume in the mountains at global scales and at resolutions needed for water resource management is an unsolved challenge to date. Snow depth mapping by differencing surface elevations from airborne lidar is a mature measurement approach filling the observation gap operationally in a few regions, primarily in mountain headwaters in the Western United States. The same concept for snow depth retrieval from stereo- or multi-view photogrammetry has been demonstrated, but these previous studies had limited ability to determine the uncertainties of photogrammetric snow depth at the basin scale. For example, assessments used non-coincident or discrete points for reference, masked out vegetation, or compared a subset of the fully snow-covered study domain. Here, using a unique data set with simultaneously collected airborne data, we compare snow depth mapped from multi-view Structure from Motion photogrammetry to that mapped by lidar at multiple resolutions over an entire mountain basin (300 km 2 ). After excluding reconstruction errors (negative depths), SfM had lower snow-covered area (~27%) and snow volume (~16%) compared to lidar. The reconstruction errors were primarily in areas with vegetation, shallow snow (< 1 m), and steep slopes (> 60°C). Across the overlapping snow extent, snow depths compared well to lidar with similar mean values (< 0.03 m difference) and snow volume (± 5%) for output resolutions of 3 m and 50 m, and with a normalized median absolute deviation of 0.19 m. Our results indicate that photogrammetry from aerial images can be applied in the mountains but would perform best for deeper snowpacks above tree line.

54 ENVIRONMENTAL SCIENCES↗

Performance of DSRC V2V Communication Networks in an Autonomous Semi-Truck Platoon Application

Autonomy for multiple trucks to drive in a fixedheadway platoon formation is achieved by adding precision GPS and V2V communications to a conventional adaptive cruise control (ACC) system. The performance of the Cooperative ACC (CACC) system depends heavily on the reliability of the underlying V2V communications network. Using data recorded on precision-instrumented trucks at both ACM and NCAT test tracks, we provide an understanding of various effects on V2V network performance: Occlusions - non-line-of-sight (NLOS) between the Tx and Rx antenna may cause network signal loss. Rain - water droplets in the air may cause network signal degradation. Antenna position - antennas at higher elevation may have less ground clutter to deal with. RF interference - interference may cause network packet loss. GPS outage - outages caused by tree cover, tunnels, etc. may result in degraded performance. Road curvature - curves may affect antenna diversity. Road grade - antenna may have limited vertical coverage. Our results, which include multiple plots and graphs and their analysis, build on those reported by others and could be of interest to researchers, practitioners, and end-users in the broader autonomous-connected vehicle community.

V2V communications, GPS, truck platoon, semi-auton↗

Development of a closed pore insulation material

A closed pore ceramic foam insulation material (CPI) has been developed that offers possibilities for use as a reusable external heat shield for the NASA manned space shuttle. The outstanding characteristics of CPI are: (1) negligible water absorption due to a noninterconnecting network of cells; (2) high emittance at room and elevated temperature; (3) ability to survive at least 10 simulated reentry cycles to 1500 K using radiant heat lamps to simulate the reentry heat fluxes; (4) ability to survive, with no change in properties or appearance, at least 10 simulated plasma arc jet cycles to 1500 K (with the exception of some stress cracks induced either by the unduly severe nature of the initial arc splash heating pulse or by improper mechanical holding of the specimen in the test fixture); (5) strength (flexure); and (6) a low thermal conductivity throughout the temperature range of interest for the space shuttle.

Tobin, A.↗

Analytical and experimental study of supersonic combustion of hydrogen in a vitiated airstream

Detailed probe measurements of total temperature, pressure, and composition were taken in a two-dimensional test section 35.6 cm downstream of hydrogen injection. A high pressure gas generator supplied Mach 2.44 vitiated air or inert gas at elevated temperatures and at a static pressure equal to that of the hydrogen. Special water-cooled probes and sampling techniques were developed for the short test times required by heat-sink hardware. Independent methods of measuring stream total temperatures are compared. For the pure mixing case, the computed composition profile agreed well with the experimental profile. The analysis takes into account the wall boundary layer and the initial boundary layer in the main stream. Ignition of hydrogen, as determined from photographic exposures of the radiating gases, varied from 30 to 10 cm downstream from injection for a 45 K increase in local free-stream static temperature.

