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At least 163 records · Page 9

Characterization of a selective, zero power sensor for distributed sensing of hydrogen in energy applications

The use of hydrogen as a clean and renewable energy source is increasing rapidly for both vehicle and stationary applications. There are safety concerns for the locations in which hydrogen is made, used, and transported (i.e., pipelines and tanker trucks). Sensors are needed to comply with safety regulations and to enable a smooth and safe rollout of hydrogen as an alternative energy. However, hydrogen sensors do not yet exist that have the combined features of small size and low power for easy deployment coupled with high-volume manufacturability and low cost. This is necessary to accommodate the emerging fixed and mobile markets while retaining critical metrological metrics, including measurement range, detection limits, selectivity, fast response, stability, and long lifetime. An amperometric gas sensor for hydrogen (AGS) has been developed using an innovative manufacturing method. The sensor was designed using scalable fabrication strategies based on “Printed Electronics” (PE) methodology which are compatible with large-scale production. Prototype sensors were batch fabricated with multiple individual elements on a substrate compatible in size with a standard 8-inch wafer to enable high-volume, low-cost manufacturing, thereby leveraging PE and semiconductor fabrication infrastructure. This novel AGS was instrumented with control circuitry and evaluated for hydrogen detection in the range of 0–5000 ppmv H2 in air. Specific performance evaluations included assessment of the sensor measurement range, repeatability, and selectivity.

08 HYDROGEN↗

Search for lightly ionizing particles in superCDMS and simulation of neutron backgrounds

The Super Cryogenic Dark Matter Search (SuperCDMS) is a direct-detection dark matter search experiment that primarily aims to search for Weakly Interacting Massive Particles (WIMPs) using state-of-the-art solid-state detection technology. During its operation at the Soudan underground laboratory, germanium detectors were operated with high bias voltage mode known as the CDMS low ionization threshold experiment (CDMSlite) to achieve below-keV thresholds. CDMSlite, for being able to measure small energy depositions in detectors, also provides sensitivity to Lightly Ionizing Particles (LIPs) with very small fractional charges. This thesis will discuss an analysis to search LIPs with the data acquired in CDMSlite mode. An important component for LIPs search is the expected energy-deposition distributions for LIPs falling on the CDMSlite detector. In this thesis, a simulation framework to calculate the energy-deposition distributions is developed. This thesis presents first direct-detection limits on the intensity of cosmogenic LIPs with electric charges smaller than e/(3 × 105) as well as the strongest limits for charges ≤ e/160, with a minimum intensity of 1.36 × 10-7 cm-2s-1sr-1 at charge e/160.In any rare-event search experiment, understanding background is crucial. Neutrons capable of mimicking dark matter signals are a major background for any dark matter search experiment. A simulationmore » study to estimate the neutron background for an India based dark matter search experiment at Jaduguda Underground Science Laboratory (JUSL) is performed. The experiment at JUSL will be the first phase of a proposed Dark matter search at India-based Neutrino Observatory (DINO). It will be a direct detection experiment with primary aims to search for WIMPs as dark matter candidates. In this thesis, we discuss the methodology of estimating neutron flux at JUSL and report the results. The total neutron flux reaching the laboratory above 1 MeV energy threshold is found to be 5.76(±0.69) × 10-6 cm-2s-1. The impact of neutron background on the sensitivity of the experiment to detect dark matter at JUSL is also discussed. The thesis is organized as follows. Chapter 1 provides a brief introduction to the Lightly Ionizing Particle (LIPs). The analysis to search LIPs in SuperCDMS is briefly outlined in the chapter. This chapter also discusses the importance of neutron background estimates in a dark matter search experiment, more specifically, in the context of a proposed India-based dark matter search experiment at Jaduguda Underground Science Laboratory. In Chapter 2, the SuperCDMS experiment is introduced. In Chapter 3, the framework developed to perform simulations for Lightly Ionizing Particles is presented. In Chapter 4, the LIPs search analysis with the CDMSlite data and the results are discussed. In Chapter 5, the simulation of neutron background and the feasibility of dark-matter search at JUSL is discussed. Finally, conclusions from all the results discussed in this thesis are presented in Chapter 6.« less

