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At least 487 records · Page 27

The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC Cathodes

Nanoscale morphology has a direct impact on the performance of materials for electrochemical energy storage. Despite this importance, little is known about the evolution of primary particle morphology nor its effect on chemical pathways during synthesis. In this work, operando characterization is combined with atomic-scale and continuum simulations to clarify the relationship between morphology of cathode primary particles and their lithiation during calcination of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC-811). This combined approach reveals a key role for surface oxygen adsorption in facilitating the lithiation reaction by promoting metal diffusion and oxidation, and simultaneously providing surface sites for lithium insertion. Furthermore, oxygen surface termination is shown to increase the activation energy for sintering, leading to smaller primary particle sizes at intermediate temperatures. Smaller particles provide both shorter diffusion lengths for lithium incorporation and increased surface site density for lithium insertion. These insights provide a foundation for more tailored syntheses of cathode materials with optimized performance characteristics.

25 ENERGY STORAGE↗

AmeriFlux US-RGF Stanislaus County Forage Farm

This is the AmeriFlux version of the carbon flux data for the site US-RGF Stanislaus County Forage Farm. Site Description - Commercially farmed field in Stanislaus County, California. Part of a multi-year, ground-truthing field study under the DOE ARPA-E SMARTFARM project (https://arpa-e.energy.gov/news-and-media/blog-posts/smartfarm-changing-whats-possible-agriculture). Field is approx. 31.3 ha in size (1,300 ft by 2,600 ft), part of a 176+ acre site in several fields with commercial corn-wheat rotation for silage, in combination with manure application.

Schuppenhauer, Michael R.↗

AmeriFlux FLUXNET-1F US-RGF Stanislaus County Forage Farm

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-RGF Stanislaus County Forage Farm. This is the FLUXNET version of the carbon flux data for the site US-RGF Stanislaus County Forage Farm produced by applying the standard ONEFlux (1F) software. Site Description - Commercially farmed field in Stanislaus County, California. Part of a multi-year, ground-truthing field study under the DOE ARPA-E SMARTFARM project (https://arpa-e.energy.gov/news-and-media/blog-posts/smartfarm-changing-whats-possible-agriculture). Field is approx. 31.3 ha in size (1,300 ft by 2,600 ft), part of a 176+ acre site in several fields with commercial corn-wheat rotation for silage, in combination with manure application.

