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Diagnostics: Chapter 8 of the special issue: on the path to tokamak burning plasma operation

This chapter presents the activity conducted by the ITPA topical group (TG) on Diagnostics over about the last 15 years. Following a general introduction of the ITER Diagnostics led by their measurement roles, the document is organized in several subchapters detailing the design support, research and development activity conducted by each of the specialist working groups (WGs) of the TG. Please note that the magnetic diagnostics were supported at the TG without a specific WG. Their status is included in the general introduction. In the following some highlights of the subchapter’s contents are provided. Recent advances in ITER first wall (FW) diagnostics for the measurements of plasma-metallic wall interaction in support of the ITER research plan are reported. An InfraRed imaging Video Bolometer for ITER has been developed and tested on several tokamaks to measure the radiated power loss. A laser-induced breakdown spectroscopy (LIBS) technique which utilizes a pulsed laser beam to ablate locally by forming a crater, will measure local tritium inventory in the FW material. Real-time Residual Gas Analyzers will measure the neutral gas composition in a divertor port and an equatorial port during plasma operation. Due to the full metallic FW environment, the plasma-wall interaction in ITER will face several challenges such as the compromised radiated power and divertor heat flux measurements by reflection. Ray tracing and analysis codes have been developed to eliminate and correct the effects of reflection in the measurements. The characteristics of the reflecting surfaces depending on the roughness and angle of the incidence have been measured by dedicated experiments, and the results were applied to the reflection elimination. For the measurement of the metallic impurity radiation induced by eroded metallic atoms, a vacuum ultraviolet spectrometer has been developed and tested. An extensive thermonuclear diagnostic suite will be required to support the operation of ITER and the planned experimental program for future burning plasma experiments. Due to the harsh environmental conditions, the implementation of diagnostic systems in ITER is a major challenge. These conditions include high levels of neutron and gamma fluxes, neutron heating, particle bombardment. Therefore, the selection and design of diagnostic systems must take into account a number of phenomena previously unseen in diagnostic design. For this reason, the measurement of neutrons and confined or lost fast ions, with particular emphasis on alpha particles, is critical to ITER. The diagnostics associated with these measurements will be important for future plasma-burning experiments at ITER. The high neutron emission and very large plasma size in ITER make neutron diagnostics the main diagnostic method used to measure plasma parameters such as fusion power, fusion power density, ion temperature, energy of fast ions and their spatial distributions in the plasma core. Active spectroscopy techniques are methods where a neutral particle beam is injected into the plasma and information on plasma parameters is extracted from the measurement of line emission resulting from the beam-plasma interaction, either by plasma ions or by beam atoms. Spatial localization is achieved by crossing the beamline and multiple observation lines. The ITER plasma will be a high temperature, moderately dense, fully ionized collisional plasma. The plasma facing surfaces are principally metallic being fashioned from beryllium or tungsten but many other elements, arising from either structural or from operational needs, may enter this plasma. The energy range of the emitted photons range from meV (infra-red) to multi keV (x-rays) and originate from all areas of the plasma volume. The primary role of passive emission diagnostics is to identify what is in the plasma from spectral signatures. Extracting quantitative information from these measurements such as impurity content, ion temperature, rotation, degree of detachment and radiated power depends on calibrated instruments, a physics model of the atomic and molecular processes and plasma transport and an analysis workflow that takes into account environmental effects such as reflections. The particular needs for ITER have prompted a multi-machine, many-year effort to address all these aspects and this chapter reviews the work on diagnostic design, experiments and new analysis techniques. An overview of the laser diagnostics to be implemented on ITER is also provided in this paper. This includes descriptions of the Thomson scattering in the core, edge and divertor regions, polarimetry and interferometry diagnostics used for measuring plasma density and also measurements of helium density in the divertor using Laser Induced Flourescence. Techniques which can allow improvements on current measurements are also addressed in particular expanding poloidal polarimetry measurements to measure field fluctuations and proposed use of dispersion interferometery which has a number of advantages over existing methods. This paper identifies particular areas where further research and testing on existing tokamaks is useful even at this advanced stage to inform the design of diagnostics for ITER. Outstanding areas of concern for the implementation of laser diagnostics, in particular with a view to reliable operation are identified. An overview of the latest developments of microwave diagnostic systems and techniques is given. The primary focus is the contributions for ITER—the next step burning plasma experiment—which is supplemented by describing recent progress of techniques applicable for fusion experiments beyond ITER. The contributions are intentionally kept concise, and are being supplemented by a rich list of references for further studies. Radiation induced effects are receiving continuous and well-deserved attention of the ITER diagnostic community and they are in many cases one of the primary design drivers of the ITER diagnostic systems. The paper summarizes recent progress in this area focusing