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At least 145 records · Page 8

Reactive transport modeling of organic carbon degradation in marine methane hydrate systems

Abstract Natural methane hydrate has often been observed in sand layers that contain no particulate organic carbon (POC), but are surrounded by organic-rich, fine-grained marine muds. In this paper, we develop a reactive transport model (RTM) of a microbially-mediated set of POC degradation reactions, including hydrolysis of POC driven by extracellular enzymes, fermentation of the resulting high-molecular weight dissolved organic carbon (HMW-DOC), and methanogenesis that consumes low-molecular weight dissolved organic carbon (LMW-DOC). These processes are mediated by two groups of microbes, fermenters and methanogens that are heterogeneously distributed in different lithologies, with the largest numbers of microbes in the large pores of coarse-grained layers. We find that the RTM can reproduce methane hydrate occurrences observed in two different geological environments, at Walker Ridge Site 313-H (Gulf of Mexico) and IODP Site U1325 (Cascadia Margin). We also find that microbes can degrade POC even if they are physically separated, as extracellular enzymes and DOC can diffuse away from where they are produced by microbes. Microbial activity is highest at relatively early times after burial at shallow depths and near lithological boundaries, where concentration gradients transport solutes to intervals that contain the most microbes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Drawing on Membrane Photocatalysis for Fouling Mitigation

Photocatalysis is an effective and environmentally friendly approach for degrading organic pollutants, particularly in scenarios where sunlight can be utilized as the energy source. Opportunities are emerging to apply materials and methods from photocatalytic pollutant degradation to address the challenge of fouling. Membrane fouling, attributed to organic foulants, is a prevalent problem for all membrane-based technologies and represents a major deleterious impact on membrane performance. Integration of tactics developed in photocatalysis more broadly to membranes reveals new strategies for membrane fouling control-an approach taken by an increasing number of researchers. Furthermore, this review summarizes key developments in photocatalytic materials and methods in water treatment and presents recent progress in the development of processes for photocatalytic alleviation of membrane fouling, including photocatalyst design and modification strategies aimed at enhancing photocatalytic efficiency, as well as different configurations of photocatalysis-membrane systems (PMS). Perspectives on future research and development opportunities for photocatalytic membrane fouling control are also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong and recyclable bio-derived poly(ester amide) hot-melt adhesive

Bio-based adhesives offer inherent advantages over conventional petrochemical-derived systems, including renewable sourcing, reduced environmental impact and potential degradability. However, most bio-based adhesives suffer from poor adhesion strength, limited substrate compatibility and a lack of chemical recyclability. Here, in this work, we present a bio-derived multiblock poly(ester amide) adhesive that leverages microphase segregation between different segments to reconcile mechanical robustness with strong interfacial bonding. Notably, this multiblock architecture is accessed through a one-pot, selective acceptorless dehydrogenative polymerization, obviating the need for multistep synthesis. The materials exhibit excellent adhesion across a range of substrates including metals, glass and wet wood surpassing commercial benchmarks, while also demonstrating thermal stability, tunable mechanical properties and closed-loop chemical recyclability even in the presence of other commodity plastics. Furthermore, the adhesive strength of these materials could be tuned for various potential applications through control over the chemical composition of the polymer. By integrating renewable feedstocks, high-performance functionality and efficient chemical circularity within a single platform, this work provides a viable pathway toward more sustainable adhesive technologies and contributes to advancing circular materials manufacturing.

09 BIOMASS FUELS↗

Compositional analysis of organosolv poplar lignin by using high-performance liquid chromatography/high-resolution multi-stage tandem mass spectrometry

