Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ION CYCLOTRON”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Large-Scale Interlaboratory DI-FT-ICR MS Comparability Study Employing Various Systems

We report ultra-high resolution mass spectrometry (UHR-MS) coupled with direct infusion (DI) electrospray ionization offers a fast solution for accurate untargeted profiling. Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers have been shown to produce a wealth of insights into complex chemical systems because they enable unambiguous molecular formula assignment even if the vast majority of signals is of unknown identity. Inter-laboratory comparisons are required to apply this type of instrumentation in quality control (for food industry or pharmaceutics), large-scale environmental studies or clinical diagnostics. Extended comparisons employing different FT-ICR MS instruments with qualitative direct infusion analysis are scarce since the majority of detected compounds cannot be quantified. The extent to which observations can be reproduced by different laboratories remains unknown. We set up a preliminary study which encompassed a set of seventeen laboratories around the globe, diverse in instrumental characteristics and applications, to analyze the same sets of extracts from commercially available standard human blood plasma and Standard Reference Material (SRM) for blood plasma (SRM1950), which were delivered at different dilutions or spiked with different concentrations of pesticides. The aim of this study was to assess the extent to which the outputs of differently tuned FTICR mass spectrometers, with different technical specifications, are comparable for setting the frames of a future DI-FT-ICR MS ring trial. We concluded that a cluster of five laboratories, with diverse instrumental characteristics showed comparable and representative performance across all experiments, setting a reference to be used in a future ring trial on blood plasma.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗
DOE OSTI2023

WHONDRS River Corridor Sediment and Water Geochemistry and In Situ Sensor Data from Machine-Learning-Informed Sites across the Contiguous United States (v6)

This dataset supports a broader study examining hyporheic zone respiration rates to improve predictive models at a contiguous United States (CONUS) scale. The CONUS-Scale Model-Sample Study (CM) was designed following ICON (integrated, coordinated, open, and networked) principles to facilitate a model-experiment (ModEx) iteration approach, leveraging crowdsourced sampling across the CONUS. New machine learning models were created every month to guide sampling locations. Data from the resulting samples were used to test and rebuild the machine learning models for the next round of sampling guidance. Sampling began in April 2022 and ended in October 2023. In addition to the widely distributed CONUS sites, a more spatially focused sampling occurred in the Yakima River Basin, WA in summer 2022. Data from this more spatially intensive sampling occurred under the label “Second Spatial Study (SSS)” and were also included in the machine learning models. Other data types collected from SSS that were not part of CM were published in a separate data package (https://data.ess-dive.lbl.gov/view/doi:10.15485/1969566). This data package was originally published in February 2023. It was updated in June 2023 (v2; new and modified files); December 2023 (v3; new and modified files); June 2024 (v4; new and modified files); April 2024 (v5; new and modified files); and September 2025 (v6; modified files). See the change history section in the readme for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. This dataset is comprised of two folders of field photos and videos, one folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data and one main data folder containing (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) readme; (5) international generic sample number (IGSN) mapping file; (6) field protocols; (7) a subfolder with sample data; and (8) a subfolder with sensor data. The sample data subfolder contains (1) surface water and sediment dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (2) surface water and sediment total nitrogen data and averages; (3) surface water major cations and anions and averages; (4) sediment grain size data; (5) sediment iron (II) data and averages; (6) wet sediment mass, dry sediment mass, water mass, and wet sediment volume in incubation and sediment ICR vials; (7) sediment incubation respiration rate data and averages; (8) normalized respiration rate data and averages; (9) methods codes; (10) sediment specific surface area; (11) sediment percent carbon and nitrogen; (12) sediment gravimetric moisture and averages; (15) sediment X-ray diffraction (XRD) data; (16) sediment adenosine triphosphate (ATP) and averages; (17) a subfolder with sediment incubation respiration data, scripts, and plots; (18) surface water and sediment FTICR methods; and (19) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains five subfolders, one containing the sediment .xml data files, one containing the water .xml files, one containing the sediment CoreMS output files, one containing the water CoreMS output files, and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS).The sensor data subfolder contains (1) a subfolder with miniDOT dissolved oxygen and temperature data and plots; (2) miniDOT dissolved oxygen and temperature summary data; and (3) miniDOT installation methods. All files are .csv, .pdf, .R, .xml, .d, .html, .Rmd, .py, .cal, .json, .jpg, .jpeg, .png, .mov, or .mp4. CORRECTION: Carbon and nitrogen content are reported as percentages. The current column headers "01395_C_percent_per_mg" and "01397_N_percent_per_mg" are incorrect. These should read "01395_C_percent" and "01397_N_percent" and will be corrected in the next version of this data package. We thank the United States Forest Service, Washington Department of Fish and Wildlife, Washington Department of Natural Resources, Cowiche Canyon Conservatory, Washington State Parks and Recreation Commission (Scientific Research Permit #210901), and the Confederated Tribes and Bands of the Yakama Nation for access to field locations where the samples labeled “SSS” were collected. We also thank the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview. WHONDRS consortium members were asked to provide any acknowledgments for the collection of samples labeled “CM” and the following is a list of acknowledgments that were submitted with their corresponding Site IDs: (MART) Research activities were conducted in part on the Wind River Experimental Forest within the Gifford Pinchot National Forest; (MP- 100379) Philadelphia is part of Lenapehoking, the ancestral homelands of the Lenape peoples; (MP-102398) Land surveyed is the ancestral homelands of the Nookhose'iinenno (Arapaho), Tsis tsis'tas (Cheyenne), and Nuuchu (Ute); (MP-100749 and MP- 100747) Georgia Coastal Ecosystem LTER, OCE-1832178; (SP-70 and SP-72) Eastern Shoshone, Shoshone-Bannock; (MP- 102944) Funded by Oregon Watershed Enhancement Board. On the traditional lands of the Confederated Tribes of the Siletz, Confederated Tribes of the Grand Rhonde, and the Clatsop-Nehalem Confederated Tribe; (MP- 100607) Holiday Creek is located on the traditional territory of the Monacan Indian Nation; (SP-45) Lafayette Blue Springs State Park; (MP-102420) NSF DEB-2016749; (MP-100019) New Hampshire Agriculture Experiment Station; (SP-35) Rayonier (land owner; https://www.rayonier.com/); (MP- 101276) US Department of Energy, Office of Science, Biological and Environmental Research, Subsurface Biogeochemical Research, Watershed Dynamics and Evolution SFA at ORNL; (MP- 103224) Watershed Dynamics and Evolution SFA at ORNL; (MP- 101584) Traditional lands of the Oceti Sakowin (Dakota, Lakota, Nakoda) and Anishinaabe Peoples.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Contributions to Lignomics: Stochastic Generation of Oligomeric Lignin Structures for Interpretation of MALDI–FT‐ICR‐MS Results

