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NASA NTRS2021

Mass Inferencing Model Creation And Deployment To Lunar Excavation Robot, RASSOR

NASA’s Regolith Advanced Surface Systems Operations Robot (RASSOR) Excavator is a teleoperated mobile robotic platform with a unique space regolith excavation capability. This research project developed functionality for inferencing regolith mass ingested during RASSOR operation, enhancing RASSOR’s ability to successfully complete ISRU missions. Radio wave propagation time to the Moon and back is ~2.56 seconds. Though teleoperation is possible with this delay, autonomous capability that enables RASSOR to plan and execute excavation missions intelligently and efficiently is preferred. To teleoperate or run autonomously, it is crucial for the quantity of regolith mass ingested by RASSOR to be available as a system state for efficient operation (e.g. knowledge of whether drums are full informs the task of highest priority, whether it be continuing to dig, or returning to a processing plant to offload regolith). A configurable data reduction and analysis pipeline was created to allow for straightforward incorporation of new data, such as that from lunar excavation, to improve model performance in new environments. Four distinct modeling approaches were employed in developing a mass inferencing approach that could work on RASSOR. All four models take in system states and output a mass prediction for each set of the robot’s bucket drums. Initial results from deployment to RASSOR and testing in a simulated lunar environment show that the models have <10% mean error during robot operation. Future work includes refinement of a model that estimates regolith mass in real-time during excavation as well as further testing of the developed models on the hardware.

ROS↗

NASA NTRS2020

KMT-2019-BLG-0842Lb: A Cold Planet below the Uranus/Sun Mass Ratio

We report the discovery of a cold planet with a very low planet/host mass ratio of q = (4.09 ± 0.27) × 10^−5, which is similar to the ratio of Uranus/Sun (q = 4.37 × 10^−5) in the solar system. The Bayesian estimates for the host mass, planet mass, system distance, and planet–host projected separation are M(host) = 0.76 ± 0.40Mꙩ, M(planet) = 10.3 ± 5.5Mꚛ, D(L) = 3.3 ± 1.3 kpc, and a(⊥) = 3.3 ± 1.4 au, respectively. The consistency of the color and brightness expected from the estimated lens mass and distance with those of the blend suggests the possibility that the most blended light comes from the planet host, and this hypothesis can be established if high-resolution images are taken during the next (2020) bulge season. We discuss the importance of conducting optimized photometry and aggressive follow-up observations for moderately or very high magnification events to maximize the detection rate of planets with very low mass ratios.

Youn Kil Jung↗

NASA NTRSDate not supplied

Equivalent Mass Benefits from Employing Vapor Compression Refrigeration on Spacecraft

Thermoelectric cooling, reversed Brayton cycles and Stirling cycle devices are common cooling technologies employed on spacecraft where temperatures below the radiator temperature are needed. Although used less often in microgravity, vapor compression refrigeration was proposed for microgravity applications as early as the 1970s. Researchers proposed the vapor compression cycle over other cooling technologies for its superior energy efficiency in the typical refrigerator/freezer and air-conditioning temperature range. The higher energy efficiency should alleviate the mass penalty of the thermal system, conceivably both for satellites and manned spacecraft. Despite numerous propositions, the literature lacks a discussion of the absolute equivalent mass benefit achievable and the value of it relative to the total mass of the thermal system of the spacecraft or the spacecraft itself. This paper presents the equivalent mass benefits of employing a vapor compression system over other cooling technologies using a mass penalty factor for power consumption. Additionally, a prototype vapor compression cooler sized to fit into an ISS locker is presented.

refrigerator↗

NASA NTRS2019

Search for Subsolar Mass Ultracompact Binaries in Advanced LIGO’s Second Observing Run