Organosolv treatment is an efficient and environmentally friendly process to degrade lignin into small compounds. The capability of characterizing the individual compounds in the complex mixtures formed upon organosolv treatment is essential for the optimization of the further lignin conversion processes and for the rational genetic engineering of plants used to produce lignin in order to improve lignin properties. In this study, an organosolv poplar lignin sample was initially analyzed by high-resolution mass spectrometry coupled with negative-ion mode electrospray ionization ((-)ESI HRMS). Lignin monomers and dimers were found to constitute the majority of the compounds in the organosolv lignin sample. Larger lignin oligomers, such as trimers and tetramers, and some not lignin-related compounds, were also detected. A high-performance liquid chromatograph/linear quadrupole ion trap/orbitrap mass spectrometer capable of multi-stage high-resolution tandem mass spectrometry experiments (HRMS n ), equipped with an (-)ESI source (HPLC/(-)ESI HRMS n ), was employed to separate the unknown compounds in the organosolv mixture and to obtain structural information for the deprotonated compounds via collision-activated dissociation (CAD) HRMS n experiments. To improve the understanding of the CAD behavior of deprotonated lignin-related compounds, 16 deprotonated model compounds with different functionalities and linkage types were examined. This approach enabled the assignment of likely structures for several lignin monomers, dimers, trimers, and tetramers, and some not lignin-related compounds, most likely fatty acids. Based on the proposed structures, compounds in the organosolv lignin sample contain β-O-4, 5–5, β-5, and possibly also 4-O-5 linkages. Most compounds contain G- and S-monomeric units although a small amount of H-units were also detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the Limits of EM Based Detection of Control Logic Injection Attacks In Noisy Environments

The difficulty in applying traditional security mechanisms in Industrial Control System (ICS) environments makes a large portion of these mission-critical assets vulnerable to cyber attacks. Therefore, there is a dire need for the development of novel security mechanisms specifically designed to protect such critical systems. Recently a lot of attention has been given to mechanisms that exploit the EM emanations of devices for defense purposes. Such practices may lead to the development of robust external and non-intrusive anomaly detection systems. Nevertheless, the majority of current work in the area neglects to consider the implications of real-life environments, particularly environmental noise. In this work, we explore the limits of EM-based anomaly detection towards identifying injection attacks in control logic software in noisy environments. Our study conducted upon both synthetically generated and real signals identified that indeed environmental noise might significantly degrade the accuracy of the anomaly detection process. Experiments done upon synthetic data indicated that assuming that signals are captured with high sampling rates, even minor code injections can be detected with above-90% accuracy in noisy environments where SNR is up to -2dB. This is true even if naive detection methods are considered. Moreover, experiments done using a real-life testbed attest that even single-instruction injections can be detected with near-perfect accuracy in relatively clean environments. Finally, noise-elimination techniques can drastically improve the reliability of the detection mechanism even in noisy environments.

97 MATHEMATICS AND COMPUTING↗

Spatially Resolved Raman Spectroscopic Investigation of Uranyl Fluoride: A Case Study in the Importance of Instrument Optimization

Raman spectroscopy is an emerging technique for rapid and nondestructive analysis of nuclear materials for forensic and nonproliferation applications as it is a powerful tool for distinguishing multiple chemical forms of materials with similar stoichiometries. Recent developments in spectroscopic software have enabled rapid data collection with high-speed Raman spectroscopic mapping capabilities. However, some uranium-rich materials are susceptible to degradation in humid air and/or laser-induced phase transformations. To mitigate environmental or measurement-related sample degradation of potential samples of interest, we have taken a systematic approach to define optimized data collection parameters for high-throughput measurements of uranyl fluoride (UO 2 F 2 ), which is an important intermediate material in the nuclear fuel cycle. First, we systematically describe the influence of optical magnification (5× to 100×), laser power, and exposure time on obtained signal for identical particles of UO 2 F 2 and find that at low laser power and exposure times, comparable signal is obtained regardless of optical magnification. Second, we ensure sample integrity during data collection, and third, collect spectroscopic maps that employ optimized parameters to reduce the time required to obtain spatially resolved spectroscopic information. Reductions of 90% and 99% in measurement times are discussed as they relate to differences in resolving spectroscopic features of particles in identical mapping areas. Finally, during this work, we found that additional data processing options were needed and thus developed a customized Python script for importing, processing, analyzing, and visualizing Raman spectroscopic map data.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Digital Engineering and Cybersecurity Decision Analysis in Early Phases of SMR-Driven IES Projects