primarily on the ITER diagnostics but in some cases provides also outlook for the possible solutions for even more demanding radiation environment of fusion reactors beyond ITER. Despite advancements in the area of modeling and simulation of various radiation induced effects, experimental testing in a nuclear environment as close as possible to the target one is still seen as unavoidable for proper qualification of particular diagnostic functional elements. Recent advancement within three diagnostic areas: optical diagnostics, magnetics and bolometers is covered. Encouraging results on qualification of silica glass vacuum window assemblies are presented. In the area of magnetic sensors, progress of irradiation tests performed on ITER in-vessel LTCC inductive sensors is presented with outlook for novel technological approaches to inductive sensors utilizing thick printing and photolithography technologies being highlighted. Summary of advancements in the area of steady state magnetic field sensors based on Hall effect is given. New results of neutron irradiation test of the ITER borosilicate glass inserts for vacuum electrical feedthroughs are summarized finding negligible swelling at target level of neutron fluence. Off-line irradiation tests of fiber optic current sensors for plasma current measurement demonstrated that both for gamma doses up to 5 MGy and a total neutron fluence up to 10 15 cm −2 , radiation induced changes are still compatible with required measurement accuracy on ITER. The ITER bolometers are given as an example how considering radiation effects may influence the diagnostic design. Finally, outlook for future main R&D directions is outlined. All optical and laser-based diagnostics in ITER will be using mirrors to guide plasma radiation toward detectors, cameras and sensors. In the hostile plasma, radiation and particle environment the optical characteristics of diagnostic mirrors will degrade directly affecting the entire performance of involved diagnostic systems. An assessment of factors affecting mirror performance is provided. Among the prime adverse factors are deposition of plasma impurities, sputtering of mirror surface and steam ingress in the vicinity of mirrors. Within the International Tokamak Physics Activity with active support by ITER central team and domestic agencies, the structured research and development (R&D) program on mitigation of risks for diagnostic mirrors is underway. Within this program the mirror material development, the passive mitigation of mirror degradation by using diagnostic ducts and shutters along with an active mirror recovery program comprising the in-situ mirror cleaning and calibration is underway. Recent developments in diagnostic mirror R&D are described in this Chapter along with an example of their implementation of R&D solutions in ITER Infrared Thermography diagnostic. An assessment of still open engineering and physics questions, considerations on mirror risks during an early phase of ITER operation are given along with an overview of diagnostic mirror evolution in the late ITER operation stage toward the demonstration fusion power plant. Several crucial areas of diagnostic R&D outlined in ITER Research Plan are addressed. The basic control groups in a fusion reactor can be broken-down in five categories: (1) plasma position, magnetic configuration, and plasma current control, (2) profile control and confinement optimization, (3) MHD control and suppression, (4) edge dissipation control, radiation and plasma exhaust control and (5) break-down optimization. These categories are coupled via the physics (a control action in one domain will affect the other domains) and via shared actuators (e.g. ECRH for impurity accumulation avoidance, current density distribution control and MHD suppression). Consequently, a supervisory control system should determine the priority of the various control tasks, their couplings, and the interfaces with the safety and interlock system. For the systematic development of the various controllers taking the complexity of the plasma and the control system into account, a model-based approach is required. A short historical overview is given of the developments in systems and control theory and control engineering with special emphasis on those developments that are most relevant for Nuclear Fusion research and operation. An overview is given of the state of the field of fusion plasma control for the control categories. It will be shown how synthetic diagnostics are being developed in ITER and how they are used in diagnostic design and design validation and how they can be in model-based controller synthesis using relatively simple models. In modern control methods, multiple diagnostics are used to constrain relatively simple models. The constrained models provide an estimate for the state. This opens the route to state controllers, such as model predictive control. A major challenge in nuclear fusion research is the coherent combination of data from heterogeneous diagnostics and modeling codes for machine control and safety as well as physics studies. Measured data from different diagnostics often provide information about the same subset of physical parameters. Additionally, information provided by some diagnostics might be needed for the analysis of other diagnostics. A joint analysis of complementary and redundant data allows, e.g. to improve the reliability of parameter estimation, to increase the spatial and temporal resolution of profiles, to obtain synergistic effects, to consider diagnostics interdependencies and to find and resolve data inconsistencies. Physics-based modeling and parameter relationships provide additional information improving the treatment of ill-posed inversion problems. A coherent combination of all kind of available information within a probabilistic framework allows for improved data analysis results. The concept of integrated data analysis (IDA) in the framework of Bayesian probability theory is outlined and contrasted with conventional data analysis. Components of the probabilistic approach are summarized and specific ingredients beneficial for data analysis at fusion devices are discussed.

