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At least 1,441 records · Page 80

A Particle-Based Conditional Sampling Scheme for the Simulation of Transport in Fractured Rock With Diffusion Into Stagnant Water and Rock Matrix

In situ experiments and field-scale characterization studies have pointed out that, in fractured crystalline media, groundwater flow is highly channelized. This implies that, at the scale of a single fracture, only part of the fracture surface area is in contact with flowing water, while the rest of in-plane water is essentially stagnant and can be accessed by solutes via molecular diffusion. Despite their importance for contaminant retention, to date, there are no numerical or analytical approaches that could be used to assess the implication of stagnant water zones on solute transport in realistic large-scale Discrete Fracture Network-based models. In this study, we present an efficient and flexible algorithm for the simulation of transport in fractured rock with diffusion into stagnant water and rock matrix. The algorithm is a generalization of a previously developed numerical framework for time domain particle tracking in sparsely fractured rock. The key of the generalization is that total time in fracture (τ f ) is first evaluated using a Monte Carlo sampling and then a second sampling is performed conditioned on τ f . The algorithm has been successfully validated against existing independent solutions and the implication of diffusion into stagnant water and secondary diffusion into the matrix has been assessed for a realistic modeling scenario. The results show that, due to diffusion into stagnant water, contaminants are more strongly retarded. This increased retention is more significant for sorbing species, as a larger number of sorption sites is accessible. A high sensitivity to the flowing channel/stagnant water zone geometry has also been observed.

54 ENVIRONMENTAL SCIENCES↗

Continuous sensor suite measurements of weather, energy, soil and flux at four PumpHouse sites at the East River, Colorado

The purpose of this package is to monitor energy and water fluxes using a comprehensive set of sensors integrated on a tripod set up at 4 locations at the East River watershed in Colorado in the Upper Colorado River Basin as part of the Scientific Focus Area (SFA) research led by the Lawrence Berkeley National Lab (LBNL). This is a continuous sensor suite measurements of weather, energy, soil and flux at four East River pumphouse sites (ER-PHS1, ER-PHS2, ER-PHS3 and ER-PHS4) include: (1) soil CO2 concentration, CO2 flux and heat flux from soil surface; (2) photosynthetic active radiation flux at 1 m; (3) incoming/outcoming short and long wave radiation at 1 m, and user calculated net short and long wave radiation; (4) oxygen concentration and surface infrared temperature; (5) soil volumetric water content, temperature, and electrical conductivity at 10, 30, 60, 115 cm depth 115 cm depth; (6) soil matric potential and temperature at 30 cm depth; (7) incoming short wave radiation at 3 m height; (8) rainfall precipitation; (9) lightning strikes and strike distances; (10) wind direction and speed, maximum wind gust at 3 m; (11) air temperature, vapor pressure and barometric pressure at 3 m; (12) X _axis_level and Y_axis_level_(degree), tilt of the ATMOS 41 sensor; (13) maximum rainfall rate; (14) relative humidity sensor temperature at 3 m; (15) internally calculated vapor pressure deficit at 3 m with vapor pressure, relative humidity and sensor temperature measurements; (16) user calculated vapor pressure.These datasets contain data from Oct 11 2019 to March 20, 2020, and new datasets will be updated on annual basis. Files uploaded in Excel and Word, with copies in csv and pdf format.

54 ENVIRONMENTAL SCIENCES↗

Hierarchical Ion Interactions in the Direct Air Capture of CO 2 at Air/Aqueous Interfaces

The direct air capture (DAC) of CO 2 using aqueous solvents is plagued by slow kinetics and interfacial barriers that limit effectiveness in combating climate change. Functionalizing air/aqueous surfaces with charged amphiphiles shows promise in accelerating DAC; however, insight into these interfaces and how they evolve in time remains poorly understood. Specifically, competitive ion interactions between DAC reagents and reaction products feedback onto the interfacial structure, thereby modulating interfacial chemical composition and overall function. In this work, we probe the role of glycine amino acid anions (Gly - ), an effective CO 2 capture reagent, that promotes the organization of cationic oligomers at air/aqueous interfaces. These surfaces are probed with vibrational sum frequency generation spectroscopy and molecular dynamics simulations. Our findings demonstrate that the competition for surface sites between Gly - and captured carbonaceous anions (HCO 3 - , CO 3 2 -, carbamates) drives changes in surface hydration, which in turn tunes oligomer ordering. This phenomenon is related to a hierarchical ordering of anions at the surface that are electrostatically attracted to the surface and their ability to compete for interfacial water. These results point to new ways to tune interfaces for DAC via stratification of ions based on relative surface propensities and specific ion effects.