Banik, Samir↗

Inline gamma-spectrometry of fission product elements after rapid high-pressure ion chromatographic separation

Analysis of irradiated material shortly after irradiation can be non-trivial due to highly radioactive activation and fission isotopes increasing dead time in gamma-ray detection systems, often requiring a “cooling-period” between receipt of a sample and the subsequent analysis. A direct separation–detection method has been developed combining ion chromatography and inductively coupled mass spectrometry for rapid, low-level analysis of fission products; it cannot, however, detect certain short-lived species below the detection limit of the system. In this paper we report the implementation of an inline gamma-ray detector, which was added post-separation, pre-analysis, to test the quality and utility of elementally-isolated gamma-ray spectroscopy.

Inline gamma-ray detection↗

Search for Lightly Ionizing Particles in SuperCDMS and simulation of neutron backgrounds

The Super Cryogenic Dark Matter Search (SuperCDMS) is a direct-detection dark matter search experiment that primarily aims to search for Weakly Interacting Massive Particles (WIMPs) using state-of-the-art solid-state detection technology. During its operation at the Soudan underground laboratory, germanium detectors were operated with high bias voltage mode known as the CDMS low ionization threshold experiment (CDMSlite) to achieve below-keV thresholds. CDMSlite, for being able to measure small energy depositions in detectors, also provides sensitivity to Lightly Ionizing Particles (LIPs) with very small fractional charges. This thesis will discuss an analysis to search LIPs with the data acquired in CDMSlite mode. An important component for LIPs search is the expected energy-deposition distributions for LIPs falling on the CDMSlite detector. In this thesis, a simulation framework to calculate the energy-deposition distributions is developed. This thesis presents first direct-detection limits on the intensity of cosmogenic LIPs with electric charges smaller than e /(3 × 10 5 ) as well as the strongest limits for charges ≤ e /160, with a minimum intensity of 1.36 × 10 -7 cm -2 s -1 sr -1 at charge e /160.In any rare-event search experiment, understanding background is crucial. Neutrons capable of mimicking dark matter signals are a major background for any dark matter search experiment. A simulation study to estimate the neutron background for an India based dark matter search experiment at Jaduguda Underground Science Laboratory (JUSL) is performed. The experiment at JUSL will be the first phase of a proposed Dark matter search at India-based Neutrino Observatory (DINO). It will be a direct detection experiment with primary aims to search for WIMPs as dark matter candidates. In this thesis, we discuss the methodology of estimating neutron flux at JUSL and report the results. The total neutron flux reaching the laboratory above 1 MeV energy threshold is found to be 5.76(±0.69) × 10 -6 cm -2 s -1 . The impact of neutron background on the sensitivity of the experiment to detect dark matter at JUSL is also discussed. The thesis is organized as follows. Chapter 1 provides a brief introduction to the Lightly Ionizing Particle (LIPs). The analysis to search LIPs in SuperCDMS is briefly outlined in the chapter. This chapter also discusses the importance of neutron background estimates in a dark matter search experiment, more specifically, in the context of a proposed India-based dark matter search experiment at Jaduguda Underground Science Laboratory. In Chapter 2, the SuperCDMS experiment is introduced. In Chapter 3, the framework developed to perform simulations for Lightly Ionizing Particles is presented. In Chapter 4, the LIPs search analysis with the CDMSlite data and the results are discussed. In Chapter 5, the simulation of neutron background and the feasibility of dark-matter search at JUSL is discussed. Finally, conclusions from all the results discussed in this thesis are presented in Chapter 6.