Schuppenhauer, Michael R.↗

Preliminary Analysis of Nuclear-Powered Data Center Scenarios

This report provides a comprehensive analysis of the potential for nuclear energy to meet the growing energy demands of data centers (DCs). It evaluates the technical, economic, and socio-environmental implications of coupling Nuclear Power Plants (NPPs) with DCs, providing initial responses to several key research questions: What is the potential increased energy demand from DCs in the U.S., in the short, medium and long term? The U.S. is experiencing a rapid increase in energy demand from DCs, with projections indicating a total increase of 24-74 GWy(e) by 2028. Meeting this demand with nuclear energy would require 27–85 GWe of installed capacity. While this surge is expected to slow in the long term, the DC industry needs reliable, scalable, and clean energy sources. How much nuclear capacity can be deployed to meet DC demand and in which timeframe? Several pathways for increasing nuclear capacity were identified, including uprates, restarts of recently retired reactors, power purchase agreements with existing fleet, and new construction. Approximately 20‒28 GWe of nuclear capacity could be dedicated to DCs by the early 2030s. How much High Assay Low Enriched Uranium (HALEU) would be needed to support some nuclear deployment scenarios for DCs? Meeting the deployment targets announced by Google and Amazon for the Kairos Power Fluoride-Salt-Cooled High-Temperature Reactor or KP-FHR (~500 MWe by 2035) and the Xe-100 (~1 GWe by 2040), respectively, requires ramping up 19.75% enriched HALEU production to ~6 t/yr by 2040. What types of nuclear energy/DC coupling options exist, and what are the different benefits/challenges? Five coupling options were analyzed, ranging from grid-connected configurations to colocated, behind-the-meter setups. Key design considerations include the proximity to high- and/or medium-voltage transmission lines, the desired internal fault tolerance, and the sources of alternative/backup power during outages. Each coupling option offers unique benefits and challenges in terms of reliability, system costs, regulation, timeline, etc. A list of NPP/DC deployment scenarios was developed, considering existing or newly built NPP or DC projects. Colocated DCs with new small modular reactors or large reactors on greenfield and brownfield sites are the focus of this report. What types of reactors, especially what size, may be incentivized by DCs? Reactor sizing optimization revealed that the ideal reactor size and number of units depend on DC demand, coupling configurations defined in this report, and other economic factors. Larger reactors are preferred for high-demand DCs and grid-connected systems, while larger number of smaller reactors are better suited for DC configurations without grid backup. Which sites may be compatible with co-located nuclear-powered DCs? Siting those projects is a complicated evaluation factoring local water resources, grid connection availability and reliability, IT infrastructure, local work force, proximity to population zones, etc. For this effort greenfield and brownfield sites such as retired coal-fired plants were used to evaluate this question. This evaluation is not meant to recommend any particular site but it highlights key siting criteria and demonstrates large-scale site availability. What are the socio-economic impacts of co-located nuclear-powered DCs? Those projects generate substantial economic benefits to the local economy, particularly in urban settings. Hyperscale DCs colocated with nuclear power plants (sized around 1 GW of power) can create nearly 1,700 jobs for annual operations and more than 7,300 jobs among the supply chain and local businesses as a result of increased household spending. Rural projects also provide significant benefits, but at lower magnitudes compared to urban deployments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Temporal variations of nucleonic abundances in solar flare energetic particle events. II - Evidence for large-scale shock acceleration

A survey of the roughly 1 MeV per nucleon ion abundance over the range H-Fe measured with 3 hr time resolution during large solar particle events from November 1973 through December 1977, under near solar minimum conditions, is presented. For all the monitored species, a strong decrease in average flux level occurred with increase of the optical flare site distance from the W 60 deg connection point. The 3 hr abundance ratios He/H, O/He, and Fe/He were observed to fluctuate by a factor of about two about their average values for given flare events, and the size of these fluctuations was independent of the distance to the optical flare site. The monitored abundance ratios exhibited no dependence on distance to the optical flare site. The physical mechanism suggested to explain these observations is large-scale shock acceleration from a shock wave originating at the flare site and propagating as far away as 100 deg heliolongitude.

Mason, G. M.↗

Magnetic properties of Apollo samples and implications for regolith formation

The magnetic properties of a number of Apollo 17 samples have been measured and confirm that regoliths of mare sites (Apollo 11, 12, 15 valley, and 17 valley) differ markedly from those of highland sites (Apollo 14, 16, and 17 massif) in the ratio of content of metallic to ferrous iron and in the grain size of metallic iron. The ratio of metallic to ferrous iron is correlated with mean particle size, a parameter representing maturity, for soils of Apollo 16 and roughly correlated with the age of the sites for soils of different sites. It is suggested that the ratio of metallic to ferrous iron may be an effective indicator of relative soil maturity for any one site and of the age of the soil material for any sites.

Pearce, G. W.↗

Lunar Meteorites and Implications for Compositional Remote Sensing of the Lunar Surface