54 ENVIRONMENTAL SCIENCES↗

Electrophoretic Deposition of Platinum Nanoparticles using Ethanol-Water Mixtures Significantly Reduces Neural Electrode Impedance

We report platinum electrodes are critical components in many biomedical devices, an important example being implantable neural stimulation or recording electrodes. However, upon implantation, scar tissue forms around the electrode surface, causing unwanted deterioration of the electrical contact. We demonstrate that sub-monolayer coatings of platinum nanoparticles (PtNPs) applied to 3D neural electrodes by electrophoretic deposition (EPD) can enhance the electrode's active surface area and significantly lower its impedance. In this work we use ethanol-water mixtures as the EPD solvent, in contrast to our previous studies carried out in water. We show that EPD coating in 30 vol.% ethanol improves the device's electrochemical performance. Computational mesoscale multiparticle simulations were for the first time applied to PtNP-on-Pt EPD, revealing correlations between ethanol concentration, electrochemical properties, and coating homogeneity. Thereto, this optimum ethanol concentration (30 vol.%) balances two opposing trends: (i) the addition of ethanol reduces water splitting and gas bubble formation, which benefits surface coverage, and (ii) increased viscosity and reduced permittivity occur at high ethanol concentrations, which impair the coating quality and favoring clustering. A seven-fold increase in active surface area and significantly reduced in vitro impedance of the nano-modified neural stimulation electrode surfaces highlight the influence of ethanol-water mixtures in PtNP EPD.

36 MATERIALS SCIENCE↗

Use of Nucleating Agent NA11 in the Preparation of Polyvinylidene Fluoride Dual-Layer Hollow Fiber Membranes

Polyvinylidene fluoride (PVDF) dual-layer hollow fiber membranes were simultaneously fabricated by thermally induced phase separation (TIPS) and non-solvent induced phase separation (NIPS) methods using a triple orifice spinneret (TOS) for water treatment application. The support layer was prepared from a TIPS dope solution, which was composed of PVDF, gamma-butyrolactone (GBL), and N-methyl-2-pyrrolidone (NMP). The coating layer was prepared from a NIPS dope solution, which was composed of PVDF, N,N-dimethylacetamide (DMAc), and polyvinylpyrrolidone (PVP). In order to improve the mechanical strength of the dual-layer hollow fiber, a nucleating agent, sodium 2,2'-methylene bis-(4,6-di-tert-butylphenyl) phosphate (NA11), was added to the TIPS dope solution. The performance of the membrane was evaluated by surface and cross-sectional morphology, water flux, mechanical strength, and thermal property. Our results demonstrate that NA11 improved the mechanical strength of the PVDF dual-layer hollow fiber membranes by up to 42%. In addition, the thickness of the coating layer affected the porosity of the membrane and mechanical performance to have high durability in enduring harsh processing conditions.

36 MATERIALS SCIENCE↗

Evaluation of Monin‐Obukhov Similarity Theory Wind Profiles in Convective Storm Environments and Cold Pools at the ARM Southern Great Plains Atmospheric Observatory

Monin-Obukhov similarity theory (MOST) is widely used in numerical weather prediction to model surface fluxes of momentum, heat, and water vapor. However, MOST is based on assumptions of steady state and horizontally homogeneous turbulence that can lead to prediction errors in and around convective storms. To understand the nature of these errors, we used wind and eddy covariance flux measurements from the Atmospheric Radiation Measurement Southern Great Plains Atmospheric Observatory to evaluate MOST wind profiles in fair-weather and convective storm environments, specifically those of mesoscale convective systems and ordinary thunderstorms. MOST wind profiles agreed well with observations in fair-weather cases, while in convective storm cases the theory systematically overestimated shear in cold pools after gust front passage. Surface layer stability was found to be important in assessing MOST within convective storm environments. The overestimation of wind shear in cold pools suggests the role of non-local fluxes in transferring momentum downward. We discuss reasons for differences and agreement with past studies, and conclude with recommendations to improve prediction of surface winds and fluxes in convective storm simulations.