Banik, Samir↗

Establishment of a reverse transcription real-time quantitative PCR method for Getah virus detection and its application for epidemiological investigation in Shandong, China

Getah virus (GETV) is a mosquito-borne, single-stranded, positive-sense RNA virus belonging to the genus Alphavirus of the family Togaviridae . Natural infections of GETV have been identified in a variety of vertebrate species, with pathogenicity mainly in swine, horses, bovines, and foxes. The increasing spectrum of infection and the characteristic causing abortions in pregnant animals pose a serious threat to public health and the livestock economy. Therefore, there is an urgent need to establish a method that can be used for epidemiological investigation in multiple animals. In this study, a real-time reverse transcription fluorescent quantitative PCR (RT-qPCR) method combined with plaque assay was established for GETV with specific primers designed for the highly conserved region of GETV Nsp1 gene. The results showed that after optimizing the condition of RT-qPCR reaction, the minimum detection limit of the assay established in this study was 7.73 PFU/mL, and there was a good linear relationship between viral load and Cq value with a correlation coefficient ( R 2 ) of 0.998. Moreover, the method has good specificity, sensitivity, and repeatability. The established RT-qPCR is 100-fold more sensitive than the conventional RT-PCR. The best cutoff value for the method was determined to be 37.59 by receiver operating characteristic (ROC) curve analysis. The area under the curve (AUC) was 0.956. Meanwhile, we collected 2,847 serum specimens from swine, horses, bovines, sheep, and 17,080 mosquito specimens in Shandong Province in 2022. The positive detection rates by RT-qPCR were 1%, 1%, 0.2%, 0%, and 3%, respectively. In conclusion, the method was used for epidemiological investigation, which has extensive application prospects.

Cao, Xinyu↗

Analysis of Respirator Cartridge Performance Testing on Hanford Tank A-101

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance1 to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPCs) from vapors emanating from the headspace of tank A-101 on the Hanford Site. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedules.[3] Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to ensure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted over a period from July 22-24, 2016, using headspace vapors from Hanford tank A-101 under static conditions2 fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and 7422-SC1 (SCOTT Safety, Monroe, North Carolina) were assessed on separate days with A-101 headspace vapors. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge, and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life. Key conclusions from the assessment of the 59 COPCs in this study are described below: • Based on d measured cartridge inlet vapor concentrations from tank A-101 headspace, both ammonia and N-Nitrosodimethylamine (NDMA) exceeded their Occupational Exposure Limits (OEL).3 These measurements were generally consistent with maximum A-101 headspace measurements previously obtained for these two compounds. • Ammonia had respirator cartridge outlet concentrations that exceeded 10% of the OEL for both cartridges tested, indicating breakthrough for each. For the SCOTT 7422-SD1 cartridge, ammonia appeared to breakthrough above 10% of its OEL after 2 hours. For the SCOTT 7422-SC1 cartridge, ammonia breakthrough appeared to occur after 8 hours. 1 “Adequate performance” refers to the breakthrough criteria used in this analysis—that is, sustained cartridge outlet concentrations above 10% of the OEL. For some COPCs, an alternate threshold has been applied when necessary due to higher detection limit (DL)/reporting limit (RL) values for specific compounds. Ultimately, Industrial Hygiene professionals will use these results along with specific hazard assessments to determine service life and cartridge use that provides the necessary performance. 2 These tests were conducted under static conditions absent waste-disturbing activities in the subject tank or tank farm. 3 Occupational Exposure Limits accepted for Hanford Tank Farm use are based on OELs established by a U.S. governmental agency or national professional organization (e.g., OSHA, National Institute for Occupational Safety and Health, American Conference of Governmental Industrial Hygienists), or if no U.S. OEL exists, standard toxicological practices are applied to develop OELs using non-U.S. exposure limits, other established OELs for chemical surrogates when available, or other standard procedures. The OEL for NDMA was established in 2005 based on the MAK (Maximale Arbeitsplatzkonzentration) Commission standard adopted in Europe. iv • Despite respirator inlet measurements for NDMA that were in excess of its OEL, all corresponding outlet measurements, from both respirator cartridges, were below analytical DL 1 for the