Lunar meteorites (LMs) are rocks found on Earth that were ejected from the Moon by impact of an asteroidal meteoroid. Three factors make the LMs important to remote-sensing studies: (1) Most are breccias composed of regolith or fragmental material; (2) all are rocks that resided (or breccias composed of material that resided) in the upper few meters of the Moon prior to launch and (3) most apparently come from areas distant from the Apollo sites. How Many Lunar Locations? At this writing (June 1999), there are 18 known lunar meteorite specimens. When unambiguous cases of terrestrial pairing are considered, the number of actual LMs reduces to 13. (Terrestrial pairing is when a single piece of lunar rock entered Earth's atmosphere, but multiple fragments were produced because the meteoroid broke apart on entry, upon hitting the ground or ice, or while being transported through the ice.) We have no reason to believe that LMs preferentially derive from any specific region(s) of the Moon; i.e., we believe that they are samples from random locations. However, we do not know how many different locations are represented by the LMs; mathematically, it could be as few as 1 or as many as 13. The actual maximum is < 13 because in some cases a single impact appears to have yielded more than one LM. Yamato 793169 and Asuka 881757 are considered "source-crater paired" or "launch paired" because they are compositionally and petrographically similar to each other and distinct from the others, and both have similar cosmic-ray exposure (CRE) histories. The same can be said of QUE 94281 and Y 793274. Thus the 13 meteorites probably represent a maximum of 11 locations on the Moon. The minimum number of likely source craters is debated and in flux as new data for different isotopic systems are obtained. Conservatively, considering CRE data only, a minimum of about 5 impacts is required. Compositional and petrographic data offer only probabilistic constraints. An extreme, but not unreasonable viewpoint, is that such data offer no constraint. For example, if one were to cut up the Apollo 17 landing site (which was selected for its diversity) into softball-sized pieces, some of those pieces (e.g., sample 70135) would be crystalline mare basalts like Y 793169 whereas others (e.g., sample 73131 would be feldspathic regolith breccias like MAC 88104/ 88105. However, nature is not so devious. Warren argues that LMs come from craters of only a few kilometers in diameter. If so, even though CRE data allow, for example, that ALHA 81005 and Y 791197) were launched simultaneously from the same crater, the probability is nevertheless low because the two meteorites are compositionally and mineralogically distinct. Thus, within the allowed range (5-11) for the number of locations represented by the LMs, values at the high end of the range are probably more likely. Mare Meteorites: Three LMs consist almost entirely of mare basalt. Two, Y 793169 and Asuka 881757, are unbrecciated, low-Ti, crystalline rocks that are compositionally and mineralogically similar (but not identical) to each other; they probably derive from a single lunar-mare location. The third, EET 87521/96008, is a fragmental breccia consisting predominantly of VLT mare basalt. Thus, these LMs probably represent only two lunar mare locations. The basaltic LMs have mineral and bulk compositions distinct from Apollo mare basalts. The petrography of Calcalong Creek has not been described in detail, but compositionally it is unique in that it corresponds to a mixture (breccia) of about one-half feldspathic material (i.e., the mean composition of the feldspathic lunar meteorites, below), one-fourth KREEP norite, one-fourth VLT mare basalt (like EET 87521), and 1% CI chondrite. With 4 micro g/g Th and correspondingly high concentrations of other incompatible elements, it is the only lunar meteorite that is likely to have come from within the Procellarum KREEP Terrane (PKT). Yamato 793274 and QUE 94281 are together distinct in being fragmental breccias containing subequal parts of feldspathic highland material and VLT mare basalt. Jolliff et al. estimate a mare to highland ratio of 54:46 for QUE 94281 and 62:38 for Y 793274; this difference is well within the range observed for soils collected only centimeters apart (in cores) at interface site like Apollo 15 and 17 [11]. Although the two meteorites were found on opposite sides of Antarctica, they are probably launch-paired. The strongest evidence is that the pyroclastic glass spherules that occur in both are of two compositional groups and the two groups are essentially the same in both meteorites. Yamato 791197 is nominally a feldspathic lunar meteorite (below), but among FLMs, it probably contains the highest abundance of clasts and glasses of mare derivation. As a consequence, its composition is at the high-Fe, low-Mg end of the range for FLMs and is not included in the FLM average of Table 1. Its composition is consistent with about 10% mare-derived material. Similarly, the two small (Y 82) pieces of Y 82192/82193186032 are more mafic than the large (Y 86) piece, probably as a result of about 7% mare-derived material. All Apollo missions went to areas in or near the PKT, and, consequently, all Apollo regolith samples are contaminated with Th-rich material from the PKT. At the nominally "typical" highland site, Apollo 16, about 30% of the regolith (<1-mm fines) is Th-rich ejecta from the Imbrium impact and about 6% is mare material probably derived from mare basins. Thus Apollo 16 regolith is not typical of the highlands. Among Apollo rocks, the compositions of the FLMs correspond most closely to the feldspathic granulitic breccias of Apollo 16 and 17. (Additional information is contained in original)