Considerable efforts are underway to ensure cybersecurity is integrated into the systems engineering lifecycle. Cyber-informed engineering and security-by-design frameworks are intended to identify and engineer out cybersecurity risks throughout the lifecycle. While these approaches are valuable for promoting the need to include cybersecurity considerations in early design phases to create more secure systems, they may not consider the entirety of digital risks. Digital risks in a digital instrumentation and control system include adversarial and unintentional risks from internal and external factors, such as human performance errors, design flaws, environmental conditions, and equipment degradation or failure. This report provides a detailed discussion on digital risk prior to describing the background and concept of operations for a small modular reactor-driven integrated energy system connected to industrial applications. The challenges of competing objectives and competing stakeholder requirements are discussed and the impacts on digital engineering, security considerations, and interdependencies are evaluated for mission-level, facility-level, and system-level decisions.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Siena College 2022 MRA Genome Announcement Narrative - 6 Isolates

Soil bacteria and endospore forming bacteria in particular play critical environmental roles in biomass degradation, plant health, and many have also been sources for commercially important secondary metabolites including antibiotics. Sequencing multiple isolates of known species also can identify new genes and gene clusters not found in other members of the same species, increasing our understanding of microbial diversity.

59 BASIC BIOLOGICAL SCIENCES↗

Experimental Investigation of Steel-Borne Acoustic Pulses for Fault Pinpointing in Pipe-Type Cable Systems: A Scaled-Down Model Approach

Pipe-type cable systems, including high-pressure fluid-filled (HPFF) and high-pressure gas-filled cables, are widely used for underground high-voltage transmission. These systems consist of insulated conductor cables within steel pipes, filled with pressurized fluids or gases for insulation and cooling. Despite their reliability, faults can occur due to insulation degradation, thermal expansion, and environmental factors. As many circuits exceed their 40-year design life, efficient fault localization becomes crucial. Fault location involves prelocation and pinpointing. Therefore, a novel pinpointing approach for pipe-type cable systems is proposed, utilizing accelerometers mounted on a steel pipe to capture fault-induced acoustic signals and employing the time difference of arrival method to accurately pinpoint the location of the fault. The experimental investigations utilized a scaled-down HPFF pipe-type cable system setup, featuring a carbon steel pipe, high-frequency accelerometers, and both mechanical and capacitive discharge methods for generating acoustic pulses. The tests evaluated the propagation velocity, attenuation, and pinpointing accuracy with the pipe in various embedment conditions. The experimental results demonstrated accurate fault pinpointing in the centimeter range, even when the pipe was fully embedded, with the acoustic pulse velocities aligning closely with the theoretical values. These experimental investigation findings highlight the potential of this novel acoustic pinpointing technique to improve fault localization in underground systems, enhance grid reliability, and reduce outage duration. Further research is recommended to validate this approach in full-scale systems.

Moutassem, Zaki↗

Hole-transport layer-dependent degradation mechanisms in perovskite solar modules

It is imperative to understand how the design of perovskite solar modules (PSMs) affects their degradation mechanisms and byproducts under environmental stressors to enable their long-term reliability. This work reports on the impact of the hole-transport layer (HTL) on thermal cyclability and degradation mechanisms of p–i–n PSMs by comparing 3 HTLs: NiO x , MeO-2PACz (a self-assembled monolayer), and a bilayer HTL of MeO-2PACz on NiO x . We observe surprising thermal cyclability from a performance standpoint despite generating clear degradation products. We find that without a fully dense HTL, seemingly insignificant moisture/oxygen ingress through the edge of the PSMs can lead to rapid destabilization of the metal halide perovskite (MHP) layer due to reactions between MHP degradation byproducts and the indium-tin oxide layer. We also show that illumination-induced cation phase segregation is dependent on the illumination of an inactive area (regions of the substrate uncovered by the rear electrode). As such, we find that a dense interface between the MHP and ITO is necessary for chemically robust PSMs and highlight criteria for testing field-relevant configurations in lab-scale architectures.