61 RADIATION PROTECTION AND DOSIMETRY↗

Advanced diagnostics to evaluate heterogeneity in lithium-ion battery modules

Battery packs for electric and stationary applications experience varied operating conditions, including abuse—e.g., fast charging, overcharging, thermal, vibration, shock, etc.—throughout their lifetimes. Innovative diagnostic tools and algorithms that go beyond single cells and deal with modules and packs are essential for early detection of off-normal issues. High-resolution tools with known detection limits are key to developing appropriate mitigation strategies. With the advent of rapid impedance spectroscopy that can generate a broadband impedance spectrum in ~10 sec, the case for impedance-based diagnostics that can be readily aligned with other methods, such as incremental capacity or dQ.dV -1 , has become promising. This study used the aforementioned diagnostic methods to identify realistic in-vehicle battery abnormalities (e.g., localized self-discharge and non-uniform aging), in series (up to 10S) and parallel (4P) strings, using 16 Ah graphite/NMC cells. The impedance-based diagnostic is found to be sensitive to the string size and state. Depending on the type of abnormality, detection frequency varied. The dQ.dV -1 method showed the potential to detect long-term aging-related heterogeneity in modules. In general, both the impedance and dQ.dV -1 methods were able to detect series strings’ abnormalities, but struggled to find those issues within parallel modules.

25 ENERGY STORAGE↗

A Sensitive Electrochemical Cholinesterase-Inhibiting Biosensor for Organophosphorus Pesticides Based on Ti 3 C 2 TX MXene Quantum Dots

Organophosphorus pesticides (OPs) pose significant environmental and health risks due to their widespread use and toxicity, primarily by inhibiting acetylcholinesterase. Traditional detection methods are often slow and costly, highlighting the urgent need for advanced, sensitive, and accessible technologies. This study developed a highly sensitive electrochemical cholinesterase-inhibiting biosensor for OP pesticides, utilizing Ti 3 C 2 T x MXene Quantum Dots (MQDs), which was synthesized via a hydrothermal method. The biosensor’s performance was characterized using electrochemical impedance spectroscopy, differential pulse voltammetry (DPV), and cyclic voltammetry. DPV proved to be the optimal technique, exhibiting an ultralow detection limit of 1 × 10 −17 M and a wide linear range (10 −14 –10 −8 M) for chlorpyrifos (a model OP) with an estimated inhibition constant of 62 nM. The biosensor demonstrated high selectivity for OPs (chlorpyrifos, acephate, glyphosate) over a non-target pyrethroid (permethrin), confirmed by distinct electrochemical signatures and compared to in vitro cholinergic activity assays in bean beetle homogenates. The enhanced performance is attributed to the high surface-to-volume ratio, quantum confinement effects, and superior conductivity of the MQDs, as well as the robust enzyme immobilization facilitated by glutaraldehyde cross-linking and a chitosan matrix. This work presents a promising platform for rapid, sensitive, and selective detection of OP pesticides, with potential applications in environmental monitoring and public health protection.

Chemistry↗

Modulating Electron Beam–Sample Interactions in Imaging and Diffraction Modes by Dose Fractionation with Low Dose Rates

Abstract Technological opportunities are explored to enhance detection schemes in transmission electron microscopy (TEM) that build on the detection of single-electron scattering events across the typical spectrum of interdisciplinary applications. They range from imaging with high spatiotemporal resolution to diffraction experiments at the window to quantum mechanics, where the wave-particle dualism of single electrons is evident. At the ultimate detection limit, where isolated electrons are delivered to interact with solids, we find that the beam current dominates damage processes instead of the deposited electron charge, which can be exploited to modify electron beam-induced sample alterations. The results are explained by assuming that all electron scattering are inelastic and include phonon excitation that can hardly be distinguished from elastic electron scattering. Consequently, a coherence length and a related coherence time exist that reflect the interaction of the electron with the sample and change linearly with energy loss. Phonon excitations are of small energy (<100 meV), but they occur frequently and scale with beam current in the irradiated area, which is why we can detect their contribution to beam-induced sample alterations and damage.