Korotev, R. L.↗

Probing Active Sites in Cu x Pd y Cluster Catalysts by Machine-Learning-Assisted X-ray Absorption Spectroscopy

Size-selected clusters are important model catalysts because of their narrow size and compositional distributions, as well as enhanced activity and selectivity in many reactions. Still, their structure-activity relationships are, in general, elusive. The main reason is the difficulty in identifying and quantitatively characterizing the catalytic active site in the clusters when it is confined within subnanometric dimensions and under the continuous structural changes the clusters can undergo in reaction conditions. Using machine learning approaches for analysis of the operando X-ray absorption near-edge structure spectra, we obtained accurate speciation of the Cu x Pd y cluster types during the propane oxidation reaction and the structural information about each type. As a result, we elucidated the information about active species and relative roles of Cu and Pd in the clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DMFS: A Data Migration File System for NetBSD

I have recently developed dmfs, a Data Migration File System, for NetBSD. This file system is based on the overlay file system, which is discussed in a separate paper, and provides kernel support for the data migration system being developed by my research group here at NASA/Ames. The file system utilizes an underlying file store to provide the file backing, and coordinates user and system access to the files. It stores its internal meta data in a flat file, which resides on a separate file system. Our data migration system provides archiving and file migration services. System utilities scan the dmfs file system for recently modified files, and archive them to two separate tape stores. Once a file has been doubly archived, files larger than a specified size will be truncated to that size, potentially freeing up large amounts of the underlying file store. Some sites will choose to retain none of the file (deleting its contents entirely from the file system) while others may choose to retain a portion, for instance a preamble describing the remainder of the file. The dmfs layer coordinates access to the file, retaining user-perceived access and modification times, file size, and restricting access to partially migrated files to the portion actually resident. When a user process attempts to read from the non-resident portion of a file, it is blocked and the dmfs layer sends a request to a system daemon to restore the file. As more of the file becomes resident, the user process is permitted to begin accessing the now-resident portions of the file. For simplicity, our data migration system divides a file into two portions, a resident portion followed by an optional non-resident portion. Also, a file is in one of three states: fully resident, fully resident and archived, and (partially) non-resident and archived. For a file which is only partially resident, any attempt to write or truncate the file, or to read a non-resident portion, will trigger a file restoration. Truncations and writes are blocked until the file is fully restored so that a restoration which only partially succeed does not leave the file in an indeterminate state with portions existing only on tape and other portions only in the disk file system. We chose layered file system technology as it permits us to focus on the data migration functionality, and permits end system administrators to choose the underlying file store technology. We chose the overlay layered file system instead of the null layer for two reasons: first to permit our layer to better preserve meta data integrity and second to prevent even root processes from accessing migrated files. This is achieved as the underlying file store becomes inaccessible once the dmfs layer is mounted. We are quite pleased with how the layered file system has turned out. Of the 45 vnode operations in NetBSD, 20 (forty-four percent) required no intervention by our file layer - they are passed directly to the underlying file store. Of the twenty five we do intercept, nine (such as vop_create()) are intercepted only to ensure meta data integrity. Most of the functionality was concentrated in five operations: vop_read, vop_write, vop_getattr, vop_setattr, and vop_fcntl. The first four are the core operations for controlling access to migrated files and preserving the user experience. vop_fcntl, a call generated for a certain class of fcntl codes, provides the command channel used by privileged user programs to communicate with the dmfs layer.

Studenmund, William↗

AVIRIS data quality for coniferous canopy chemistry

An assessment of AVIRIS data quality for studying coniferous canopy chemistry was made. Seven flightlines of AVIRIS data were acquired over a transect of coniferous forest sites in central Oregon. Both geometric and radiometric properties of the data were examined including: pixel size, swath width, spectral position and signal-to-noise ratio. A flat-field correction was applied to AVIRIS data from a coniferous forest site. Future work with this data set will exclude data from spectrometers C and D due to low signal-to-noise ratios. Data from spectrometers A and B will be used to examine the relationship between the canopy chemical composition of the forest sites and AVIRIS spectral response.