58 GEOSCIENCES↗

Unequal {110} Facets: The Potential Role of Intraparticle Heterogeneity and Facet Termination in Photoelectrochemical Activity of Single BiVO 4 Particles

BiVO 4 photoanodes are promising for solar water splitting, with photogenerated electrons and holes preferentially reacting at top {010} and lateral {110} facets, respectively. However, the mechanisms driving this facet-dependent reactivity remain unclear. Here, in this study, we investigate facet-dependent photocurrent and material heterogeneity using correlative scanning photoelectrochemical microscopy (SPCM), electron beam induced current (EBIC) mapping, and mid-IR scattering scanning near-field optical microscopy (s-SNOM). SPCM measurements of 62 BiVO 4 particles confirmed higher photocurrents at lateral {110} facets compared to top {010} facets, but unexpectedly revealed variations in photocurrent among lateral facets within the same particle. Variations in lateral facet surface termination could explain the intraparticle-level reactivity heterogeneity, consistent with theoretical predictions. Nano-FTIR spectroscopy and Raman microspectroscopy indicated significant materials chemistry heterogeneity within individual particles and facets that could be attributed to variations in lattice vibration distortions that enhance the overlap between Bi 6s and O 2p orbitals. The increased orbital overlap is significant as it potentially increases hole mobility in the valence band and potentially explains the lateral facet-dependent charge separation efficiency observed in photocurrent maps. Facet-dependent electrical and EBIC measurements showed no space charge regions at interfacet junctions or metal-BiVO 4 contacts under vacuum, suggesting that photogenerated holes beneath top {010} facets are unlikely to transport to lateral {110} facets to drive water/sulfite oxidation. These findings indicate the potential influence of distinct bulk properties and surface termination chemistries across different particles and facets, highlighting the importance of carefully controlling defects and surface chemistry during sample growth to optimize photocatalytic performance.

BiVO4↗

Earth System Model Simulations of Ameriflux sites using dynamic roots and dynamic leaf to root allocation

This data package contains point-scale Earth System Model simulations run with DOE's E3SM Model. The package includes four sets of simulations, one set of simulations run in the default configuration, a second set of simulations run with the dynamic root module enabled, the third set with dynamic leaf to fine root allocation, and the fourth with the combination of dynamic roots and dynamic allocation. These simulations were run in point mode a Ameriflux sites, US-MMS, US-Moz, US-Syv, and US-NR1. These datasets can be used to assess the impact that dynamic roots have on Land Surface fluxes such as carbon and water. The simulations were run with atmospheric forcing from the Global Soil Wetness Project. We provide specifically here Gross Primary Production, Transpiration, relative root fraction per soil layer as well as Air Temperature, Precipitation and all the parameterizations used for the simulations. Our purpose for generating and analyzing these simulations was to assess the role that root dynamics and foraging for water has in the recovery timescale of ecosystems following climate perturbation. All data provided are in the "netcdf" format using standard CF-1 (Climate and Forecast) Convention. The data are all machine readable using various software platforms including Matlab, NCO, Panoply and R.

54 ENVIRONMENTAL SCIENCES↗

Viral community analysis in a marine oxygen minimum zone indicates increased potential for viral manipulation of microbial physiological state

Microbial communities in oxygen minimum zones (OMZs) are known to have significant impacts on global biogeochemical cycles, but viral influence on microbial processes in these regions are much less studied. Here we provide baseline ecological patterns using microscopy and viral metagenomics from the Eastern Tropical North Pacific (ETNP) OMZ region that enhance our understanding of viruses in these climate-critical systems. While extracellular viral abundance decreased below the oxycline, viral diversity and lytic infection frequency remained high within the OMZ, demonstrating that viral influences on microbial communities were still substantial without the detectable presence of oxygen. Viral community composition was strongly related to oxygen concentration, with viral populations in low-oxygen portions of the water column being distinct from their surface layer counterparts. However, this divergence was not accompanied by the expected differences in viral-encoded auxiliary metabolic genes (AMGs) relating to nitrogen and sulfur metabolisms that are known to be performed by microbial communities in these low-oxygen and anoxic regions. Instead, several abundant AMGs were identified in the oxycline and OMZ that may modulate host responses to low-oxygen stress. We hypothesize that this is due to selection for viral-encoded genes that influence host survivability rather than modulating host metabolic reactions within the ETNP OMZ. Together, this study shows that viruses are not only diverse throughout the water column in the ETNP, including the OMZ, but their infection of microorganisms has the potential to alter host physiological state within these biogeochemically important regions of the ocean.

