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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Comparison of Geochemical Reactivity of Marcellus and Caney Shale Based on Effluent Analysis

ABSTRACT: In this comparative study, we analyzed the changes in elemental concentrations of hydraulic fracturing fluids after interaction with the Marcellus and Caney Shale formations. The focus was on assessing the inherent risks and environmental implications associated with flowback waters, including their impact on soil, ground, and drinking water quality, and human health safety. The chemical compositions of effluents were determined through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Mass spectrometry (ICP-MS). The Marcellus Shale, showed concentrations of Cd, averaging 0.380 ppm far exceeding safe water thresholds. Significant levels of As, Se, B, and Pb were detected in both shales, raising concerns about soil and water contamination. Analyzing the effluents from representative samples of sections of the Marcellus (S2 and S7) and Caney (R1 and R2) indicates different geochemical responses over 4 weeks of experiments. This comparison underscores the chemical changes and environmental considerations linked to hydraulic fracturing across shale formations, suggesting the value of tailored monitoring and regulatory measures for each type. 1. INTRODUCTION The Caney and Marcellus shales, differing in geology and geochemistry, represent distinct unconventional reservoirs. The Caney shale, is more ductile, with higher produced water volumes, (Smith et al., 2022) contrasts with the brittle Marcellus shale known for lower brine production but significant data availability. This study aims to elucidate the possible environmental health and safety issues that may arise from the hydraulic fracturing processes. The interaction between fracturing fluids and clays presents a significant challenge. The primary base of these fluids is water, which, when introduced to clay, can induce swelling and constrict flow pathways. This phenomenon is attributed to water molecules infiltrating the layers of clay, particularly in 2:1-type clays, leading to an increased distance between layers. To counteract this, clay stabilizers are employed (Awejori et al., 2021). Despite their effectiveness, these stabilizers are considered temporary solutions. Upon completion of the fracturing process, a concomitant amount of contaminated waters (flow back), with varied content is collected at the surface. From these, we can infer the geochemical reactions and the environmental challenges associated with these waters. Flowback waters can be reinjected or used for other purposes such as irrigation. This requires adequate screening and treatment for safe use.

Dje, L. B.↗
DOE OSTI2022

Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS

In this article, a novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N 2 , air, or O 2 gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O 2 -purging DNAN degradation rate was slightly enhanced, but most notably O 2 significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Flue-Gas Desulfurization Effluent Management using an Innovative Low-Energy Biosorpotion Treatment System to Remove Key Contaminants

Among the most critical water contaminants of concern affecting wide geographical regions and a number of industries and natural systems is selenium. Selenium found in surface, ground and wastewater in originates from natural sources, as well as industrial sources such as petroleum refineries, electronics manufacturing, pesticides, and coal power plants and mining also contribute to selenium contamination in water in the US. At high concentrations, selenium is toxic to human and wildlife. There are a number of technologies that have been used to treat selenium and other similar contaminants in water. Biological treatment of selenium has been used in the past to reduce soluble SeVI and/or SeIV to insoluble Se0, which is then filtered in the same vessel. The insoluble selenium (Se0) is then backwashed from the system and solids are separated for subsequent disposal, if they meet the leaching and water content criteria. In order to promote biological reduction to insoluble Se0, heating of bioreactor is needed in some applications, and excess food source (electron donor) is added so that all selenium can be filtered. An additional disadvantage of these systems is the significant amount of water lost due to extensive and frequent backwash and rinse cycles. When comparing the advantages and energy requirements of the various treatment technologies, RO membrane filtration immediately stands out due to the excessive energy expenditure needed to pump water across the membrane although RO is an effective way to remove selenium. In addition, RO requires extensive pretreatment, such as MF membrane, and frequent maintenance, rendering it an expensive option that may be out of reach for certain applications. In fact, although the performance was good during the pilot testing by the NSMP Working Group for treatment naturally occurring selenium in the surface water, the high electricity requirements and significant reject water stream made it an infeasible alternative. While conventional ion exchange maybe an effective treatment option, it requires frequent regeneration of the resin when applied to highly contaminated water, which leads to several tons of contaminant-laden, high-salinity brine that needs to be disposed off-site each day. One of the water systems in the west coast currently uses ion exchange for selenium treatment and has been trucking selenium laden hazardous brine waste weekly in the last several years. Pneumatic pumping and rinse water pumping required for ion exchange also increase the energy usage. In comparison, adsorption process is a passive treatment system where contaminated water comes in contact with an adsorption media in a vessel. Typically, there is no mixing, backwash, or recycle pumping required, thus significantly reducing the energy usage. A passive single-use adsorption system does not require backwash, thereby generating small amount of process waste, and producing the highest water yield among the alternatives. The energy and water efficiencies, and applicability for SeVI and SeIV are summarized in Table 1. Despite these benefits though, adsorption typically does not work for the most oxidized form of selenium (SeVI). The innovative biosorption process integrates both process to increase the treatment efficiency while minimizing energy, chemical, and time required to treat both SeVI and SeIV. Additional advantages include simple partial biological reduction with reduced on-site waste generation, which lead to water and electricity savings, and less operational need compared to biological treatment alone. This makes biosorption especially suitable for remote areas, where liquid backwash and brine disposal may be cost prohibitive or infeasible.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Manufacturing-induced contamination in common multilayerdielectric gratings