14 SOLAR ENERGY↗

Restoring Soil Fertility on Degraded Lands to Meet Food, Fuel, and Climate Security Needs via Perennialization

A continuously growing pressure to increase food, fiber, and fuel production to meet worldwide demand and achieve zero hunger has put severe pressure on soil resources. Abandoned, degraded, and marginal lands with significant agricultural constraints—many still used for agricultural production—result from inappropriately intensive management, insufficient attention to soil conservation, and climate change. Continued use for agricultural production will often require ever more external inputs such as fertilizers and herbicides, further exacerbating soil degradation and impeding nutrient recycling and retention. Growing evidence suggests that degraded lands have a large potential for restoration, perhaps most effectively via perennial cropping systems that can simultaneously provide additional ecosystem services. Here we synthesize the advantages of and potentials for using perennial vegetation to restore soil fertility on degraded croplands, by summarizing the principal mechanisms underpinning soil carbon stabilization and nitrogen and phosphorus availability and retention. We illustrate restoration potentials with example systems that deliver climate mitigation (cellulosic bioenergy), animal production (intensive rotational grazing), and biodiversity conservation (natural ecological succession). Perennialization has substantial promise for restoring fertility to degraded croplands, helping to meet future food security needs.

54 ENVIRONMENTAL SCIENCES↗

Detection and Screening of Organic Contaminants in A Riverine System of Georgia Using Non-Targeted Analysis

Numerous organic chemicals exist within aquatic environments, yet effectively screening and prioritizing them is a huge challenge. This study provides a comprehensive investigation into the ecological dynamics of the North Oconee River within Athens-Clarke County, Georgia, with a specific focus on the distribution of 33 identified compounds, including a prominent pesticide. The research, conducted in the riverine ecosystems proximal to the Firefly trail, employs advanced analytical techniques to elucidate potential contamination sources arising from agricultural and urban runoff. Intriguingly, the study reveals North Oconee River near the Firefly Trail as a notable site for heightened pesticide contamination, warranting a meticulous exploration of its origins. Furthermore, the investigation unveils the intricate microbial degradation processes of malathion within the North Oconee River, elucidating the pivotal role played by microbial activity in river water. The detection of degradant byproducts prompts the considerations of bioavailability and toxicity, associating potential implications for the river’s overall ecological health. Ongoing research endeavors to precisely quantify environmental risks and unravel indigenous microbial degradation pathways, presenting pivotal contributions to the scientific community’s understanding of complex riverine ecosystems. This research serves as a foundational piece in informing sustainable environmental management practices and emphasizes the urgency of comprehensive stewardship in safeguarding aquatic ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Unraveling disadhesion mechanism of epoxy/CSH interface under aggressive conditions

Almost all FRP-reinforced concrete exposed to the marine environment are susceptible to durability deficiencies due to failure of the FRP/epoxy/concrete interface, especially the vulnerable epoxy/concrete interface, which is frequently attacked by water and ions. Herein, molecular dynamics simulations of epoxy/CSH interface under different environmental exposures are utilized to specifically elucidate the degradation principles of water and ions on the bonding properties and mechanical responses of the epoxy/concrete interface. The environmental sequences associated with the interfacial bonding degradation are arranged as Na{sub 2}SO{sub 4} + NaCl>NaCl>Na{sub 2}SO{sub 4} > Water>Dry. Remarkably, water molecules weaken the interaction between the epoxy and CSH by robbing interfacial H- and Ca-O bonds, thereby reducing the energy barrier to interfacial peel and shear failure. The weakening effects are exacerbated by the presence of aggressive ions, as Na{sup +} ions attracted to the CSH surface accumulate more water molecules in the interfacial region by forming hydrated ions clusters, which ultimately accelerates the epoxy/CSH interfacial degradation.