59 BASIC BIOLOGICAL SCIENCES↗

Estuarine nutrient pollution impact reduction assessment through euphotic zone avoidance/bypass considerations

The feasibility of reducing nutrient pollution impact by redirecting the effluent to depths below the euphotic zone was investigated for the deep estuarine Puget Sound region of the Salish Sea in the Pacific Northwest of America. The hypothesis tested was that the thickness of the outflow layer in deep estuaries may be greater than the euphotic zone depth, allowing a fraction of nutrients to be exported out passively through the layers immediately below. The euphotic zone depth in Puget Sound varies from 8 to 25 m while the depth of the outflow layer can reach up to ≈ 60 m. Outfall relocation strategies were tested on 99% of the anthropogenic nutrient loads currently delivered to Puget Sound. The impact was quantified using the previously established biophysical Salish Sea Model, using gross primary production and exposure to low dissolved oxygen (DO) levels as the metric (< 2 mg/L for hypoxia and < 5 mg/L for impairment). Eliminating nutrient pollution (above natural) from rivers and wastewater reduced hypoxia exposure by 8.1% and 11.2%, respectively. Relocating the outfalls to deeper waters resulted in improvements, but only in the sill-less sub-basins such as Whidbey, where hypoxia and DO impairment exposure decreased (7.9% and 6.8%, respectively). The presence of multiple sills and circulation cells in Puget Sound resulted in increased exposure and rendered nutrient bypass goals unfeasible as originally envisioned. However, an alternate nutrient export pathway was identified through bottom exchange flow out of Puget Sound via Whidbey Basin and Deception Pass. An unexpected reduction in the exchange outflow magnitude (≈ 4%) due additional (22%) freshwater discharged to the estuary bottom was also noted. The potential loss in circulation strength due to rerouting of natural surface freshwater through submerged deep-water outfalls is identified as a new unforeseen anthropogenic impact.

54 ENVIRONMENTAL SCIENCES↗

Integrating fine root diameter and watershed mapping to characterize rhizosphere hydrology

Root morphology and soil hydraulic characteristics were integrated using watershed distance mapping to show water distribution and uptake across the plant-soil interface. Poplar (Populus deltoides, P. trichocarpa), maize (Zea mays), juniper (Juniperus virginiana), grape (Vitis rotundifolia) and maple (Acer saccharum) seedlings were grown in sand, after which root diameter and soil water dynamics were assessed via sequential neutron radiography. Three local soil regions (root-soil interface or edge, rhizosphere, bulk soil) were classified based on both radial distance from the root surface and diameter of the nearest root, from which changes in water content and distribution were characterized using digital image processing. Water content dynamics across the rhizosphere showed two different species-independent processes: a consistently elevated water content at the root-soil edge interface which increased with root diameter, and hysteresis as the rhizosphere transitioned to bulk soil (~0.5 cm from the root), independent of root diameter. Water uptake per unit root surface area declined exponentially with root diameter, independent of species. Results highlight the species-independent hydrologic characteristics of the rhizosphere and the potential for evaluating them in a local spatially connected soil context. Avenues for improved integration of soil and root characteristics are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Demonstration of neutron radiation-induced nucleation of supercooled water

In this study, we present direct evidence for neutrons causing nucleation of supercooled water. Highly purified water (20 nm filtration) is cooled to well below freezing (as low as −20 °C) with a radioactive calibration source of neutrons/gamma-rays either present or removed during each of many control cooling runs for the same volume of water. When it is primarily neutrons irradiating the sample bulk, the non-equilibrium freezing point (also known as the “supercooling point”) is, on average, +0.7 °C warmer than the control equivalent, with a statistical significance of greater than 5 Sigma, with systematic uncertainty included. This effect is not observed with water in the presence of gamma-rays instead of neutrons. While these neutrons should have theoretically had sufficient energy to mount the energy barrier, corroborating our results, their raising of supercooling temperature has never been reported experimentally to the best of our knowledge. The potential to use deeply supercooled solutions, not only water, as metastable detectors for radiation and perhaps dark matter or neutrino physics presents now a new avenue for exploration.