Swanberg, Nancy A.↗

Suppression of low temperature magnetic ordering in samarium nanoparticles

The role of finite size effects on magnetic order has been investigated in samarium nanoparticles prepared by physical vapor deposition. In this study, a dense layer composed of distinct nanoparticles with a mean particle diameter of 26 nm was deposited on a diamagnetic substrate. M(T) measurements identify the expected pair of antiferromagnetic ordering temperatures in the bulk Sm precursor, at 113 K and 14 K, where the magnetic unit cell for the lower ordering temperature is 10.36 nm along the c-axis. The high temperature ordering of the hexagonal sites in the Sm nanocrystals is slightly decreased with respect to that of bulk Sm, while the low temperature transition associated with the cubic sites is significantly suppressed. The observed changes are attributed to finite size effects, with ordering suppressed as the particle radius approaches the length of the magnetic unit cell, and surface moments become more prominent.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Geometric Assessment of PlanetScope Imagery

Commercial companies such as Maxar, Planet Labs, and BlackSky have built large archives of high resolution (1-3 m) Earth observing data. The high temporal resolution and global coverage of these satellites makes commercial satellite images ideal for scientists studying rapidly changing processes such as flooding and fires. The high spatial resolution allows scientists to push studies to a fine scale such as monitoring agricultural growth experiments or detecting vehicles for traffic management. Scientists using these data need to know geolocation accuracy, band-to-band registration (BBR), and pixel footprint size to best determine appropriate applications as well as what extra steps they will need to take to use the data. Here, we find those key geometric properties for images from Planet Labs’ SuperDove constellation. Geolocation accuracy is assessed relative to WorldView images at globally distributed cities, band-to-band registration (BBR) is examined for every image we acquired (200+ images), and pixel footprint sizes are calculated from edge responses of the images over Cal/Val sites in China, India, or USA both near launch time and 1+ years after launch. We find that SuperDove geolocation is highly self-consistent with average global offsets among SuperDove images of 3.80 m (1.27 pixels). Despite this self-consistency, relative geolocation accuracy (with WorldView images as reference) varies by location from 3.20 m – 28.09 m mean offset. SuperDove BBR is sub-pixel and varies by band, with a mean radial offset relative to red band varying from 0.39 - 1.13 m. SuperDove image footprint size improves after 1+ years in orbit, with an average footprint size of 3.41 pixels (10.24 m) soon after launch and 3.23 pixels (9.7 m) 1+ years after launch. The BBR and self-consistency offsets are relatively small, given the large footprint sizes. A similarly extensive investigation is in progress for Planet Labs’ Dove-R series.

Alana G. Semple↗

The Preservation of Climate‐Driven Landslide Dams in Western Oregon

Abstract Bedrock landsliding, including the formation of landslide dams, is a predominant geomorphic process in steep landscapes. Clarifying the importance of hydrologic and seismic mechanisms for triggering deep‐seated landslides remains an ongoing effort, and formulation of geomorphic metrics that predict dam preservation is crucial for quantifying secondary landslide hazards. Here, we identify >200 landslide‐dammed lakes in western Oregon and utilize dendrochronology and enhanced 14 C dating (“wiggle matching”) of “ghost forests” to establish slope failure timing at 20 sites. Our dated landslide dataset reveals bedrock landsliding has been common since the last Cascadia Subduction Zone earthquake in January 1700 AD. Our study does not reveal landslides that date to 1700 AD. Rather, we observe temporal clustering of at least four landslides in the winter of 1889/1890 AD, coincident with a series of atmospheric rivers that generated one of the largest regionally recorded floods. We use topographic and field analyses to assess the relation between dam preservation and topographic characteristics of the impounded valleys. In contrast to previous studies, we do not observe systematic scaling between dam size and upstream drainage area, though dam stability indices for our sites correspond with “stable” dams elsewhere. Notably, we observe that dams are preferentially preserved at drainage areas of ∼1.5 to 13 km 2 and valley widths of ∼25 to 80 m, which may reflect the reduced downstream influence of debris flows and the accumulation of mature conifer trees upstream from landslide‐dammed lake outlets. We suggest that wood accumulation upstream of landslide dams tempers large stream discharges, thus inhibiting dam incision.