The lack of standards to identify oligomeric molecules is a challenge for the analysis of complex organic mixtures. High-resolution mass spectrometry—specifically, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS)—offers new opportunities for analysis of oligomers with the assignment of formulae (C x H y O z ) to detected peaks. However, matching a specific structure to a given formula remains a challenge due to the inability of FT-ICR MS to distinguish between isomers. Additional separation techniques and other analyses (e.g., NMR spectroscopy) coupled with comparison of results to those from pure compounds is one route for assignment of MS peaks. Unfortunately, this strategy may be impractical for complete analysis of complex, heterogeneous samples. In this study we use computational stochastic generation of lignin oligomers to generate a molecular library for supporting the assignment of potential candidate structures to compounds detected during FT-ICR MS analysis. Furthermore, this approach may also be feasible for other macromolecules beyond lignin.

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

Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high‐resolution mass spectrometry data across a freshwater stream network

Abstract Advancing our understanding of dissolved organic matter (DOM) chemistry in aquatic systems necessitates the integration of data streams from multiple analytical platforms. Some measurements require pretreatment with solid phase extraction (SPE), while others are performed directly on whole water samples. Evidence has suggested that SPE will be biased against select DOM fractions, leading to concerns over the ability to establish data linkages across platforms with variable needs for SPE pretreatment, such as those from optical measurements and those that provide high‐resolution molecular information. Here, we directly addressed this concern by assessing the impact of SPE on DOM optical properties through excitation–emission matrices with parallel factor analysis (PARAFAC) for 47 samples across a stream network within a single watershed reflective of variable DOM sources. PARAFAC data was further paired with molecular information obtained by Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). A comparison of PARAFAC models first revealed no systematic qualitative differences in major components between whole water DOM and DOM isolated by SPE (SPE‐DOM); however, quantitative biases against select components were observed. Further linkages with FTICR‐MS data revealed that the molecular fingerprint associated with each PARAFAC component was consistent between the whole water DOM and SPE‐DOM. Our results suggest that bulk scale linkages across these analytical platforms could be inferred irrespective of the observed quantitative biases resulting from SPE for samples within this example watershed. This work represents a key step toward the systematic evaluation of linkages between optical and high‐resolution mass spectrometry datasets in freshwater lotic environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