Szydagis, Matthew↗

Challenges in the study of chemistry and photochemistry at air–water interfaces: Toward in situ monitoring of reaction kinetics with spectroscopic techniques

Air–water interfaces, including those on droplet surfaces, have been the subject of many recent experiments due to their propensity for unique chemistry. Here, in this study, an overview of some recent advancements in understanding interfacial reaction kinetics is provided, highlighting non-surface-specific methods—such as mass spectrometry—compared with the advantages of surface-specific techniques—such as reflection–absorption spectroscopy, sum frequency generation, and photoelectron spectroscopy. This Perspective discusses the information depth and time constraints of common surface-specific spectroscopic methods that need to be addressed to monitor interfacial chemistry in situ and uses a few key examples from the literature as case studies. It concludes by advocating for the continued development of advanced spectroscopic methods to further investigate interfacial chemistry, underscoring the need for interdisciplinary collaboration to bridge the gap between molecular-level insights and macroscopic observations in future research.

Air-water interface↗

Effect of Ambient Organic Acids on the Water Structure at ${\rm TiO}_{2}$ Interfaces

A molecular-level understanding of the effects of ambient organic compounds on the wettability of titanium dioxide ( ${\rm TiO}_{2}$ ) surfaces is relevant to many of its energy-related and environmental applications. Herein, we focus on two common atmospheric carboxylic acids, formic and acetic acid, and characterize their adsorption/ desorption at the aqueous interfaces of anatase and rutile ${\rm TiO}_{2}$ using molecular dynamics with an ab initio deep neural network potential. Our simulations show that these acids prefer to be localized in the interfacial water layers close to the ${\rm TiO}_{2}$ surface where they are stabilized by the interaction/exchange of their acid proton with a surface oxygen, rather than chemisorb at the surface Ti sites by displacing the adsorbed water. Notably, these acids make the surface of anatase hydrophobic, whereas the larger fraction of adsorbed water dissociation can offset their effect on rutile. Furthermore, these results provide a picture where carboxylic acids control the wettability of ${\rm TiO}_{2}$ largely through acid-base chemistry at the interface rather than chemisorption on the oxide surface, a finding that can help improve the design of self-cleaning surfaces and photocatalytic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Acidities of MgO surface sites: implications for the formation mechanism of Mg(OH) 2

The hydroxylation of periclase (MgO) to brucite (Mg(OH) 2 ) is thought to be an important intermediate step when using MgO to capture CO 2 from the atmosphere. However, the mechanism of hydroxylation of MgO to form Mg(OH) 2 is poorly understood. In this work, we used atomic-scale density functional tight binding simulations coupled with the metadynamics rare event method to analyze the surface chemistry of MgO and the acid dissociation equilibrium constants (pK a ) of its surface sites. The method and parameters were validated by calculating the pK a for hydroxylation of the first shell water bound to aqueous Mg 2+ ion. The pK a value derived using a probabilistic method was 12.3, which is in fair agreement with the accepted value of 11.4, with the difference between them equal to a ∼5 kJ mol −1 error in the calculations. We then extended these pK a calculations to probe the hydroxylation reactions of the surface sites of the MgO(100)–water interface, arriving at pK a s of 5.4 to deprotonate terminal water molecules bound to the surface magnesium sites (η-OH 2 or 〉MgOH 2 ), and 13.9 to deprotonate hydroxylated bridging oxygen sites (μ 5 -oxo or 〉O). Hydroxide (OH − ) adsorption on the surface was also probed and found to be less thermodynamically favorable than deprotonation of the terminal water molecule. The plausibility of the computed pK a s was verified using an activity-based speciation model and compared to pH measurements of water equilibrated with MgO nanoparticles and single crystals. The model predicted a solution pH of 7.1 when surface sites buffered and the pH of 12.0 when MgO dissolution dominated. These are close to the experimental initial solution pHs of 7–7.5 and the long term pHs of ∼10.5. The similarity suggests that the calculated pK a values from the DFTB+/metadynamics simulations are plausible and that these methods can be a useful tool to probe reaction mechanisms involving covalent bonds.