Struble, William T.↗

Mercury Removal from Contaminated Water by Wood-Based Biochar Depends on Natural Organic Matter and Ionic Composition

Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl – ), nitrate (NO 3 – ), calcium (Ca 2+ ), and sodium (Na + ) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca 2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl – and Ca 2+ could still facilitate it. The ability of Ca 2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl – followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl – , forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl – was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl – : NOM and Ca 2+ : NOM, Hg(II) removal can still be effective with SWP700.

54 ENVIRONMENTAL SCIENCES↗

Spatial Study 2022: Water Column, Sediment, and Total Ecosystem Respiration Rates across the Yakima River Basin, Washington, USA (v2)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin and is associated with the manuscript “Sediment-associated processes account for most of the spatial variation in ecosystem respiration in the Yakima River basin” submitted to Nature Communications Earth & Environment (Garayburu-Caruso et al., in review). The dataset provides ecosystem metabolism estimates generated from streamMetabolizer (Appling et al.; 2018) using data collected during the same five-week period at 48 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Additionally, it includes the scripts used for the analysis and producing the figures in the manuscript. The contents include streamMetabolizer inputs and outputs and additional relevant data needed to generate the main manuscript results. The data included are: total ecosystem respiration, water respiration, calculated sediment-associated respiration, gross primary production outputs from the river corridor model for the Yakima River Basin, median grain size (d50), depth, dissolved oxygen, water temperature, pressure, and annual oxygen consumption. The associated GitHub repository can be found at https://github.com/river-corridors-sfa/SSS_metabolism. Samples collected during this study were labeled as “Second Spatial Study” or “SSS.” Raw time series sensor data, total suspended solids, and depth data from SSS were published at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1969566. A subset of data from the SSS samples were published in the contiguous United States (CONUS)-Scale Model-Sample (CM) study data package available at https://data.ess-dive.lbl.gov/view/doi:10.15485/1923689 that presents data from across the CONUS. They include dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), total nitrogen (TN), grain size, aerobic sediment respiration, dissolved oxygen (DO), and temperature. Parent IDs and Site IDs are consistent between the SSS and CM data packages, and they can be mapped directly so data across packages can be used together. Field metadata for the samples in this da This dataset is comprised of one main data folder with four subfolders. The main data folder contains of (1) file-level metadata; (2) data dictionary; (3) total/water column/sediment respiration; (4) gross primary production (GPP); (5) median grain size (d50); and (6) annual oxygen consumption. The “Figures” subfolder contains the figures used in the paper and all intermediate files (including geospatial files). The “Published_Data” contains a readme directing the user to download the public data to reproduce analyses and figures. The “Scripts” folder contains all scripts used in the analyses that were not part of running StreamMetabolizer. Lastly, the “Stream_Metabolizer” folder contains all files associated with running StreamMetabolizer including (1) model input files, (2) model output files, (3) processing scripts, (4) histogram plots of the outputs, and (5) an R project. All files are .csv, .pdf, .R, .Rmd, .Rproj, .html, .png, .txt, .qgz, .cpg, .dbf, .prj, .shp, .shp.ea.iso.xml, .shp.iso.xml, .shx, .sbn. ta package can be found at either link. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

Carbonic Anhydrase Variants Catalyze the Reduction of Dialkyl Ketones with High Enantioselectivity

Abstract Human carbonic anhydrase II (hCAII) naturally catalyzes the reaction between two achiral molecules—water and carbon dioxide—to yield the achiral product carbonic acid through a zinc hydroxide intermediate. We have previously shown that a zinc hydride, instead of a hydroxide, can be generated in this enzyme to create a catalyst for the reduction of aryl ketones. Dialkyl ketones are more challenging to reduce, and the enantioselective reduction of dialkyl ketones with two alkyl groups that are similar in size and electronic properties, is a particularly challenging transformation to achieve with high activity and selectivity. Here, we show that hCAII, as well as a double mutant of it, catalyzes the enantioselective reduction of dialkyl ketones with high yields and enantioselectivities, even when the two alkyl groups are similar in size. We also show that variants of hCAII catalyze the site‐selective reduction of one ketone over the other in an unsymmetrical aliphatic diketone. Computational docking of a dialkyl ketone to variants of hCAII containing the zinc hydride provides insights into the origins of the reactivity of various substrates and the high enantioselectivity of the transformations and show how a confined environment can control the enantioselectivity of an abiological intermediate.