A History of Molecular Level Analysis of Natural Organic Matter by FTICR Mass Spectrometry and The Paradigm Shift in Organic Geochemistry

Natural organic matter (NOM) is a complex mixture of biogenic molecules resulting from the deposition and transformation of plant and animal matter. It has long been recognized that NOM plays an important role in many geological, geochemical, and environmental processes. Of particular concern is the fate of NOM in response to a warming climate in environments that have historically sequestered carbon (e.g., peatlands and swamps) but may transition to net carbon emitters. In this review, we will highlight developments in the application of high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in identifying the individual components of complex NOM mixtures, focusing primarily on the fraction that is dissolved in natural waters (dissolved organic matter or DOM). We will first provide some historical perspective on developments in FTICR technology that made molecular-level characterizations of DOM possible. In conclusion, a variety of applications of the technique will then be described, followed by our view of the future of high-field FTICR MS in carbon cycling research, including a particularly exciting metabolomic approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Topography and canopy cover influence soil organic carbon composition and distribution across a forested hillslope in the discontinuous permafrost zone

Abstract Topography and canopy cover influence ground temperature in warming permafrost landscapes, yet soil temperature heterogeneity introduced by mesotopographic slope positions, microtopographic differences in vegetation cover, and the subsequent impact of contrasting temperature conditions on soil organic carbon (SOC) dynamics are understudied. Buffering of permafrost‐affected soils against warming air temperatures in boreal forests can reflect surface soil characteristics (e.g., thickness of organic material) as well as the degree and type of canopy cover (e.g., open cover vs. closed cover). Both landscape and soil properties interact to determine meso‐ and microscale heterogeneity of ground warming. We sampled a hillslope catena transect in a discontinuous permafrost zone near Fairbanks, Alaska, to test the small‐scale (1 to 3 m) impacts of slope position and cover type on soil organic matter composition. Mineral active layer samples were collected from backslope, low backslope, and footslope positions at depths spanning 19 to 60 cm. We examined soil mineralogical composition, soil moisture, total carbon and nitrogen content, and organic mat thickness in conjunction with an assessment of SOC composition using Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). Soils in the footslope position had a higher relative contribution of lignin‐like compounds, whereas backslope soils had more aliphatic and condensed aromatic compounds as determined using FT‐ICR‐MS. The effect of open versus closed tree canopy cover varied with the slope position. On the backslope, we found higher oxidation of molecules under open cover than closed cover, indicating an effect of warmer soil temperature on decomposition. Little to no effect of the canopy was observed in soils at the footslope position, which we attributed, in part, to the strong impact of soil moisture content in SOC dynamics in the water‐gathering footslope position. The thin organic mat under open cover on the backslope position may have contributed to differences in soil temperature and thus SOC oxidation under open and closed canopies. Here, the thinner organic mat did not appear to buffer the underlying soil against warm season air temperatures and thus increased SOC decomposition as indicated by the higher oxidation of SOC molecules and a lower contribution of simple molecules under open cover than the closed canopy sites. Our findings suggest that the role of canopy cover in SOC dynamics varies as a function of landscape position and soil properties, namely, organic mat thickness and soil moisture. Condition‐specific heterogeneity of SOC composition under open and closed canopy cover highlights the protective effect of canopy cover for soils on backslope positions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Soil properties and biochemical composition of ground-dwelling bee nests in agricultural settings

Soils deliver underrecognized ecosystem services by supplying habitat for ground-dwelling pollinators, such as wild bees and other organisms, that pollinate 80% of insect-pollinated plants and play a critical role in securing resilient pollination provisions. Our objective is to identify soil properties of ground nesting bee nests in agricultural settings of western Oregon, USA. We confirmed ground nesting bee and sand wasp activity in 7 agricultural sites and 1 recreational park. Soils from 17 bee and sand wasp nests were analyzed for pH, particle size distribution, and carbon and nitrogen content. We visually confirmed that 8 of the nesting bees were sweat bees from the Halictidae family and identified a captured bee specimen as Lasioglossum (Dialictus) (Hymenoptera: Halictidae). We located 2 sites with sand wasps where specimens were identified as Cerceris and Bembix (Hymenoptera: Crabronidae). The organic matter composition of three soil samples scraped from the linings of active nests were assessed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The FTICR-MS results identified unknown lipid compounds in the nest soil samples, which we hypothesize are waterproofing lipids secreted to line cell walls. Bee nests occurred in slightly acidic, bare-ground soils with low rock/vegetation coverage, low organic carbon content (<1%), and exhibited significantly higher silt-plus-clay fractions (>75%) versus data published for bee nests in prior work. Our findings present important implications for textural controls on nest site selection in wet, cool environments and demonstrate the importance of integrating soil properties to improve our understanding of ground-dwelling organisms and associated soil habitats.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Single-Cell Metabolomics with Rapid Determination of Chemical Formulas from Isotopic Fine Structures