ITER↗

Multi-Scale Integrated Monitoring System for Enhancing Methane Emission Detection, Quantification & Prediction

This report details the progress and findings of a comprehensive study on reviewing existing solutions, identifying technology gaps, and formulating an “all-in-one” integrated strategy for developing the next-generation multiscale methane monitoring and modeling platform, conducted under grant number DE-FE0032292. Co-led by Dr. David Ebert, Dr. Binbin Weng, and Dr. Chenghao Wang at the University of Oklahoma, the project’s goal was to develop an integrated approach for building this engineering platform to detect, quantify, and mitigate methane emissions across various temporal scale, spatial scales, and sectors. The planning grant study began with an extensive review of various methane sensing and monitoring technologies and systems, surveying over 100 technology providers globally. This review revealed the prevalence of optical methods over chemical methods in commercially available sensors, with Non-Dispersive Infrared (NDIR), Tunable Diode Laser Absorption Spectroscopy (TDLAS), and Optical Gas Imaging (OGI) cameras being the most prevalent options. A trend towards more advanced optical techniques was observed, driven by increased regulatory focus and technological advancements. The technical evaluation of these sensing technologies provided crucial insights into their capabilities and limitations. The study examined emerging technologies such as Differential Absorption LiDAR (DIAL), which show promise for high-precision and long-range detection. The team then investigated the features and application bandwidth of various sensing platforms, including handheld, fixed/stationary, mobile, aerials, and spaceborne monitors. Pilot field studies were conducted to assess the capabilities of solutions for different emission scenarios. Field work with sensor deployments was conducted at three distinct site types: an oil & gas industry site, a cattle ranching operation, and a waste processing facility. The team also conducted a thorough review of methane flux inverse modeling approaches, focused on physically based methods. These approaches were categorized into simple, intermediate, and advanced methods. A realtime WRF-GHG (Weather Research and Forecasting-Greenhouse Gas) modeling system was developed and applied, incorporating multiple data sources to guide field experiments and inform methane plume detection. The project identified and analyzed numerous categories of methane data sources, including satellite measurements, ground-based sensors, and inventory databases. Key platforms examined include EDGAR, EPA GHGI, NASA TROPOMI, Carbon Mapper, and Climate TRACE, among others. The team proposed an architecture for a comprehensive methane monitoring platform. This system incorporates multi-source data acquisition, advanced data processing and assimilation, interactive visualization tools, and analytical capabilities for emissions forecasting and scenario analysis. The proposed platform aims to provide a user-friendly interface catering to various stakeholders, from researchers to policymakers. The architecture includes sophisticated data ingestion methods, a centralized data warehouse, and advanced analytical tools for data fusion and interpretation. To ensure the relevance and effectiveness of the proposed system, a comprehensive survey was conducted to gather stakeholder input on system requirements. Key findings include a strong need for integrating various data types and formats, a preference for real-time data updates and advanced visualization tools, and a demand for user-friendly interfaces catering to different expertise levels.