We present a search for subsolar mass ultracompact objects in data obtained during Advanced LIGO’s second observing run. In contrast to a previous search of Advanced LIGO data from the first observing run, this search includes the effects of component spin on the gravitational waveform. We identify no viable gravitational-wave candidates consistent with subsolar mass ultracompact binaries with at least one component between 0.2 𝑀 ⊙ –1.0 𝑀 ⊙ . We use the null result to constrain the binary merger rate of (0.2 𝑀 ⊙ , 0.2 𝑀 ⊙ ) binaries to be less than 3.7×10 5 Gpc −3 yr −1 and the binary merger rate of (1.0 𝑀 ⊙ , 1.0 𝑀 ⊙ ) binaries to be less than 5.2×10 3 Gpc −3 yr −1 . Subsolar mass ultracompact objects are not expected to form via known stellar evolution channels, though it has been suggested that primordial density fluctuations or particle dark matter with cooling mechanisms and/or nuclear interactions could form black holes with subsolar masses. Assuming a particular primordial black hole (PBH) formation model, we constrain a population of merging 0.2 𝑀 ⊙ black holes to account for less than 16% of the dark matter density and a population of merging 1.0 𝑀 ⊙ black holes to account for less than 2% of the dark matter density. We discuss how constraints on the merger rate and dark matter fraction may be extended to arbitrary black hole population models that predict subsolar mass binaries.

B. P. Abbott↗

NASA NTRS2022

Along-Orbit Analysis of GRACE Follow-On Inter-Satellite Laser Ranging Measurements for Sub-Monthly Surface Mass Variations

We examined the sensitivity of GRACE Follow-On (GRACE-FO) laser ranging interferometer (LRI) measurements to sub-monthly time-variable gravity (TVG) signals caused by transient, high-frequency mass changes in the Earth system. GRACE-FO LRI provides complementary inter-satellite ranging measurements with higher precision over a wider range of frequencies than the baseline K-band microwave ranging system. The common approach for studying mass variation relies on the inverted TVG or mascon solutions over a period of, for example, one month or 10 days which are adversely affected by temporal aliasing and/or smoothing. In this article, we present the alternative along-orbit analysis methodology in terms of line-of-sight gravity difference (LGD) to fully exploit the higher precision LRI measurements for examination of sub-monthly mass changes. The discrepancy between “instantaneous” LGD LRI observations and monthly mean LGD (from Level-2 data) at satellite altitude indicates the sub-monthly gravitational variability not captured by monthly-mean solutions. In conjunction with the satellite ocean altimetry observations, high frequency non-tidal atmosphere and ocean models, and hydrology models, we show that the LGD LRI observations detect the high-frequency oceanic mass variability in the Argentine Basin and the Gulf of Carpentaria, and sub-monthly variations in surface (river) water in the Amazon Basin. We demonstrate the benefits gained from repeat ground track analysis of GRACE-FO LRI data in the case of the Amazon surface water flow. The along-orbit analysis methodology based on LGD LRI time series presented here is especially suitable for quantifying temporal and spatial evolution of extreme, rapidly changing mass variations.

Khosro Ghobadi-Far↗

NASA NTRSDate not supplied

Mass-Specific Power at the Organism and Biosphere Level

The concept of mass-specific power (MSP) quantitatively relates energy flux to the biomass that flux can sustain. We sought to assess the range and distribution of MSP as expressed at both the organism and biosphere level. The former serves to establish what is possible, and what predominates, in physiological terms; the latter reflects the expression of that physiological potential in an environmental context. To assess the potential range of MSP across a diversity of organisms and physiological states, we compiled a data set of more than 10,000 individual MSP measurements, encompassing more than 2900 unique species and spanning 22 orders of magnitude in body mass. Across the data set, MSP varies over six orders of magnitude, from 3 x 10-5 to 49 Watts per gram biomass carbon (W/gC), but the majority of measured values fall within a relatively narrow range of 0.018 ± 6.4-fold W/gC. It is well documented, and clearly expressed in the data set, that MSP exhibits a strong mass dependence within specific taxa (e.g., birds, mammals, and many others); however, MSP exhibits no mass dependence when considering the data set overall. To assess the expression of MSP in environmental context, we estimated energy utilization rates within eight distinct components of the global biosphere, and for the biosphere overall, and used recently published estimates of biomass within those components to compute MSP. We estimate MSP of 0.005 W/gC for the global biosphere as a whole. The close agreement with the organism-level all-species mean (within 4-fold) is noteworthy because the organism-level data set is dominated in statistical terms by animals, while the global biosphere is dominated in mass terms by trees and microorganisms. The various components of the microbe-dominated marine biosphere exhibit a systematic 5 order of magnitude decrease in MSP from the top of the water column (marine primary producers: 0.9 W/gC) to the depths of the sediment column (> 1m sediment biota: 3 x 10-6 W/gC). Biomass turnover rates, combined with the microbial capacity for both high specific growth rates and low maintenance rates, appear to underlie this large range in MSP, which is not expressed to the same extent in the terrestrial biosphere.