Contamination of pulse compression gratings during the manufacturing process is known to give rise to reduced laser damage performance and represents an issue that has not yet been adequately resolved. The present work demonstrates that the currently used etching methods introduce carbon contamination inside the etched region extending to a 50- to 80-nm layer below the surface. This study was executed using custom samples prepared in both, a laboratory setting and by established commercial vendors, showing results that are very similar. The laser-induced-damage performance of the etched and unetched regions in the grating-like samples suggest that contaminants introduced by etching process are contributing to the reduction of the laser-induced damage threshold.

42 ENGINEERING↗
DOE OSTI2024

Interpretation of large‐scale, long‐term electrical geophysical monitoring guided by a process simulation

Abstract Surface electrical resistivity tomography (ERT) was used at a waste site to monitor vadose zone changes in electrical properties as a proxy for contaminant flux over a span of 17 years. The BC Cribs and Trenches (BCCT) site at the Hanford site contains 20 disposal trenches and six disposal cribs. Wastes include a large inventory of technetium‐99 and large masses of nitrate and uranium‐238. ERT data were collected along 41 profiles in 2005 to characterize regions of elevated bulk electrical conductivity (BEC) associated with past liquid waste discharges. Previous analyses performed on samples from four boreholes showed a high correlation between nitrate concentration and BEC. In 2022, ERT data were re‐collected along the same profiles and six additional profiles in an area not previously surveyed. Compared to background uncontaminated areas, BEC was higher in contaminated areas at the waste sites. Given the correlation between nitrate concentration and BEC previously found at this site, ERT images show the spatial distribution and relative ionic concentration of vadose zone contaminants at BCCT. Between 2005 and 2022, ERT difference images showed a decrease in BEC surrounding most waste sites, with exceptions where there were known anthropogenic surface changes. An evaluation of recharge‐driven nitrate migration using synthetic flow and transport simulations showed that downward migration causes a decrease in BEC from the decrease in ionic strength at the trailing end of the plume where contaminants migrated downward. From this, we interpret ERT difference images as showing the predominant regions of downward ion flux.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Reaction of Hydrazine with Solution- and Vacuum-Prepared Selectively Terminated Si(100) Surfaces: Pathways to the Formation of Direct Si–N Bonds

Here, the reactivity of liquid hydrazine (N 2 H 4 ) with respect to H-, Cl-, and Br-terminated Si(100) surfaces was investigated to uncover the principles of nitrogen incorporation into the interface. This process has important implications in a wide variety of applications, including semiconductor surface passivation and functionalization, nitride growth, and many others. The use of hydrazine as a precursor allows for reactions that exclude carbon and oxygen, the primary sources of contamination in processing. In this work, the reactivity of N 2 H 4 with H- and Cl-terminated surfaces prepared by traditional solvent-based methods and with a Br-terminated Si(100) prepared in ultrahigh vacuum was compared. The reactions were studied with X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy, and the observations were supported by computational investigations. The H-terminated surface led to the highest level of nitrogen incorporation; however, the process proceeds with increasing surface roughness, suggesting possible etching or replacement reactions. In the case of Cl-terminated (predominantly dichloride) and Br-terminated (monobromide) surfaces, the amount of nitrogen incorporation on both surfaces after the reaction with hydrazine was very similar despite the differences in preparation, initial structure, and chemical composition. Density functional theory was used to propose the possible surface structures and to analyze surface reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Investigating the Impact of Absorbed Surface Impurities (CO, CO 2 , CH 4 , and H 2 O) on Getter Rate Performance