47 OTHER INSTRUMENTATION↗

Mapping of lanthanide-tagged proteins on western blot paper using microextraction-inductively coupled plasma-mass spectrometry

A microextraction (ME) sampling system, paired with inductively coupled plasma-mass spectrometry (ICP-MS), was employed to spatially analyze proteins tagged with lanthanum (La), gadolinium (Gd), or terbium (Tb) on the surface of western blot paper. The proteins were covalently tagged, separated via gel electrophoresis, and transferred to western blot paper for analysis by ME-ICP-MS. The ME-ICP-MS method enables the direct sampling of the tagged species on the western blot paper, without any sample preparation. Traditionally, the tagged analyte would need to be stained, excised, and digested to be analyzed by ICP-MS for its elemental and isotopic characterization. Preliminary detection limits for the ME-ICP-MS method applied to western blot paper were established to be 564, 54, and 2.5 fg for La, Gd, and Tb, respectively. The developed ME-ICP-MS method was compared to laser ablation (LA) ICP-MS, another direct solid sampling technique; it was readily determined that ME-ICP-MS can effectively map the elemental constituents on the western blot paper with comparable analysis time and measurement sensitivity. The analysis time per 2 × 4 mm extraction is ∼1 minute; if protein spots are directly targeted (rather than systematically mapping the entire blot paper), the analysis time per protein spot is ∼1 min. This developed method proved to be fast, effective, and accessible for correlating protein molecular weight with the detection of the inorganic tagant. The ME-ICP-MS approach could be widely applicable in research areas that involve metal-tagged protein bioconjugates, such as in the development of diagnostic and therapeutic agents and other biochemical probes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chelation ion chromatography as an automated, and cost-effective analytical technique for REE determination: method development and applications

Rare earth elements (REEs), as critical minerals, have important uses in modern energy and technologies, yet are vulnerable to potential supply chain disruptions. To establish domestic REE supply chain, efficient REE detection methods for resource characterization and mineral processing will be needed to accelerate innovations for domestic REE recovery. This study developed a rapid, novel, and cost-effective for REE detection method using ion chromatography (IC) for aqueous samples. Various REE-targeted eluent gradients and post-column agent compositions were tested on the chelation ion chromatography (CIC) with UV-vis detector for optimal separation and quantification of REEs within approximately 20 min. The single-channel pump to deliver the post-column solution to UV-vis detector was replaced with a 4-channel gradient pump, to increase operation and maintenance efficiencies. After method optimization, resulting calibration curves for more than ten REEs achieved high coefficients of determination (R2>0.999) and low relatively standard deviations (below 3.24%), demonstrating sub-ppm level detection limits (0.0897 to 0.1149 mg/L). The reliability of the CIC method was validated through comparison with inductively coupled plasma mass spectrometry (ICP-MS), showing strong agreement in REE recovery from certified standards. The impact of metal ions and salts on REE recovery using CIC was also systematically investigated. CIC consistently exhibited reliable performance in the presence of salt solutions such as NaCl and Na₂SO₄ (up to 10,000 mg/L). Our study also found the presence of high concentrations of Al ions (at 10,000 mg/L) significantly influenced REE determination, and elevated concentrations of Ca ions affected the recovery of specific REEs, including La, Ce, and Pr. The CIC method was further tested on REE-containing eluents from solvent extraction tests out of fly ash leachates. REE detection from these real processing fluids were reported to achieve 90% to 100% recovery rate from our IC method, compared to ICP-MS results. This study underscores the potential of CIC as a reliable and efficient alternative for REE determination in complex matrices. It also highlights the importance of minimizing select interfering metal ions in solutions to ensure accurate results. The REE CIC method presents a promising, low-maintenance, salt-tolerant, and cost-effective alternative to traditional analytical methods for REE analysis.

detection of rare earth elements (REE)↗

Inactivation of Human Coronavirus by FATHHOME’s Dry Sanitizer Device: Rapid and Eco-Friendly Ozone-Based Disinfection of SARS-CoV-2