03 NATURAL GAS↗

Accumulation of Soil Microbial Necromass Controlled by Microbe–Mineral Interactions

Soil organic matter (SOM) is a key reservoir for global carbon (C), supporting soil fertility and influencing greenhouse gas emissions. Microbial residues, composed of dead cells and cellular fragments, are major contributors to SOM formation. Yet, mechanisms by which minerals enhance the accumulation of microbial residues remain poorly understood. Here, we used 13 C-labeled glucose in a year-long incubation to trace microbial residue in sandy and silty soils. Across both soils, approximately 89% of retained microbial 13 C was recovered in the fine (<53 μm) mineral-associated organic matter (MAOM) pool. Within this pool, the light MAOM fraction, enriched in poorly crystalline Fe minerals, held 4.3 times more 13 C than the heavy, phyllosilicate-dominated MAOM fraction, despite accounting for only 17.2% of the total MAOM mass and 12.3% of the total soil mass. Along with 13 C enrichment, the light MAOM fraction showed greater abundance of N-containing groups, e.g., (amides and amino groups), indicative of microbial-derived compounds like proteins and amino sugars. Fe oxides in light MAOM from both soils were spatially dispersed. Microbial residue accumulation was greater in finer-textured silty soil. These findings demonstrate that mineral composition and texture jointly regulate microbial necromass accrual, highlighting light MAOM as a key pool for enhancing soil C storage.

13C isotope labeling↗

Plutonium Signatures in Molten-Salt Reactor Off-Gas Tank and Safeguards Considerations

Fluid-fueled molten-salt reactors (MSRs) are actively being developed by several companies, with plans to deploy them internationally. The current IAEA inspection tools are largely incompatible with the unique design features of liquid fuel MSRs (e.g., the complex fuel chemistry, circulating fuel inventory, bulk accountancy, and high radiation environment). For these reasons, safeguards for MSRs are seen as challenging and require the development of new techniques. This paper proposes one such technique through the observation of the reactor’s off-gas. Any reactor design using low-enriched uranium will build up plutonium as the fuel undergoes burnup. Plutonium has different fission product yields than uranium. Therefore, a shift in fission product production is expected with fuel evolution. The passive removal of certain gaseous fission products to the off-gas tank of an MSR provides a valuable opportunity for analysis without significant modifications to the design of the system. Uniquely, due to the gaseous nature of the isotopes, beta particle emissions are available for observation. The ratios of these fission product isotopes can, thus, be traced back to the relative amount and types of fissile isotopes in the core. This proposed technique represents an effective safeguards tool for bulk accountancy which, while avoiding being onerous, could be used in concert with other techniques to meet the IAEA’s timeliness goals for the detection of a diversion.

Dunkle, Nicholas (ORCID:000000027323011X)↗

Assessment of MQXF Quench Heater Insulation Strength and Test of Modified Design

The HL-LHC interaction region magnet triplets (Q1,Q2, and Q3) will be composed of superconducting Nb 3 Sn quadrupoles. The MQXF quadrupole protection system is based on CLIQ (Coupling-Loss Induced Quench system) and outer layer quench heaters. Furthermore, this paper reports a summary of quench heaters to coil high voltage tests performed on MQXF short and long coils in air after fabrication, and in air and He gas after magnet training. Breakdown voltage values demonstrate good margin with respect to the Electrical design criteria for the HL-LHC inner triplet mag-nets. A modification in the quench heater installation-with an extra layer of fiber glass between the coil and the quench heater trace-has been proposed and tested in a mirror magnet to further increase electrical margins. Results demonstrated improvements of high voltage margin at the expense of a clear increase of hot spot temperature.The baseline heater to coil insulation was assessed to be able to guarantee safe operation for the Nb 3 Sn quadrupole magnets for the interaction regions of HL-LHC.