This report provides an overview of engineering and experimental efforts to establish a new capability for measuring H2 uptake rates for Tritium Producing Abosrber Rod (TPBAR) getter materials. This new system was used to gain a better understanding of the impact of contaminant species (CO 2 , CO, CH 4 , and H 2 O) on getter performance under relevant hydrogen uptake conditions (350 °C, 20 torr). Herein, we successfully established a high-resolution gravimetric sorption (HRGS) system in a flow through configuration that can measure sample mass changes with high resolution (1 µg or 10 µg) over long experiment times (days), high temperature, and varying pressures. We coupled this capability with an in-line universal gas analyzer (UGA) system to characterize potential surface chemistry side reactions occurring after contaminant gas exposure. The major findings of this study suggest that methane and CO have the most detrimental effects on getter H 2 uptake performance showing large changes in rate after exposure compared to CO 2 and water. The effect of these contaminant species did not influence getter sample capacity (~ 1.8 wt% H 2 ). After CO and methane exposure, changes in getter rate were accompanied by observable Ni-surface defects and pinholes via SEM imaging suggesting possible Ni- layer corrosion. Additionally, the increase in C and O signal in the zircaloy layer, observed via EDX, point to C and O species transport through the getter sample resulting in the formation of carbides and oxide species. Thus, co-exposure studies where mixed gases or water vapor are introduced together will be important to further understand what mechanisms are contributing to Ni-layer corrosion and changes in getter performance.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An improved oxygen reduction reaction activity and CO 2 -tolerance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ achieved by a surface modification with barium cobaltite coatings

Solid oxide fuel cells (SOFCs) cathode often suffers from the poisoning effect of the contaminants commonly encountered in air such as CO 2 . Here we report an effective approach to enhancing the activity and CO 2 tolerance of the state-of-the-art La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) cathode enabled by a coating of BaCoO 3-δ (BCO), as verified by the electrochemical testings, Raman analyses, and density functional theory calculations. When surface modified with a thin-film BCO coating, LSCF displays a much enhanced ORR activity and an improved durability against CO 2 . For example, anode supported SOFCs with the LSCF cathode coated with BCO coatings show a remarkable peak power density (Pmax) of 0.41 Wcm -2 and a significantly reduced degradation rate in current density of ~0.08% h -1 at 0.8 V and 700 °C for a period of 300 hs when humidified H2 (with 3 vol%H2O) was used as fuel and air with 8 vol% CO 2 as oxidant. The demonstrated performance is improved when compared with those of the cells with a blank LSCF electrode (a Pmax of ~0.36 Wcm -2 and a degradation rate of ~0.15% h -1 ) under the same conditions. Furthermore, the adsorption energy calculations suggests that BCO coating makes CO 2 adsorption much weaker than LSCF (-0.54 eV versus -1.07 eV).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Direct Chemical Vapor Deposition Synthesis of Porous Single-Layer Graphene Membranes with High Gas Permeances and Selectivities

Single-layer graphene containing molecular-sized in-plane pores is regarded as a promising membrane material for high-performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching-based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade-off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. Here in this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single-layer graphene membranes with the highest H 2 /CH 4 separation performances recorded to date (H 2 permeance > 4000 GPU and H 2 /CH 4 selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non-covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single-layer graphene exploits its tremendous potential as high-performance gas-sieving membranes.

chemical vapor deposition↗
DOE OSTI2022

Examining the effects of chemical cleaning, leaching, and partial dissolution on zinc and cadmium isotope fractionation in marine carbonates