The pandemic of SARS-CoV-2/COVID-19 was reported in December 2019 in Wuhan, China. Pertaining to its high transmissibility and wide host adaptability, this unique human coronavirus spread across the planet inflicting 115 million people and causing 2.5 million deaths (as of March 3rd, 2021). Limited or negligible pre-existing immunity to multiple SARS-CoV-2 variants has resulted in severe morbidity and mortality worldwide, as well as a record-breaking surge in the use of medical-surgical supplies and personal protective equipment. In response to the global need for effective sterilization techniques, this study evaluated the virucidal efficacy of FATHHOME’s self-contained, ozone-based dry-sanitizing device, by dose and time response assessment. We tested inactivation of human coronavirus, HCoV-OC43, a close genetic model of SARS-CoV-2, on porous (N95 filtering facepiece respirator/FFR) and nonporous (glass) surfaces. We started our assays with 20 ppm-10 min ozone exposure, and effectively reduced 99.8% and 99.9% of virus from glass and N95 FFR surfaces, respectively. Importantly, the virus was completely inactivated, below the detection limit (over 6-log10 reduction) with 25 ppm-15 min ozone exposure on both tested surfaces. As expected, a higher ozone exposure (50 ppm-10 min) resulted in faster inactivation of HCoV-OC43 with 100% inactivation from both the surfaces, with no residual ozone present after completion of the 5-min post exposure recapture cycle and no measurable increase in ambient ozone levels. These results confirmed that FATHHOME’s device is suitable for rapid decontamination of SARS-CoV-2- from worn items, frequently touched items, and PPE including N95 FFRs, face shields, and other personal items. View Full-Text

59 BASIC BIOLOGICAL SCIENCES↗

Bismuth Subcarbonate Decorated Reduced Graphene Oxide Nanocomposite for the Sensitive Stripping Voltammetry Analysis of Pb(II) and Cd(II) in Water

In this paper, bismuth subcarbonate (BiO)2CO3-reduced graphene oxide nanocomposite incorporated in Nafion matrix ((BiO)2CO3-rGO-Nafion) was synthesized and further applied, for the first time, in the sensitive detection of Pb(II) and Cd(II) by square-wave anodic stripping voltammetry (SWASV). The as-synthesized nanocomposites were characterized by energy-dispersive spectroscopy (EDS), Raman spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). (BiO)2CO3 composite plays a key role in the improvement of the detection sensitivity, which can form multicomponent alloy with cadmium and lead. Additionally, the unique structure of rGO can enlarge the surface area and provide abundant active sites. Moreover, Nafion incorporation in the nanocomposite can effectively increase the adhesion and mechanical strength of the film, and further improve the preconcetration ability due to the cation-exchange capacity of its abundant sulfonate groups. As expected, the (BiO)2CO3-rGO/Nafion nanocomposite-modified glassy carbon electrode ((BiO)2CO3-rGO-Nafion/GCE) achieved low detection limits of 0.24 μg/L for Pb(II) and 0.16 μg/L for Cd(II), in the linear range of 1.0–60 μg/L, and showed some excellent performance, such as high stability, good selectivity, and sensitivity. Finally, synthetic water samples were prepared and further used to verify the practicability of the (BiO)2CO3-rGO-Nafion/GCE with satisfactory results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Review: PFAS Adsorption, Sensing, and Remediation with Engineered Nanoporous Materials

Per- and polyfluoroalkyl substances (PFAS) are among the most abundant environmental contaminant species. They are widespread due to uncontrolled industrial and commercial use and have been linked to health risks such as cancer. With rising global concerns about the public health effects of PFAS, there is an incentive to develop strategies for reliable monitoring and effective PFAS removal, particularly in drinking water. Traditional PFAS sensing techniques are inefficient due to long measurement times, high labor input, high costs, and limitations to ex situ analysis. Current commercially available sorbents for PFAS removal generally lack the ability to capture PFAS components rapidly and quantitatively. Furthermore, existing sorbents are notably inefficient in removing the more toxic, smaller PFAS chemical chains. Large-scale applications of these methods tend to be costly and resource-intensive. Pacific Northwest National Laboratory has developed unique strategies for PFAS sensing and removal with capture probe technology that has an affinity for fluorocarbons, including PFAS. For both sensing and removal, the customizable capture probes can target specific PFAS compounds since they used a metal-organic framework (MOF)-based technology that can be fine-tuned and molecularly tailored. This tailoring of the materials enables high PFAS sensitivity, selectivity, and faster uptake. PNNL’s capture probe materials have been developed into a sensing technique based on the interactions of the capture probes with PFAS at the molecular level and further transduced that to a quantifiable electrochemical response. The materials have been integrated into a sensor platform developed by New Jersey Institute of Technology (NJIT). Tunable capture probes with a range of detection sensitivities allow for faster and more sensitive PFAS detection limits as low as what appears to be 0.5 ng/L (compared to the U.S. Environmental Protection Agency health advisory level of 70 ng/L). Customization of the capture probe results in improved sorption capacities (fast kinetics and high capacities) compared to commercial granular activated carbons. This research applied various experimental and modeling tools to improve understanding the molecular level interactions between the sorbents towards PFAS adsorption properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Linker-Free Magnetite-Decorated Gold Nanoparticles (Fe3O4-Au): Synthesis, Characterization, and Application for Electrochemical Detection of Arsenic (III)