Burrows, M. C.↗

The use of snowcovered area in runoff forecasts

Long-term snowcovered area data from aircraft and satellite observations have proven useful in reducing seasonal runoff forecast error on the Kern river watershed. Similar use of snowcovered area on the Kings river watershed produced results that were about equivalent to methods based solely on conventional data. Snowcovered area will be most effective in reducing forecast procedural error on watersheds with: (1) a substantial amount of area within a limited elevation range; (2) an erratic precipitation and/or snowpack accumulation pattern not strongly related to elevation; and (3) poor coverage by precipitation stations or snow courses restricting adequate indexing of water supply conditions. When satellite data acquisition and delivery problems are resolved, the derived snowcover information should provide a means for enhancing operational streamflow forecasts for areas that depend primarily on snowmelt for their water supply.

Rango, A.↗

Potential Mars Surveyor 2001 Landing Sites: Low-Elevation Cratered "Highlands" in Central and Eastern Sinus Meridiani and Near Amenthes Fossae

The main scientific goal for the Mars Surveyor Program 2001 (MSP 01) landed mission is to collect and characterize 91 rock and 13 soil core samples using an integrated instrument suite onboard the Athena Rover. If possible, these samples will be retrieved and returned to Earth via a MSP 05 or MSP 07 mission. Preliminary engineering constraints for the MSP 01 landing site call for a location that lies between 15 S and 30 N, and below about 2 km elevation (based on Viking-era topography). Desirable landing sites for MSP 01 are to be located "in the ancient highlands where the environmental conditions may have been favorable to the preservation of evidence of possible prebiotic or biotic processes including the emergence (and, potentially, the persistence) of life". We interpret this to mean that the desirable sites include those that have evidence of aqueous sediments that might have been deposited during the Noachian and/or Hesperian Epochs of Mars' history. In addition to the search for subaqueous sedimentary deposits, we took into consideration the fact that the rover, Athena, will need to be able to access these materials. Thus, a site where aeolian deflation has occurred might be desirable because it might expose, in situ, layered sedimentary deposits. Deflated areas, of course, might include potential landing hazards in the form of meterscale buttes and mesas (e.g., Christmas Lake Valley, OR), thus careful study of such sites with high resolution images will be required before a decision is made to land. We have been examining three regions that have potential to be considered for MSP 01 landing sites. This work is based on Viking (VIS, IRTM) and Phobos 2 (Termoskan) observations and should be regarded as preliminary because we believe that the final site selection should also be based upon analysis of Mars Global Surveyor observations that help constrain mineralogy (TES) and local geomorphology (MOC, MOLA). (1) Eastern Sinus Meridiani Region (proposed by K. S. Edgett) Sinus Meridiani is a persistent low-albedo (< 0. 16) region on the martian equator that has been recognized for about 400 years. All of Sinus Meridiani is below the 2 km elevation constraint for MSP 01. The region includes cratered highlands, valley networks, aeolian dunes, and possible aqueous sedimentary deposits. The landing site study region is located in the eastern portion of Sinus Meridiani. It is bounded by latitudes 10 S to 2 N, longitudes 355 W to 345 W, and the elevations are mostly 1-2 km. The center of this area contains a medium-albedo (0.19-0.21), relatively smooth-surfaced deposit that was suggested by Rice to be a lacustrine deposit. Several potential landing areas can be suggested within this region. Based on Viking and Phobos 2 data, the favored sites so far are centered at 7.6 S, 346.9 W and 0.8 S, 349 W. Thermal inertias are 3.2-7.0 x 10(exp -3) cal /sq cm s(exp -0.5)/K; and rock abundances are around 2-6%. The site at 7.6 S, 346.9 W is at the southern end of the smooth, medium-albedo unit that might have a lacustrine origin. At this location, numerous channels appear to have drained toward the smooth unit. Viking images from orbit 747A show this area at about 15 m/pixel ground resolution. The images reveal that aeolian deflation has occurred along the deposit's margins. Bright (i.e., albedo >= 0.21) aeolian dunes are present on the channel floors and in some of the depressions on the smooth unit. The bright, apparently active dunes might consist of material (perhaps lakedeposited sands) that has been eroded from the smooth unit. The site at approximately 0.8 S, 349 W is selected because it offers an opportunity to solve a long-standing puzzle about Mars remote sensing. There are three main "color" units on Mars: "dark red, dark gray, and bright red". This landing site would allow the Athena rover an opportunity to investigate all three materials within close proximity (the best place on Mars to do so). There are no high resolution (better than 100 m/pixel) Viking or Mariner images of this site. (2) Central Sinus Meridiani Region (proposed by K. S. Edgett and T. J. Parker) Central Sinus Meridiani is characterized by two types of surfaces [4]. One is like typical martian cratered highlands elsewhere- there are old valley networks and old impact craters. The other is relatively smooth and flat. These two units are in contact around 3.1 S between 5 W and 4 E longitudes. Valley networks- including one at 6'S, 358 W that rivals the Grand Canyon of Arizona- once drained toward the smooth unit. Edgett and Parker [4] proposed that the smooth unit might consist of sediments laid down in a large Noachian-aged sea/ocean that would have covered much of the northern hemisphere. Schultz and Lutz [I I I suggested that it is a paleopolar layered deposit. Regardless, the smooth unit where it contacts the cratered terrain would make an excellent site for Athena rover to investigate. The site is best seen in Viking high resolution images from orbits 408B (about 30 m/pixel) and 746A (about 12 m/pixel). These images suggest that aeolian deflation has occurred along the margin of the smooth unit, and this deflation has exposed horizontal larrs of material. The elevation is about 0.5 km; thermal inertias are 6.5-8.0 x 10(exp -3) cal /sq cm s(exp -0.5) / K; rock abundances are 2-4%; and the surface is probably sandy with dark drifts and ripples but almost no actual dunes. We suggest a landing around 3.2 S, 3.0 W would test the aqueous sediment hypothesis and provide a potentially smooth surface on which to land. (3) Amenthes Fossae Region (proposed by S. N. Huntwork and K. S. Edgett) The Amenthes Fossae are a series of graben/fissures that are circumferential to the southeast side of Isidis Planitia. These fissures cross a variety of ancient, heavily cratered Noachian terrain and younger, Hesperian and Amazonian terrain. We focused our search on a region 0-15 N, 250 - 270 W. Elevations are -0.5 to 2 km. Depending upon whether Isidis Planitia was ever a water-rich environment, this region might have been influenced by aqueous sedimentation. Valley networks are common, and they drained toward the north and northwest. We focused our work on a set of Viking orbiter high-resolution images, 719A 1-48. These have resolutions 16-24 rri/pixel. We examined images 20-23, centered at 2 N, 258 W. This site, on the plains just southwest of a 42 km-diameter crater, includes a valley network channel, a relatively young crater ejecta deposit, a few buttes composed of presumably ancient, Noachian bedrock, and a "plains" unit. The plains might make an ideal landing surface, except for the presence of some fine-scale ridges (oriented approximately N-S). The ridges are probably yardangs, thus this site offers a place where aeolian deflation has probably exposed some of the layered rock units that comprise the "plains". Thermal inertias are 7.9-8.3 x 10(exp -3) cal/sq cm s(exp -0.5) /K and rock abundances are 10-15%. A rover traverse might include the opportunity to go down to the floor (and sample along the walls) of the valley network channel at 2 N 258.1 W.