Chen, Reichi↗

Diatom influence on the production characteristics of hydrate-bearing sediments: Examples from Ulleung Basin, offshore South Korea

The Ulleung Basin Gas Hydrate field expeditions in 2007 (UBGH1) and 2010 (UBGH2) sought to assess the Basin's gas hydrate resource potential. Coring operations in both expeditions recovered evidence of gas hydrate, primarily as fracture-filling (or vein type) morphologies in mainly silt-sized, fine-grained sediment, but also as pore-occupying hydrate in the coarser-grained layers of interbedded sand and fine-grained systems. A commonality across many of these occurrences is the presence of diatoms in the fine-grained sediment. Here we tested fine-grained sediment (median grain size <12.5 μm) associated with hydrate occurrences at four UBGH2 sites (UBGH2-2-2, UBGH2-3, UBGH2-6 and UBGH2-11) to investigate potential impacts of diatoms on efforts to extract methane from hydrate, or to tap hydrocarbon reservoirs beneath hydrate-bearing sediment. Two key considerations are: the extent to which diatoms control sediment mechanical properties, and the extent to which pore-water freshening, which occurs as gas hydrate breaks down during resource extraction, alters the diatom control on sediment mechanical properties. We conducted experiments to measure sediment index properties, sedimentation behavior and compressibility to address these considerations. We relied on scanning electron microscope (SEM) imagery and X-ray powder diffraction (XRD) to characterize the sediment mineralogy. Our high-level findings are that at the ~20–45% (by volume) diatom concentrations observed at these UBGH2 sites, sediment compressibility increases with diatom content, but diatoms only appear to increase porosity and permeability at the highest diatom concentration (~45%). Our measurements suggest in situ compression indices of 0.35–0.55 and permeabilities on the order of 0.01milliDarcies (1 × 10 -17 m 2 ) can be anticipated at these sites. Importantly, these properties are not expected to vary significantly upon pore water freshening that accompanies gas hydrate dissociation during production.

58 GEOSCIENCES↗

Hairy nanoparticles by atom transfer radical polymerization in miniemulsion

Polymer nanoparticles with various architectures and functionalities are promising materials in numerous fields. Miniemulsion polymerization is one of the suitable pathways to prepare polymer nanoparticles since each droplet could act as a “nanoreactor”. A “smart” atom transfer radical polymerization (ATRP) catalytic system comprising Cu-TPMA/DS – (TPMA = tris(2-pyridylmethyl)amine, DS – = dodecyl sulfate anion) ion pair catalyst was efficiently applied in miniemulsion ATRP at low catalyst concentrations. Herein, hairy nanoparticles consisting of hydrophobic poly(n-butyl methacrylate) (P(BMA/EGDMA), EGDMA = ethylene glycol dimethacrylate) network “core” and hydrophilic oligo(ethylene oxide) methyl ether methacrylate (OEOMA) chains as “hair” were prepared by miniemulsion ATRP and a successive chain extension by aqueous ATRP from the particle surface. The addition of an inimer, 2-(α-bromoisobutyryloxy)ethyl methacrylate (HEMA-iBBr) to the P(BMA/EGDMA) network introduced more ATRP initiation sites for ATRP of OEOMA, enabling adjustment of the particle size from >400 nm to <150 nm. The miniemulsion system remained stable after the one pot synthesis of P(BMA/EGDMA)-g-POEOMA and P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA, and the resulting polymer nanoparticles were re-dispersed in water for further modification. A zwitterionic monomer, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was grafted from P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA. The resulting hairy nanoparticles provide an avenue for the design and preparation of novel nanostructured materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