43 PARTICLE ACCELERATORS↗

Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties**

Abstract The study presents an ab‐initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF‐vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first‐principles‐based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange‐correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT‐constrained microkinetic model optimization for other heterogeneously catalyzed systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

For this work, hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ~50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ~100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca 2+ , Mg 2+ , Na + , Sr2 + , Fe, Mn, Cl – , Br – ) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time. Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87 Sr/ 86 Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO 4 2– fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site. Water oxygen (δ 18 O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ 18 O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ 37 Cl in the FP fluids varied from ~ –0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ 37 Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition. Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO 4 2– in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reproducibility of Radiokrypton in Deep Desert Aquifers: Insights from a Decade of Research

Great technical advances have been achieved since the first atom-trap trace analysis (ATTA) -based radiokrypton application in Egypt, where 1 Myr old groundwater was discovered. Beyond advances in ATTA measurement capabilities, including reduction in sample size, analysis duration, and analytical uncertainty, major progress has been achieved over the past two decades in the sample collection and preparation techniques. These advances paved the expansion of ATTA-based noble gas applications to many other aquifers worldwide, illuminating the nature and flow pattern of deep groundwater systems. While the potential of this new analytical technique for old groundwater dating is well recognized, another important aspect yet to be examined is the reproducibility of radiokrypton in aquifers over time, i.e., how representative is a discrete groundwater sample, collected at a specific time and location, for the natural groundwater system? The likelihood of a negative answer is increased by flow-field disturbance in aquifers following massive groundwater abstraction. Here, in this work, we present repeated 81 Kr sampling and measurements in twenty-one sites over Israel, mostly of deep (up to 1 km) wells tapping confined aquifers in the arid to hyperarid Negev desert. The results demonstrate that radiokrypton measurements are indeed reproducible, even in cases where samples were collected as long as nine years apart and from highly productive (∼1 Mm 3 /yr order) pumping wells. Furthermore, many of the repeated measurements in this study (17 out of the 21 sites) were conducted with different ATTA Instruments in two different laboratories using slightly different sampling, preparation, and analysis techniques, yet with an overall good agreement. The consistency in the ATTA-based 81 Kr-dating results over time highlights the robustness of this state-of-the-art technique as a tool to unravel groundwater flow patterns and encourages further applications to many other yet-to-be-explored deep aquifers.

atom-trap trace analysis↗

Methane flux measurements in rice by static flux chamber and eddy covariance

Abstract Understanding methane (CH 4 ) fluxes from rice ( Oryza sativa L.) at the field scale is paramount to reducing environmental impacts while ensuring global food security. Greenhouse gas (GHG) measurements at the plot scale using static flux chambers (SFC) have long informed the understanding of flux dynamics and have largely been the basis of global flux estimates. However, in many parts of the world, the landscapes where agricultural fluxes are generated come from larger fields. Eddy covariance (EC) can measure trace gases on larger fields, but there are few studies available quantifying CH 4 emissions under typical practices at a field scale. Furthermore, few of these studies are from the U.S. Midsouth, the largest producer of U.S. rice. This study compares and quantifies field‐scale SFC and EC flux measurements on a large commercial system in northeastern Arkansas during the 2015 and 2016 growing seasons, following typical producer practices. Daily measured SFC CH 4 fluxes did not differ from EC‐daily CH 4 fluxes ( p = .108). Total season CH 4 emissions, calculated as the sum of daily fluxes ranged from 50 to 156 kg CH 4 ha −1 season −1 , with SFC reporting greater emissions than EC. Although SFC and EC‐daily flux measurements were similar early ( p = .382) and late ( p = .543) in the season, they differed mid‐season ( p < .001) with SFC consistently reporting greater fluxes than EC. The findings of this study help unify season long plot‐scale and field‐scale flux measurements and signify an advancement of our understanding of GHG fluxes from rice systems.

Reba, Michele L.↗

Influence functions for the Delaware Oil and Gas Basin Tower Network

This data consists of influence functions created for the Delaware tower network for the purpose of calculating methane enhancements in the region. Two different footprint models were used. The Lagrangian Particle Dispersion model (LPDM, Uliasz 1993) was run from March 2020-May 2023. The model uses in-house WRF simulations for the meteorological transport as described in Barkley et al., (2023). Nine hundred (900) particles were released during each hourly period and are traced back 72 hours backwards in time. A static binning height of 110 m AGL was used to calculate surface influence. After May 2023, the LPDM simulations were phased out and replaced with influence functions created using HYSPLIT under the STILT configuration (Lin et al., 2003). The STILT influence functions use HRRR for the meteorological transport (Dowell et al., 2022). Nine hundred (900) particles were released during each hourly period and are traced back 72 hours backwards in time. A binning height of half the boundary layer height was used to calculate surface influence. Footprints are currently available from Sept 2020-December 2024 and will be updated periodically as more are generated in time. No STILT influence functions were created for tower site Maljimar, which was decommissioned in March 2022. Lat/Lon grid information for the LPDM influence functions is contained in lpdm-lat-lon-grid.nc. STILT grid information is contained within the influence functions themselves. Tower coordinates and heights can be found in tower-info.csv