36 MATERIALS SCIENCE↗

Polypeptide organic radical batteries

In only a few decades, lithium-ion batteries have revolutionized technologies, enabling the proliferation of portable devices and electric vehicles, with substantial benefits for society. However, the rapid growth in technology has highlighted the ethical and environmental challenges of mining lithium, cobalt and other mineral ore resources, and the issues associated with the safe usage and non-hazardous disposal of batteries. Only a small fraction of lithium-ion batteries are recycled, further exacerbating global material supply of strategic elements. A potential alternative is to use organic-based redox-active materials to develop rechargeable batteries that originate from ethically sourced, sustainable materials and enable on-demand deconstruction and reconstruction. Making such batteries is challenging because the active materials must be stable during operation but degradable at end of life. Further, the degradation products should be either environmentally benign or recyclable for reconstruction into a new battery. Here we demonstrate a metal-free, polypeptide-based battery, in which viologens and nitroxide radicals are incorporated as redox-active groups along polypeptide backbones to function as anode and cathode materials, respectively. These redox-active polypeptides perform as active materials that are stable during battery operation and subsequently degrade on demand in acidic conditions to generate amino acids, other building blocks and degradation products. Here, such a polypeptide-based battery is a first step to addressing the need for alternative chemistries for green and sustainable batteries in a future circular economy.

25 ENERGY STORAGE↗

Constitutive Modeling of the Cross-Linked Polymers During the Trio-Aging Mechanism: Effects of Water, Oxygen, UV

Abstract The synergized effects of diverse environmental conditions such as humidity, temperature, UV, and oxygen, are considered through a generic model by combining the concepts of network alteration, hygrothermal, and Photo-thermo oxidation Models [1–4]. Hygrothermal and Photo-oxidation are considered dual aging mechanisms which are due to the synergized effects of moisture-oxygen, and UV-oxygen, respectively at elevated temperatures. Here Trio-aging is considered as the synergized effects of Hygrothermal, and Photo-oxidation which the main environmental elements involved in polymer degradation are oxygen, water, and UV radiation where each of which has a different micro-structural impact on the polymer matrix. While oxygen imposes chain scission and cross-link formation, water, and UV radiation mainly cause chain scission. Similar to our recent models, the dual network hypothesis of Topolosky is utilized and as a result, the strain energy of the polymer matrix is written in terms of two states namely unaged and infinity. The infinity state network, itself, is decomposed into three networks, namely brittle, flexible, and dead networks. While the brittle network models the cross-link formation as sub-structural phenomena, the flexible and dead networks are utilized to represent the cross-link reduction and chain scission. The contribution of these networks in the infinity state is based on the amount of relevant environmental elements. The model is developed for a domain with plenty of oxygen and holds true for a gradual aging process that happens in super-thin samples.

Bahrololoumi, Amir↗

Mitigation Methods for Piperazine Oxidation in Post-Combustion Carbon Capture

Piperazine is a promising second-generation solvent for amine scrubbing in post-combustion CO2 capture. However, the oxidative degradation of PZ can cause environmental problems and economic loss. This work presents the effects of two mitigation methods: carbon treating and N2 sparging, on the PZ oxidation in long-term operations. The species and their respective quantities adsorbed by the activated carbon were tested in a bench-scale device. The carbon was then tested in the High Temperature Oxidation Reactor (HTOR), where the solvent oxidizes at a reasonably fast rate. Pilot plant campaigns were also performed at the UT Austin SRP and the National Carbon Capture Center (NCCC) and the effects were verified. When dissolved Fe is removed by carbon treating or other methods, available soluble Fe in the system dissolves and replaces the dissolved Fe. Therefore, all available Fe and ligands need to be removed for the mitigation to be effective. The sources of soluble Fe include fly ash and the corrosion of stainless steel, and the ligands are degradation products. 8 All PZ degraded solvents have two absorbance peaks at 320 nm and 538 nm. The 320 nm peak is caused by dissolved metals, especially Fe, complexed by degradation products. The 320 nm peak is related to the amine degradation level and can be used as a simple and efficient method to estimate the amine degradation rate. The pilot plant data suggest that NO2 can oxidize PZ significantly, possibly through radical reactions. 0.01 mmol/kg-hr absorption of NO2 increased the PZ oxidation rate from 1.2 mmol/kg-hr to 2.5 mmol/kg-hr.

Yuying, Wu↗