The application of zinc (Zn) and cadmium (Cd) isotopes as palaeo-proxies in carbonate sediment is rapidly expanding due to their potential for tracing changes in biological productivity in the modern and past oceans. However, there are limited investigations into the chemical cleaning methods required to produce the most consistent and accurate data for these novel isotope systems. This could impact their use as palaeo-proxies to reconstruct ocean-atmosphere-climate interactions throughout Earth's history. To address this concern and expand the utility of the Zn and Cd stable isotope systems as palaeo-productivity tracers, the performance of two standard chemical cleaning protocols for acquiring robust and reliable Zn and Cd isotope datasets were assessed. These include (i) the Cd-cleaning method that uses a reductive step to selectively leach contaminating secondary iron (Fe)-manganese (Mn) (oxyhydr)oxide coatings from the carbonate surface, and an oxidative step that is used to remove post-depositional organic matter and sulphide precipitates; and (ii) the magnesium/calcium cleaning protocol that includes an oxidative step only, leaving secondary Fesingle bondMn (oxyhydr)oxide coatings largely intact. Well-preserved Holocene-, and Mesozoic-aged carbonate sediments were used to test the reliability of these two chemical cleaning methods. The Holocene samples comprised not only aliquots of bulk sediment, but also individual species of planktic and benthic foraminifera. Our results show that the best practice chemical cleaning method for retrieving consistent and accurate Zn and Cd isotope, and Zn/Ca and Cd/Ca datasets for carbonate sediments, requires both reductive and oxidative cleaning following the Cd-cleaning method. This differs from most methodological approaches applied to date that remove the reductive step from the chemical cleaning protocol and apply an oxidative step only, or no chemical cleaning at all. Inclusion of the reductive step in the chemical cleaning method typically shifts δ 66 Zn by ~0.1‰ lower and δ 114 Cd by 0.3‰ higher in the solid phase, while Zn/Ca and Cd/Ca typically decrease 2-fold. The benthic foraminifera, C. wuellerstorfi, that live in ocean bottom waters where the seawater Zn and Cd isotope composition is homogeneous display evidence of Zn and Cd isotope fractionation between seawater and carbonate on the order of 0.08 ± 0.08‰ (2SE, n = 4) and -0.25 ± 0.13‰ (2SE, n = 4), respectively, in agreement with experimental constraints. Furthermore, evidence of Zn isotope fractionation effects are recorded in a naturally-dissolved carbonate sediment, together with laboratory-controlled carbonate dissolution experiments. Based on these results, we recommend the Cd-cleaning method and the application of Zn and Cd isotope fractionation factors to accurately reconstruct past seawater Zn and Cd isotope compositions from carbonate sediments.

58 GEOSCIENCES↗
DOE OSTI2023

High-performance strategies for the recent MRSF-TDDFT in GAMESS

Multiple ERI (Electron Repulsion Integral) tensor contractions (METC) with several matrices are ubiquitous in quantum chemistry. In response theories, the contraction operation, rather than ERI computations, can be the major bottleneck, as its computational demands are proportional to the multiplicatively combined contributions of the number of excited states and the kernel pre-factors. Here, this paper presents several high-performance strategies for METC. Optimal approaches involve either the data layout reformations of interim density and Fock matrices, the introduction of intermediate ERI quartet buffer, and loop-reordering optimization for a higher cache hit rate. The combined strategies remarkably improve the performance of the MRSF (mixed reference spin flip)-TDDFT (time-dependent density functional theory) by nearly 300%. The results of this study are not limited to the MRSF-TDDFT method and can be applied to other METC scenarios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Method and apparatus for removal of microscopic contaminant particulates from superconducting radio frequency cavities and cavity strings

A method and apparatus for removing microscopic contaminant particulates by high pressure liquid nitrogen jet cleaning from the inner surface of a superconducting radio frequency cavity or a string of multiple cavities and transporting the removed particulates out of the inner space enclosed by the cleaned surfaces. The cleaning method of the invention suppresses field emission, resulting in an increase of the usable accelerating gradient of the cavities and a reduction of the activated radioactivity in accelerator components around cavities.