Edgett, K. S.↗

Forecasting of Storm-Surge Floods Using ADCIRC and Optimized DEMs

Increasing the accuracy of storm-surge flood forecasts is essential for improving preparedness for hurricanes and other severe storms and, in particular, for optimizing evacuation scenarios. An interactive database, developed by WorldWinds, Inc., contains atlases of storm-surge flood levels for the Louisiana/Mississippi gulf coast region. These atlases were developed to improve forecasting of flooding along the coastline and estuaries and in adjacent inland areas. Storm-surge heights depend on a complex interaction of several factors, including: storm size, central minimum pressure, forward speed of motion, bottom topography near the point of landfall, astronomical tides, and, most importantly, maximum wind speed. The information in the atlases was generated in over 100 computational simulations, partly by use of a parallel-processing version of the ADvanced CIRCulation (ADCIRC) model. ADCIRC is a nonlinear computational model of hydrodynamics, developed by the U.S. Army Corps of Engineers and the US Navy, as a family of two- and three-dimensional finite-element-based codes. It affords a capability for simulating tidal circulation and storm-surge propagation over very large computational domains, while simultaneously providing high-resolution output in areas of complex shoreline and bathymetry. The ADCIRC finite-element grid for this project covered the Gulf of Mexico and contiguous basins, extending into the deep Atlantic Ocean with progressively higher resolution approaching the study area. The advantage of using ADCIRC over other storm-surge models, such as SLOSH, is that input conditions can include all or part of wind stress, tides, wave stress, and river discharge, which serve to make the model output more accurate. To keep the computational load manageable, this work was conducted using only the wind stress, calculated by using historical data from Hurricane Camille, as the input condition for the model. Hurricane storm-surge simulations were performed on an eight-node Linux computer cluster. Each node contained dual 2-GHz processors, 2GB of memory, and a 40GB hard drive. The digital elevation model (DEM) for this region was specified using a combination of Navy data (over water), NOAA data (for the coastline), and optimized Interferometric Synthetic Aperture Radar data (over land). This high-resolution topographical data of the Mississippi coastal region provided the ADCIRC model with improved input with which to calculate improved storm-surge forecasts.