Tori M Hoehler↗

NASA NTRSDate not supplied

Component-level Performance and Mass Sensitivity Analysis of NEP MW-class Power System

Nuclear electric propulsion (NEP) is a promising option towards enabling missions to Mars and is an area of interest for NASA’s Space Nuclear Propulsion project. This project is currently investigating technology development opportunities for an NEP vehicle. Physics-based modeling can be used in the early stages of technology development to gain understanding of the effects of technology and performance assumptions on the system performance and mass. This information can then inform technology maturation planning for near term development. By using a Brayton power conversion model and vehicle mass model for megawatt class NEP applications, a sensitivity analysis is performed to assess the impact of individual components’ performance on the power conversion system performance and system mass. A Monte Carlo simulation is also used to determine the variability in system mass based on uncertainty within the modeling parameters. The sensitivity analysis shows a high sensitivity to power conversion inlet temperature, compressor inlet temperature, and recuperator performance. A Monte Carlo analysis suggests a range of -10% to +15% for a 90% confidence interval on system mass based on the uncertainties in the model inputs.

Nuclear electric propulsion↗

NASA NTRS2022

Direct-imaging Discovery and Dynamical Mass of a Substellar Companion Orbiting an Accelerating Hyades Sun-like Star with SCExAO/CHARIS

We present the direct-imaging discovery of a substellar companion in orbit around a Sun-like star member of the Hyades open cluster. So far, no other substellar companions have been unambiguously confirmed via direct imaging around main-sequence stars in Hyades. The star HIP 21152 is an accelerating star as identified by the astrometry from the Gaia and Hipparcos satellites. We detected the companion, HIP 21152 B, in multiple epochs using the high-contrast imaging from SCExAO/CHARIS and Keck/NIRC2. We also obtained the stellar radialvelocity data from the Okayama 188 cm telescope. The CHARIS spectroscopy reveals that HIP 21152 B’s spectrum is consistent with the L/T transition, best fit by an early T dwarf. Our orbit modeling determines the semimajor axis and the dynamical mass of HIP 21152 B to be 17 +7.2 −3.8 and 27.8 +8.4 −5.4 M Jub , respectively. The mass ratio of HIP 21152 B relative to its host is ≈2%, near the planet/brown dwarf boundary suggested by recent surveys. Mass estimates inferred from luminosity-evolution models are slightly higher (33–42 MJup). With a dynamical mass and a well-constrained age due to the system’s Hyades membership, HIP 21152 B will become a critical benchmark in understanding the formation, evolution, and atmosphere of a substellar object as a function of mass and age. Our discovery is yet another key proof of concept for using precision astrometry to select direct-imaging targets.

Masayuki Kuzuhara↗

NASA NTRSDate not supplied

Effect of Nuclear Thermal Propulsion Engine Thrust and Isp Tradeoffs and Alternate Propellants on ΔV Budget and Architecture Mass for Crewed Mars Vehicles

This paper will provide an overview of a spacecraft architecture model developed at AMA as well as an insight into some of the results provided. Currently, preliminary analysis has been completed with this model on evaluating different thrust to weight ratios of Nuclear Thermal Propulsion based vehicles using hydrogen as the propellant by altering the number of engines in the engine block. Gravity losses are incorporated into this analysis as different thrust to weight ratios will provide different burn times. So far, this analysis has shown that in terms of the vehicle mass, it is best to trade the gravity losses for lower vehicle mass as the engines considered add significant dry mass to the vehicle. The final version of this paper will compare gravity losses and vehicle masses for vehicles using different engine masses as well as the ammonia propellant.