Geng, Rongli↗
DOE OSTI2020

Modeling, analysis, and code/data validation of DIII-D tokamak divertor experiments on ELM and non-ELM plasma tungsten sputtering erosion

Abstract We analyzed recent DIII-D tokamak tungsten divertor probe experiments using advanced, coupled, sputter erosion/redeposition, plasma, and surface response code packages. Modeling is done for ELMing H-mode, and L-mode plasmas, impinging on various size tungsten deposits on Divertor Material Evaluation System (DiMES) carbon probes. The simulations compute 3D, full kinetic, sub-gyromotion, impurity sputtering and transport, including changes in tungsten surface composition and response due to mixed deuterium and carbon ions irradiation. Per our analysis, ELM (edge localized mode) plasma sputtering in DIII-D mostly involves free-streaming high energy (∼500–1000 eV) D + and C +6 ions, with high near-surface plasma density. L-Mode sputtering is due to impurity sputtering (C, W) only, with lower density. All cases show complete redeposition of tungsten on the divertor, with significant redeposition on the tungsten spots themselves, and low self-sputtering. Comparison of ELM plasma gross tungsten erosion simulation results with in-situ spectroscopic data is good, as are code/data comparisons of net erosion using post-exposure Rutherford backscattering (RBS) data for the L-mode probes. The analysis, extrapolated to a full tungsten divertor, implies low net erosion and negligible plasma contamination from sputtering. These results support the use of high-Z plasma facing surfaces in ITER and beyond.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Metagenomic Methods for Addressing NASA's Planetary Protection Policy Requirements on Future Missions: A Workshop Report

Molecular biology methods and technologies have advanced substantially over the past decade. These new molecular methods should be incorporated among the standard tools of planetary protection (PP) and could be validated for incorporation by 2026. To address the feasibility of applying modern molecular techniques to such an application, NASA conducted a technology workshop with private industry partners, academics, and government agency stakeholders, along with NASA staff and contractors. The technical discussions and presentations of the Multi-Mission Metagenomics Technology Development Workshop focused on modernizing and supplementing the current PP assays. The goals of the workshop were to assess the state of metagenomics and other advanced molecular techniques in the context of providing a validated framework to supplement the bacterial endospore-based NASA Standard Assay and to identify knowledge and technology gaps. In particular, workshop participants were tasked with discussing metagenomics as a stand-alone technology to provide rapid and comprehensive analysis of total nucleic acids and viable microorganisms on spacecraft surfaces, thereby allowing for the development of tailored and cost-effective microbial reduction plans for each hardware item on a spacecraft. Workshop participants recommended metagenomics approaches as the only data source that can adequately feed into quantitative microbial risk assessment models for evaluating the risk of forward (exploring extraterrestrial planet) and back (Earth harmful biological) contamination. Participants were unanimous that a metagenomics workflow, in tandem with rapid targeted quantitative (digital) PCR, represents a revolutionary advance over existing methods for the assessment of microbial bioburden on spacecraft surfaces. The workshop highlighted low biomass sampling, reagent contamination, and inconsistent bioinformatics data analysis as key areas for technology development. Finally, it was concluded that implementing metagenomics as an additional workflow for addressing concerns of NASA's robotic mission will represent a dramatic improvement in technology advancement for PP and will benefit future missions where mission success is affected by backward and forward contamination.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

High fidelity ground deposition measurement with robots after explosive radiological dispersion

A team of scientists from the Remote Sensing Laboratory at Joint Base Andrews, Maryland, has assembled a remote-controlled robot to field a few sodium iodide scintillators of different size and shape 18″ above ground for measurement of ground deposition of gamma-emitting particles after an explosion of a radiological dispersal device. This system uses a high-precision differential GPS device with submeter accuracy for radiation mapping. The system is most useful in characterizing large-area contamination and detecting gamma radioactivity in invisible, submicron particulate debris deposited on the ground at surface level or embedded in subsurface up to 3″ deep. The system was assembled as part of a larger effort to integrate advanced radiological detection devices into autonomous or remote-controlled robotic systems to eliminate or minimize the need for emergency responders to enter areas that pose significant health and safety risks to humans following a major radiological incident or accident. Research into autonomous algorithms is required to develop automated robotic systems for radiological survey and characterization activities in highly contaminated areas. The scope of this project also includes developing communications pathways and supporting infrastructure capabilities for different types of robotic technologies. The expected result is an advanced autonomous robotic system with integrated radiation detection electronics that allows emergency response personnel to view data remotely and in real time for radiological emergency response and consequence management purposes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Borehole breakout modeling in arkose and granite rocks