Adapa, Sai Krishna Reddy [Oak Ridge National Labor↗

Historical global Earth System Model simulations with E3SM's dynamic root module

This data package contains global-scale Earth System Model simulations run with DOE's E3SM Model. The package includes one set of simulations run in the default configuration and a second set of simulations run with the dynamic root module enabled. These two datasets can be used to assess the impact that dynamic roots have on Land Surface fluxes such as carbon and water. The outputs are provided here on a 0.5 x 0.5 global grid at monthly resolution. The simulations were run with atmospheric forcing from the Global Soil Wetness Project. We provide specifically here Gross Primary Production, Transpiration, relative root fraction per soil layer as well as Air Temperature, Precipitation and all the parameterizations used for the simulations. Our purpose for generating and analyzing these simulations was to assess the role that root dynamics and foraging for water has in the recovery timescale of ecosystems following climate perturbation. All data provided are in the "netcdf" format using standard CF-1 (Climate and Forecast) Convention. The data are broken up into 20 year chunks to facilitate easier read-in. The data are all machine readable using various software platforms including Matlab, NCO, Panoply and GrADS.

54 ENVIRONMENTAL SCIENCES↗

Autonomous Infrared and Small (Wide) Angle X-Ray Scattering (IR-S(W)AXS) Capability

Thin water films are 2-D, nanoconfined layers that form on solid surfaces exposed to humid atmospheres—environments ubiquitous across catalysis, corrosion science, soil science, and subsurface geochemistry. At relative humidity (RH) values below saturation, these films are Å–nm thick and exhibit properties that differ sharply from bulk water, including disrupted H-bonding and impeded mass transport. Owing to their high surface-to-volume ratio, dissolution of the solid can rapidly drive strong supersaturation with respect to secondary phases. Reactivity in thin water films is highly sensitive to film thickness, and critically, thickness evolves during reaction because the hygroscopicity of the interfacial system changes as ions accumulate or diminish in the film and as reaction products transform. To accurately probe and control these dynamics, a capability is needed that can measure and automatically maintain a constant water-film thickness while simultaneously monitoring solid dissolution, nucleation, and growth. This project developed an autonomous Infrared/Small Angle X-ray Scattering-Wide Angle X-ray Scattering (IR/(W)SAXS) for investigating reactivity in thin water films on solid surfaces exposed to humidified gases. The capability consists of an IR spectrometer, a (W)SAXS instrument, and a mass flow controller system for generating variably humidified gas flows to a custom reaction cell. Progress on each of the major components of the capability are detailed below.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemical Impacts of Potential CO2 and Brine Leakage on Groundwater Quality with Quantitative Risk Assessment: A Case Study of the Farnsworth Unit

Potential leakage of reservoir fluids is considered a key risk factor for geologic CO2 sequestration (GCS), with concerns of their chemical impacts on the quality of overlying underground sources of drinking water (USDWs). Effective risk assessment provides useful information to guide GCS activities for protecting USDWs. In this study, we present a quantified risk assessment case study of an active commercial-scale CO2-enhanced oil recovery (CO2-EOR) and sequestration field, the Farnsworth Unit (FWU). Specific objectives of this study include: (1) to quantify potential risks of CO2 and brine leakage to the overlying USDW quality with response surface methodology (RSM); and (2) to identify water chemistry indicators for early detection criteria. Results suggest that trace metals (e.g., arsenic and selenium) are less likely to become a risk due to their adsorption onto clay minerals; no-impact thresholds based on site monitoring data could be a preferable reference for early groundwater quality evaluation; and pH is suggested as an indicator for early detection of a leakage. This study may provide quantitative insight for monitoring strategies on GCS sites to enhance the safety of long-term CO2 sequestration.

58 GEOSCIENCES↗