Barkley, Z. R.↗

[C ιι] Map of the Molecular Ring and Arms of the Spiral Galaxy NGC 7331*

We present the [C ιι] 157.7 μm map of galaxy NGC 7331 obtained with the Field-Imaging Far-Infrared Line Spectrometer on board the Stratospheric Observatory for Infrared Astronomy (SOFIA). This map extends an existent Herschel/Photodetector Array Camera and Spectrometer observation of the central strip of the galaxy to encompass the entire molecular ring and much of the disk, including multiple spiral arms with intense far-IR emission. We also present Herschel archival data of the [N ιι] 205 μm line, which covers a substantial part of the [C ιι] SOFIA observations and allows us to estimate the neutral fraction of the [C ιι] emission along the ring and disk of the galaxy. We find that the neutral fraction rises with the distance from the center. In addition, by tracing the azimuthal variation of the neutral fraction, we are able to see how our observing perspective affects this measurement. The high inclination of NGC 7331 allows us to glimpse the internal walls of the molecular ring. There, young bright stars emit UV radiation causing more [C ιι] emission to be produced in the ionized gas. On the outer walls, opaque dust shrouds the rest of the ring, making the neutral medium the dominant source of [C ιι] emission. Through spatial analysis comparing the [C ιι] emission to tracers of gas heating, we are able to investigate how the photoelectric heating efficiency varies throughout NGC 7331 and extend global measurements of the [C ιι] deficit to local environments. Since the origin of [C ιι] emission has typically been studied in face-on galaxies, our results shed a new light on the interpretation of [C ιι] emission, especially when studying distant galaxies with unknown inclination.

79 ASTRONOMY AND ASTROPHYSICS↗

Direct Observation of Morphological and Chemical Changes during the Oxidation of Model Inorganic Ligand-Capped Particles

Functionalization and volatilization are competing reactions during the oxidation of carbonaceous materials and are important processes in many different areas of science and technology. Here, we present a combined ambient pressure X-ray photoelectron spectroscopy (APXPS) and grazing incidence X-ray scattering (GIXS) investigation of the oxidation of oleic acid ligands surrounding NaYF 4 nanoparticles (NPs) deposited onto SiO x /Si substrates. While APXPS monitors the evolution of the oxidation products, GIXS provides insight into the morphology of the ligands and particles before and after the oxidation. Our investigation shows that the oxidation of the oleic acid ligands proceeds at O 2 partial pressures of below 1 mbar in the presence of X-rays, with the oxidation eventually reaching a steady state in which mainly CH x and –COOH functional groups are observed. The scattering data reveal that the oxidation and volatilization reaction proceeds preferentially on the side of the particle facing the gas phase, leading to the formation of a chemically and morphologically asymmetric ligand layer. This comprehensive picture of the oxidation process could be obtained only by combining the X-ray scattering and APXPS data. The investigation presented here lays the foundation for further studies of the stability of NP layers in the presence of reactive trace gases and ionizing radiation and for other nanoscale systems where chemical and morphological changes happen simultaneously and cannot be understood in isolation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Novel Charfuel® Coal Refining Process 18 TPD Pilot Plant Project for Co- Producing an Upgraded Coal Product, and Commercially Valuable Co- Products: Area of Interest #3 – Coal Beneficiation Pilot Plant Testing (Final Report)