The existence of a deep borehole in the Earth’s crust disturbs the local stresses and creates a stress concentration that may result in breakout and damage to the borehole. Maintaining wellbore integrity mitigates environmental impacts such as groundwater contamination, gas leakage to the atmosphere, and fluid spills and seepage at the surface. In this paper, the stability of deep boreholes (5 km) is examined by laboratory experiments and numerical models in the context of nuclear waste disposal in Israel. Two rock types in southern Israel are considered: the crystalline basement (granite) and the Zenifim Formation (arkose). A series of room-temperature triaxial rock deformation experiments were conducted at different confining pressures. This mechanical characterization was then used to parameterize the elastic properties and damage behavior of the rocks. This facilitated modeling the stability of the deep boreholes by two different formulations of damage rheology: a dynamic-oriented formulation used to model deformation immediately after the creation of the open hole and a quasi-static formulation used to model longer stress corrosion regime. The calibrated modeling results indicate greater stability with Zenifim arkose than the crystalline granite for deep borehole conditions despite the granite having a greater triaxial compressive strength. Dissipation associated with dilation and porous compaction in the arkose during deformation plays a significant stabilizing role in the borehole compared to crystalline rocks. These results suggest that common strength-based borehole stability assessment may lead to inaccurate predictions. Three-dimensional modeling of bottom-hole stress conditions and the effects of transient borehole geometry show conventional two-dimensional analysis may not be conservative when predicting borehole damage.

58 GEOSCIENCES↗
DOE OSTI2024

Interfacial dynamics mediate surface binding events on supramolecular nanostructures

The dynamic behavior of biological materials is central to their functionality, suggesting that interfacial dynamics could also mediate the activity of chemical events at the surfaces of synthetic materials. Here, we investigate the influence of surface flexibility and hydration on heavy metal remediation by nanostructures self-assembled from small molecules that are decorated with surface-bound chelators in water. We find that incorporating short oligo(ethylene glycol) spacers between the surface and interior domain of self-assembled nanostructures can drastically increase the conformational mobility of surface-bound lead-chelating moieties and promote interaction with surrounding water. In turn, we find the binding affinities of chelators tethered to the most flexible surfaces are more than ten times greater than the least flexible surfaces. Accordingly, nanostructures composed of amphiphiles that give rise to the most dynamic surfaces are capable of remediating thousands of liters of 50 ppb Pb 2+ -contaminated water with single grams of material. These findings establish interfacial dynamics as a critical design parameter for functional self-assembled nanostructures.

42 ENGINEERING↗
DOE OSTI2020

Arsenite oxyanions affect CeO 2 nanoparticle dissolution and colloidal stability

While highly reactive cerium oxide nanoparticles (CeO 2 NPs) are widely used in industry, their transport in aquatic systems is not well understood. To fill this knowledge gap, the interactions of CeO 2 NPs with arsenite (As 3+ ), a toxic metalloid and potential co-present contaminant, were investigated with respect to CeO 2 NP colloidal stability, dissolution, and surface redox reactions. Arsenite showed distinctive effects at different concentrations, with a high As 3+ concentration (10 –4 M) inducing 90% of CeO 2 NPs to settle from solution after 8 hours, while lower As 3+ concentrations (10 –5 or 10 –6 M) led to only 20% of CeO 2 NPs settling. The dissolution of NPs was most significant in the 10 –5 M As 3+ system owing to a lesser extent of aggregation, exposing more CeO 2 surface for dissolution. In the three As 3+ concentration systems, >97% of aqueous arsenic remained as As 3+ over 6 hours. On the NP surface, adsorbed As III was oxidized to As V , resulting in 58–70% of the adsorbed arsenic remaining as As III . Simultaneously Ce IV was reduced to Ce III , increasing Ce III on the CeO 2 NP surface from 17% (without arsenite) to 21–25% (with arsenite). Further mechanistic analyses revealed that the adsorption of arsenite was the main contributor to neutralizing the CeO 2 NP surface potential, enhancing particle sedimentation. These findings suggest that the fate and transport of CeO 2 NPs in our experimental systems are strongly affected by arsenite concentration and its adsorption on NPs. Here, the results also highlight the importance of the interplay between NP aggregation, oxidation, and dissolution in predicting the behaviors of CeO 2 NPs and associated toxic elements in aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