Metabolomic measurements can provide functional readouts of cellular states and phenotypes. Here, we present a protocol for single-cell metabolomics that permits direct untargeted detection of a broad number of metabolites under ambient conditions, without the need for sample processing, and with high confidence in the discovery and identification of the molecular formulas for detected metabolites. This protocol describes combining fiber-based laser ablation electrospray ionization (f-LAESI) with a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer (21T-FTICR-MS) to obtain high confidence molecular formula information about detected metabolites. The f-LAESI source utilizes mid-infrared laser ablation through a sharp optical fiber tip, affording direct ambient analysis of cells without the need for sample processing. Using the 21T-FTICR-MS as a mass analyzer enabled measurement of the isotopic fine structure (IFS) for numerous metabolites simultaneously from single cells, and the IFSs were in turn computationally processed to rapidly determine the corresponding elemental compositions. This metabolomics technique complements other single cell omics measurement methods, helping to resolve complex molecular interactions that take place within cells unattainable from single cell transcriptomic and proteomics methods.

mass spectrometry, FTICR, FTMS, ultrahigh mass res↗
DOE OSTI2021

The importance of nutrients for microbial priming in a bog rhizosphere

Wetlands host anaerobic microbes which convert organic carbon into methane (CH 4 ), a powerful greenhouse gas. Wetland plants can influence which carbon compounds are available for microbial processing by exuding freshly fixed carbon from their roots. Notably, exudation of carbon from plant roots can trigger microbial priming: the process of new carbon stimulating the microbial community into processing more soil carbon than they otherwise would have. This study utilized high resolution Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) analysis to probe the chemical composition of soil organic compounds from the rhizosphere of Carex aquatillis, a common wetland sedge, which is known to have stimulated microbial priming within a peat soil. The goal was to identify what types of molecules are created or lost during microbial priming in the wetland rhizosphere and thus advance mechanistic understanding of the process. FT-ICR-MS analysis demonstrated that more microbial transformations of carbon occurred among water-soluble compounds than among hydrophobic compounds, but that some hydrophobic compounds were processed as well. Crucially for understanding microbial priming, the root exudates triggered increased processing of high molecular weight molecules regardless of nutrient content but processed low molecular weight compounds only if they contained essential nutrients. Furthermore, the pattern of which molecules are processed and which are not is evidence for a selective priming effect in which some types of carbon compounds are used at an increased rate, while others are not.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Soil porous microstructure control over soil organic matter mobility: A multimethod workflow for understanding chemistry-dependent organic matter binding in soil

Soil organic matter (SOM) has attracted a great deal of interest; particularly for its potential to mitigate human derived CO 2 emissions. Studies have demonstrated that SOM plays a critical role in carbon storage and CO 2 sequestration. However, the sorption properties of SOM, which influence its transport in pore water and stabilization within the soil, remain poorly understood. This study develops a workflow to: (1) examine compound-specific advective and diffusive transport and desorption behaviors, (2) quantify desorption rates through stop-flow and continuous-flow column experiments, and (3) evaluate the impact of soil microporosity on SOM mobility using high-resolution imaging and extractions. Intact core column experiments were conducted on Uncultivated (Natural) and Cultivated soil samples, both were arid soils, collected in Washington State. X-ray computed tomography was employed to measure porosity and pore connectivity, while Fourier-transform ion cyclotron resonance mass spectrometry was used to analyze SOM composition. The findings revealed that cultivation increased total carbon and nitrogen levels due to irrigation and fertilization, enhancing carbon capture potential in arid soils. In contrast, the Natural soil, characterized by higher porosity and connectivity, contained more oxidized carbon. Pore network analysis indicated that soil compaction in the Cultivated soil may lead to longer diffusion pathways, significantly influencing SOM transport and stability.