Operation of Carbon Fuels, LLC’s (“CF”) existing, permitted 18 TPD pilot plant located in Golden, Colorado using two individually ranked (ASTM D 388) coal types (two campaigns), employing the novel Charfuel® coal refining process to produce an upgraded coal product and a number of high-valued organic and inorganic coproducts (for which there presently exists large commercial markets) in order to produce engineering and product data which will then be utilized toward the design of a commercial scale integrated facility (pre-feed document). Carbon Fuels, LLC has developed the Charfuel® Coal Refining Process which refines domestically abundant, raw coal (in the same manner as crude oil is refined) to produce the identical, high value co-products that are refined from crude oil. Thus, gasoline, jet fuel, “green diesel”, fuel oil, and marine fuels, as well as petrochemicals such as benzene, toluene, xylene, and methanol are refined from raw coal using this process. The Charfuel® Coal Refining Process is not a coal conversion process, like pyrolysis, or indirect liquefaction. Nor is it an alternative energy system. Rather it is a coal refining process that has the ability to economically produce products traditionally associated with the refining of crude oil but using only abundant, raw coal as the refinery feed stock. The Charfuel® Coal Refining Process is more economical than crude oil refining and is environmentally benign. Therefore, this value added process yields a return on investment well above 50% for a commercial facility. Furthermore, the Charfuel® process, unlike alternatives such as ethanol and hydrogen, can utilize the existing transportation, delivery, and other petroleum based systems. Hence, there is no need for new engines, pipelines, tankers, or product acceptance. As a result, the profitability of the process is increased. Objectives: (1) Operation of the integrated 18 tpd pilot plant, using two coal types (ranks); (2) Demonstration of process flexibility in being able to produce different products (gas, liquid, and char), as well as determination of operating parameters for identifying scale up criteria for two coal types (ranks); (3) Generation of engineering and design information (process specifications) for use in designing a commercial scale plant (scale-up); (4) Determination of important environmental issues surrounding the process and the products such as fate of trace elements (mercury and other heavy metals) and distributions of SO2, NOx, and CO 2 by analysis of effluent streams; (5) Production of sufficient product to allow reliable commercial economic evaluation of both the refined coal product and the coproducts; and, (6) Assessment of longer-term reliability of unit operations. Period 1: reconfiguration of the 18 TPD plant to meet specific FOA requirements and to qualify the facility for operation; and, Period 2: operation of the 18 TPD plant for two campaigns using two coals types (ranks) which are widely commercially used and abundant - the first being a subbituminous (Powder River Basin (“PRB”)) coal, and the second a bituminous (Illinois #6) coal.

01 COAL, LIGNITE, AND PEAT↗

Geochemistry and Multiomics Data Differentiate Streams in Pennsylvania Based on Unconventional Oil and Gas Activity

Unconventional oil and gas (UOG) extraction is increasing exponentially around the world, as new technological advances have provided cost-effective methods to extract hard-to-reach hydrocarbons. While UOG has increased the energy output of some countries, past research indicates potential impacts in nearby stream ecosystems as measured by geochemical and microbial markers. Here, we utilized a robust data set that combines 16S rRNA gene amplicon sequencing (DNA), metatranscriptomics (RNA), geochemistry, and trace element analyses to establish the impact of UOG activity in 21 sites in northern Pennsylvania. These data were also used to design predictive machine learning models to determine the UOG impact on streams. We identified multiple biomarkers of UOG activity and contributors of antimicrobial resistance within the order Burkholderiales. Furthermore, we identified expressed antimicrobial resistance genes, land coverage, geochemistry, and specific microbes as strong predictors of UOG status. Of the predictive models constructed (n = 30), 15 had accuracies higher than expected by chance and area under the curve values above 0.70. The supervised random forest models with the highest accuracy were constructed with 16S rRNA gene profiles, metatranscriptomics active microbial composition, metatranscriptomics active antimicrobial resistance genes, land coverage, and geochemistry (n = 23). The models identified the most important features within those data sets for classifying UOG status. These findings identified specific shifts in gene presence and expression, as well as geochemical measures, that can be used to build robust models to identify impacts of UOG development.