Valenti, Elizabeth↗

Anomalous DOC Signatures Reveal Iron Control on Export Dynamics in the Pacific Southern Ocean

Here we shed light on two mechanisms that stimulate deep particle export via upper-ocean iron fertilization in the Southern Ocean: deep frontal mixing and melting of sea ice. We present data collected a decade apart in the Pacific sector of the Southern Ocean when, serendipitously, seasonal Antarctic ice melt was anomalously low (2008) and anomalously high (2017). In 2008, the low ice melt year, we concluded that vertical mixing of iron into the euphotic zone via deep-mixing fronts was the primary stimulant of export that reached depths of ~1500 meters. This process was evidenced by localized enhancements of dissolved organic carbon (DOC) concentrations up to 4 μmol C kg-1 beneath seven branches of fronts embedded within the Antarctic Circumpolar Current (ACC). We used these enhanced DOC concentrations in the bathypelagic as primary indications of the depths and locations of recent export, as it is a logical residue of such. In 2017, the year in which sea ice melt was anomalously high, we concluded that the main driver of a widespread export event to the seafloor was the lateral influx of iron within the melt. Indications of this event included substantial enhancements of DOC concentrations (2 - 31 6 μmol C kg-1), elevated beam attenuation, and enhanced surface iron concentrations associated with a layer of low salinity water at a nearby station. Further, significant deficits of upper ocean silicic acid during the 2017 occupation indicated that deep export was likely stimulated by an iron-fueled diatom bloom. This analysis highlights the impact of iron supplied from frontal vertical mixing and sea ice melt on export and ultimately for long-term carbon sequestration in the Southern Ocean, as well as the utility of deep DOC enrichments as signatures of particle export. Understanding the impact that ice melt events have on carbon export is crucial given that anomalous events are occurring more often as our climate changes.

Dissolved Organic Carbon↗

Impact of SO 2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe 0.9 Ni 0.1 O 3 Perovskite Oxides

Ni-doped LaFeO 3 perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO 2 /H 2 O coelectrolysis. Here, the performance of LaFe 0.9 Ni 0.1 O 3 is being investigated under real-world conditions that include exposure to acid gases, such as SO 2 , relevant to SOEC operation. Experiments show that LaFe 0.9 Ni 0.1 O 3 exsolves NiFe nanoparticles, along with the formation of surface SO 4 2– and SO 3 2– after being exposed to 200 ppm of SO 2 . This suggests that the ionic diffusion of Ni 3+ and Fe 3+ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO 2 , the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO 2 to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO 2 affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.

Najimu, Musa [Univ. of Southern California, Los An↗

Calibration of Atmospherically Induced Delay Fluctuations Due to Water Vapor

We have completed a new generation of water vapor radiometers (WVR), the A- series, in order to support radio science experiments with the Cassini spacecraft. These new instruments sense three frequencies in the vicinity of the 22 GHz emission line of atmospheric water vapor within a 1 degree beamwidth from a clear aperture antenna that is co-pointed with the radio telescope down to 10 degree elevation. The radiometer electronics features almost an order of magnitude improvement in temperature stability compared with earlier WVR designs. For many radio science experiments, the error budget is likely to be dominated by path delay fluctuations due to variable atmospheric water vapor along the line-of-sight to the spacecraft. In order to demonstrate the performance of these new WVRs we are attempting to calibrate the delay fluctuations as seen by a radio interferometer operating over a 21 km baseline with a WVR near each antenna. The characteristics of these new WVRs will be described and the results of our preliminary analysis will be presented indicating an accuracy of 0.2 to 0.5 mm in tracking path delay fluctuations over time scales of 10 to 10,000 seconds.

Resch, George↗