Hydraulic Properties↗
DOE OSTI2020

The Material Plasma Exposure eXperiment: Mission and conceptual design

Mastering Plasma Material Interactions (PMI) is key for obtaining a high performance, high duty-cycle and safe operating fusion reactor. Numerous gaps exist in PMI which have to be addressed before a reactor can be built. In particular the lack of data at high ion fluence, fusion reactor divertor relevant plasma conditions and neutron displacement damage requires new experimental devices to be able to develop plasma facing materials and components. This has been recognized in the community and the U.S. fusion program is addressing this need with a new linear plasma device—the Material Plasma Exposure eXperiment (MPEX). MPEX will be a superconducting linear plasma device with magnetic fields of up to 2.5 T. The plasma source is a high-power helicon source (200 kW, 13.56 MHz). The electrons will be heated via Electron Bernstein Waves with microwaves using multiple 70 GHz gyrotrons (up to 600 kW in total). Ions will be heated via ion cyclotron heating in the so-called “magnetic beach heating” scheme in the frequency range of 6–9 MHz (up to 400 kW in total). An overview of the conceptual design and the project/design requirements is given in this paper.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Simultaneous H/D/T and 3He/4He absolute concentration measurements with an optical Penning gauge on JET

The Optical Penning (or Species-Selective Penning) Gauge technique is used for the measurement of the H2/D2/T2 fuel isotopic composition and He/D2 concentration in the neutralized particle exhaust of fusion devices. An Optical Penning detection system has already been used in JET during its first deuterium-tritium campaigns (DTE1) and has been chosen by ITER. Recent improvements to the sub-divertor diagnostic suite as well as the optical instrumentation, in preparation for the next DT campaign, have improved the optical throughput of the measurement and enabled 3He/D2 detection down to 0.1 %. For the first time, the 3He/4He isotopic ratio can be measured simultaneously with the H/D/T ratio. This technique is of particular interest for ion cyclotron resonance frequency (ICRF) heating scenarios.

Vartanian, S.↗
DOE OSTI2026

Composition and persistence of soil organic matter along eroding and depositional transects in buried vs. modern soil layers: A case of the Brady paleosol at Wauneta, Nebraska

Paleosols form when soils are buried through deposition by aeolian, colluvial, alluvial or other processes. Burial of former topsoil isolates soil organic matter (SOM) from surface conditions, allowing carbon to accumulate and potentially remain stable for millennia. In this study, SOM composition, distribution, and persistence were analyzed in the Brady Soil of Nebraska, USA to compare SOM spatial variability in modern and buried soils, as well as the impact of erosional exposure on SOM stability. The Brady Soil, formed as a surface soil during the Pleistocene-Holocene transition and now a paleosol buried up to 6 m deep (or more) by loess deposition during the Holocene, was sampled along burial (up to 5.8 m depth) and erosional (up to 1.8 m depth) transects to compare SOM dynamics in different geomorphic settings. Fourier Transform Infrared Spectroscopy (FTIR) and Fourier Transform ion cyclotron resonance mass spectrometry (FTICR-MS) were used to analyze SOM composition, while δ 13 C isotope analyses identified SOM sources and radiocarbon values were used to estimate turnover rates. Results confirmed a vegetation shift from C3 to C4 plants after Brady Soil formation, reflecting warming climatic conditions. Increasing SOM age and decreasing δ 13 C and δ 15 N values with depth indicated slowing of decomposition rate in buried soils. Higher pH in the Brady Soil suggested greater base cation content, supporting SOM stabilization through organo-mineral associations and aggregate formation. However, exposure of the Brady Soil due to surface erosion caused faster SOM turnover. This result suggested susceptibility of buried SOM to losses via decomposition upon erosional exposure, possibly accelerated by priming in response to modern SOM inputs. These findings highlight the potential loss of carbon stocks in buried soils under future climate change, as shifts in soil physicochemical properties may destabilize long-preserved SOM.