16S rRNA↗

Trace gases at TRACER ANC site

Speciated volatile organic compounds (VOCs) were measured using an Ionicon PTR-TOF 8000 from 20 June to 3 July 2022 at the TRACER ancillary (TRACER ANC) site in Guy, TX. The dataset is reported at 1-min time resolution. Mixing ratios (ppb) are provided for acetone, methanol, acetaldehyde, dimethyl sulfide (DMS), furan, isoprene, methyl vinyl ketone plus methyl ethyl ketone (MVK + MEK), terpenes, xylene, and trimethylbenzene. Instrument calibrations for these species were performed weekly using a certified gas standard.

acetaldehyde↗

On the influence of halo mass accretion history on galaxy properties and assembly bias

Halo assembly bias is the secondary dependence of the clustering of dark matter haloes on their assembly histories at fixed halo mass. This established dependence is expected to manifest itself on galaxy clustering, a potential effect commonly known as galaxy assembly bias. Using the IllustrisTNG300 magnetohydrodynamical simulation, in this work we analyse the dependence of the properties and clustering of galaxies on the specific mass accretion history of their hosting haloes (sMAH). We first show that several halo and galaxy properties strongly correlate with the slope of the sMAH (β) at fixed halo mass. Haloes with increasingly steeper β increment their masses faster early on, and their hosted galaxies present larger stellar-to-halo mass ratios, lose their gas faster, reach the peak of their star formation histories at higher redshift, and become quenched earlier. We also demonstrate that β provides a more stable link to these key galaxy formation properties than other broadly employed halo proxies, such as formation time. Finally, we measure the secondary dependence of galaxy clustering on β at fixed halo mass. By tracing back the evolution of individual haloes, we show that the amplitude of the galaxy assembly bias signal for the progenitors of z = 0 galaxies increases with redshift, reaching a factor of 2 at z = 1 for haloes of Mhalo = 10 11.5 –10 12 h –1 M ⊙ . The measurement of the evolution of assembly bias along the merger tree provides a new theoretical perspective to the study of secondary bias. Our findings have also important implications for the generation of mock catalogues for upcoming cosmological surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

Quantitation of olefins in sustainable aviation fuel intermediates using principal component analysis coupled with vacuum ultraviolet spectroscopy

Olefins, a common intermediate from biomass conversion processes, are undesirable in jet fuel because of their poor thermal stability. This paper presents an approach for olefin quantitation using 2D gas chromatography coupled with vacuum ultraviolet spectroscopy. Principal component analysis was used to reduce the dimensionality of the spectroscopic data from a highly olefinic fuel intermediate. A principal component template was created that enabled olefin quantitation, which was compared to the existing GCxGC-VUV approach from the literature. The principal component method was able to identify and quantify trace amounts of cyclodienes, which were present at only 0.01 wt% in the fuel sample. The principal component approach also identifies species that fall outside of the GCxGC template. For instance, quantitation with the literature method resulted in an olefin concentration of 0.95 times that of the principal component method due to olefins falling outside of the expected GCxGC regions. The principal component results were compared with 13 C and 1 H NMR data, which confirmed that the fuel had a high concentration of olefins and alkanes with little aromatic content.

Kosir, Shane↗

A Bayesian approach to time-domain photonic Doppler velocimetry analysis

Photonic Doppler velocimetry (PDV) is an established technique for measuring the velocities of fast-moving surfaces in high-energy-density experiments. In the standard approach to PDV analysis, the short-time Fourier transform (STFT) is used to generate a spectrogram from which the velocity history of the target is inferred. The user chooses the form, duration, and separation of the window function. Here, in this study, we present a Bayesian approach to infer the velocity directly from the PDV oscilloscope trace, without using the spectrogram for analysis. This is clearly a difficult inference problem due to the highly periodic nature of the data, but we find that with carefully chosen prior distributions for the model parameters, we can accurately recover the injected velocity from synthetic data. We validate this method using PDV data collected at the STAR two-stage light gas gun at Sandia National Laboratories, recovering shock-front velocities in quartz that are consistent with those inferred using the STFT-based approach and are interpolated across regions of low signal-to-noise data. Although this method does not rely on the same user choices as the STFT, we caution that it can be prone to misspecification if the chosen model is not sufficient to capture the velocity behavior. Analysis using posterior predictive checks can be used to establish whether a better model is required, although more complex models come with additional computational cost, often taking more than several hours to converge when sampling the Bayesian posterior. We, therefore, recommend it be viewed as a complementary method to that of the STFT-based approach.

Allison, James R. [First Light Fusion Ltd., Yarnto↗