Linker-free magnetite nanoparticles (Fe3O4NPs)-decorated gold nanoparticles (AuNPs) were grown using a new protocol that can be used as a new platform for synthesis of other intact metal–metal oxide nanocomposites without the need for linkers. This minimizes the distance between the metal and metal oxide nanoparticles and ensures the optimum combined effects between the two material interfaces. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy confirmed the successful synthesis of the Fe3O4-Au nanocomposite, without any change in the magnetite phase. Characterization, using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, revealed the composite to consist of AuNPs of 70 ± 10 nm diameter decorated with tiny 10 ± 3 nm diameter Fe3O4NPs in Au:Fe mass ratio of 5:1. The prepared Fe3O4-Au nanocomposite was embedded in ionic liquid (IL) and applied for the modification of glassy carbon electrode (GCE) for the electrochemical detection of As(III) in water. By combining the excellent catalytic properties of the AuNPs with the high adsorption capacity of the tiny Fe3O4NPs towards As(III), as well as the good conductivity of IL, the Fe3O4-Au-IL nanocomposite showed excellent performance in the square wave anodic stripping voltammetry detection of As(III). Under the optimized conditions, a linear range of 1 to 100 μg/L was achieved with a detection limit of 0.22 μg/L (S/N = 3), and no interference from 100-fold higher concentrations of a wide variety of cations and anions found in water. A very low residual standard deviation of 1.16% confirmed the high precision/reproducibility of As(III) analysis and the reliability of the Fe3O4-Au-IL sensing interface. Finally, this proposed sensing interface was successfully applied to analyzing synthetic river and wastewater samples with a 95–101% recovery, demonstrating excellent accuracy, even in complex synthetic river and wastewater samples containing high concentrations of humic acid without any sample pretreatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

Oxide derived Cu nanofibril assembly for enhanced nonenzymatic glucose sensing

In this report, we have prepared copper nanofibril assembly via thermal oxidation followed by electrochemical reduction processes, exhibiting superior glucose detection ability. The morphological analysis evidenced the formation of rough islands or nanofibril structure on the Cu surface depending on initial thermal oxidation temperature. The glucose detection performance was investigated by performing cyclic voltammetry and chronoamperometry with varying glucose concentration. A high sensitivity (4131.57 μA mM – 1 cm – 2 ), low detection limit (1.41 μM), wider linear range (0–3.9 mM) and long–term stability (30 days) have been recorded for electrode thermally oxidized at 400 °C followed by electrochemical reduction process (rCu_400). The sensitivity is almost three times higher in comparison to the planner Cu surface. This significantly enhanced glucose sensing ability rCu_400 has been attributed to the nanofibril morphology, origination of Cu (111) facet and formation of a stable oxide layer evidenced by scanning electron microscopy, X-ray diffraction and energy dispersive spectroscopy analysis. Despite higher sensitivity, rCu_400 electrode does not show any response to the chloride ion, dopamine, ascorbic acid and uric acid. Finally, these results indicate that the Cu nanofibril structure prepared via simple oxidation/reduction process can be an excellent candidate to be used as an electrode for glucose sensing application.

36 MATERIALS SCIENCE↗

Near-Zero Power MOF-Based Sensors for NO 2 Detection

Detection and capture of toxic nitrogen oxides (NO x ) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5–5 ppm) NO 2 by a metal–organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO 2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO 2 ; a 725× decrease in resistance at 5 ppm NO2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO 2 over N 2 , SO 2 , and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm 2 with 0.8 mg MOF-74. Finally, this represents a 10 4 –10 6 × decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.

47 OTHER INSTRUMENTATION↗