Environmental sciences↗
DOE OSTI2023

Presence of aromatic-rich organic matter and its characterization in grout materials: Implications for radionuclide immobilization

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESIFTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Here, evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Investigation of the silicon coated film characteristics on tungsten surface in EAST fusion device

Siliconization using 10 % SiD 4 + 90 % He assisted by ion cyclotron range of frequency discharge (ICRF) or glow discharge (GD) was performed in EAST with full tungsten (W) diverters. It was found that the coated Si film on W sample at a higher baking temperature (160 °C) was smoother than that at a lower baking temperature (60 °C). This was mainly because physically adsorbed gaseous impurities were released at a higher baker temperature. This process improved the adhesion between the film and the surface of W. An increase in the ICRF working power from 20 kW to 40 kW further increased the Si content and the film thickness by 1.5 times. The cleaning efficiency of ICRF on the surface of the W sample before siliconization was higher at 40 kW than that at 20 kW, which facilitated the removal of oxides and other compounds from the surface of W. The ratio of silicon/oxygen (Si/O) and the thickness improved considerably due to greater ionization and deposition of SiD 4 . Additionally, siliconization via GD was more uniform and 1.5 nm thicker than that via ICRF, which was because of the greater working gas pressure, coating duration, and homogeneity in GD. These results might be used as a reference for evaluating the effect of siliconization on plasma performance and its application in fusion devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Annotation of DOM metabolomes with an ultrahigh resolution mass spectrometry molecular formula library

Current approaches to analyzing metabolomic data often rely on matching MS/MS fragmentation data to sparse libraries or databases. This approach results in limited identification of features, often with less than 10% of the dataset being annotated. A complementary approach is to assign molecular formula to features based on accurate mass measurements, but the platforms commonly used for metabolomics do not have the needed accuracy or resolving power to do this robustly, particularly for larger molecules. Using our newly modified analysis tool, CoreMS, we generated a library of molecular formula from pooled samples analyzed with LC-21T FT-ICR MS. This library successfully annotated approximately 53.2% of features identified from the exometabolome of marine diatom Phaeodactylum tricornutum – a nearly ten-fold increase over the 5.9% annotation rate achieved using a conventional MS/MS library matching approach. Using this FT-ICR MS library approach, we were able to differentiate differences in the exometabolome of P. tricornutum in iron replete and iron limited conditions, with 668 metabolites being differentially expressed (p < 0.05, 2 x intensity difference) under these conditions. The traditional MS/MS fragmentation-based annotation approach only annotated 61 of these metabolites, while our novel pipeline annotated 450 metabolites and revealed 12 metabolites that were significantly more abundant under low iron conditions. Our results demonstrate the utility of ultrahigh resolution mass spectrometry for generating more comprehensive and confident molecular annotations.

21T-FTICR-MS, CoreMS↗
DOE OSTI2022

Natural organic matter composition and nanomaterial surface coating determine the nature of platinum nanomaterial-natural organic matter corona

Natural organic matter corona (NOM corona) is an interfacial area between nanomaterials (NMs) and the sur- rounding environment, which gives rise to NMs' unique surface identity. While the importance of the formation of natural organic matter (NOM) corona on engineered nanomaterials (NMs) to NM behavior, fate, and toxicity has been well-established, the understanding of how NOM molecular properties affect NOM corona composition remains elusive due to the complexity and heterogeneity of NOM. This is further complicated by the variation of NOMs from different origins. Here we use eight NOM isolates of different molecular composition and ultrahigh resolution Fourier-transform ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) to determine the mol- ecular composition of platinum NM-NOM corona as a function of NOM composition and NM surface coating. We observed that the composition of PtNM-NOM corona varied with the composition of the original NOM. The per- centage of NOM formulas that formed PVP-PtNM-NOM corona was higher than those formed citrate-PtNM-NOM corona, due to increased sorption of NOM formulas, in particular condensed hydrocarbons, to the PVP coating. The relative abundance of heteroatom formulas (CHON, CHOS, and CHOP) was higher in the PVP-PtNM-NOM corona than in citrate-PtNM-corona which was in turn higher than those in the original NOM isolate, indicating preferential partitioning of heteroatom-rich molecules to NM surfaces. The relative abundance of CHO, CHON, CHOS, CHOP and condensed hydrocarbons in PtNM-NOM corona increased with their increase in NOM isolates. Furthermore, PtNM-NOM corona is rich with compounds with high molecular weight. This study demonstrates that the composition and properties of PtNM-NOM corona depend on NOM molecular properties and PtNM sur- face coating. The results here provide evidence of molecular interactions between NOM and NMs, which are crit- ical to understanding NM colloidal properties (e.g., surface charge and stability), interaction forces (e.g., van der Waals and hydrphobic), environmental behaviors (e.g., aggregation, disso.

Baalousha, Mohammed↗