Master equipment list↗

NASA NTRSDate not supplied

Results from the Radio Frequency Mass Gauge Technology Demonstration on the Intuitive Machines Nova-C Lunar Lander

A cryogenic propellant mass gauge known as the Radio Frequency Mass Gauge (RFMG) was integrated into the Intuitive Machines (IM) Nova-C lunar lander and provided an estimate of the liquid oxygen and liquid methane mass in the lander propellant tanks throughout the IM-1 mission, including during microgravity coast phases. An RFMG electronics controller was used to measure and record the spectrum of the RF signal reflected from an antenna sensor in each tank over the frequency range 100 to 1,300 MHz. The RF spectrum of each of the tanks is unique and is sensitive to the index of refraction of the propellants and the spatial distribution of the liquid within the tanks. Electromagnetic simulation software was used to simulate the antenna response spectra for a given tank geometry, fluid properties, and liquid–vapor configurations within the tank. Over 10,000 antenna response simulations were completed for each propellant tank prior to the IM-1 mission and represented various volumetric fill levels and fluid configurations. The simulated spectra served as a database against which measured tank spectra were compared. For analysis, a spectral matching algorithm was used to find the best match between measured and simulated spectra, and the gauged mass was calculated from the most highly correlated fluid mass simulations. RFMG measurements were recorded during tank loading on the launch pad and during translunar coast, lunar orbit insertion, low lunar orbit, powered descent to the lunar surface, and postlanding on the Moon. This paper describes the RF and fluid simulations, the RFMG measurements and analysis of spectral data, the RFMG instrument, and the gauged results throughout all phases of the IM-1 mission.

lunar lander↗

NASA NTRS2024

Masses of Sunyaev-Zel’dovich Galaxy Clusters Detected by the Atacama Cosmology Telescope: Stacked Lensing Measurements with Subaru HSC Year 3 Data

We present a stacked lensing analysis of 96 galaxy clusters selected by the thermal Sunyaev-Zel’dovich (SZ) effect in maps of the cosmic microwave background (CMB). We select foreground galaxy clusters with a 5σ-level SZ threshold in CMB observations from the Atacama Cosmology Telescope, while we define background source galaxies for the lensing analysis with secure photometric redshift cuts in Year 3 data of the Subaru Hyper Suprime Cam survey. We detect the stacked lensing signal in the range of 0.1 < R[h −1 Mpc] < 100 in each of three cluster redshift bins, 0.092 < z ≤ 0.445, 0.445 < z ≤ 0.695, and 0.695 < z ≤ 1.180, with 32 galaxy clusters in each bin. The cumulative signal-to-noise ratios of the lensing signal are 14.6, 12.0, and 6.6, respectively. Using a halo-based forward model, we then constrain statistical relationships between the mass inferred from the SZ observation (i.e. SZ mass) and the total mass derived from our stacked lensing measurements. At the average SZ mass in the cluster sample (2.1 − 2.4 × 10 14 h −1 M⊙), our likelihood analysis shows that the average total mass differs from the SZ counterpart by a factor of 1.3 ± 0.2, 1.6 ± 0.2, and 1.6 ± 0.3 (68%) in the aforementioned redshift ranges, respectively. Our limits are consistent with previous lensing measurements, and we find that the cluster modeling choices can introduce a 1σ-level difference in our parameter inferences.

Masato Shirasaki↗

NASA NTRSDate not supplied

Results from the Radio Frequency Mass Gauge Technology Demonstration on the Intuitive Machines Nova-C Lunar Lander

lunar lander↗

DOE OSTI2021

URANIUM HOLDUP MONITORING WITH COMPTON IMAGING AS FUNCTION OF DEPTH AND MASS

Mass quantification using standoff gamma detection is a logical progression for MC&A applications in uranium processing facilities. While obtaining a ground truth from physical collection and weighing of masses is ideal and routine, it poses a logistical problem from both a standpoint of ALARA programs as well as interruptions to operations. The standard approach is the Generalized Geometry in Holdup (GGH) method that can apply for many cases where geometries of the holdup match simulated models; however, there are many cases where a model may not exist or a feature of the holdup geometry is such that it does not match a model particularly well.1 Gamma imaging at standoff distances and outside process equipment has potential to address these shortcomings and improve mass estimations while reducing personnel exposure; however, algorithms still require a significant degree of benchmarking to build sufficient confidence in algorithms before displacing GGH in some procedures. This paper presents the creation of a set of laboratory standards of depleted U3O8 in fixed size containers covering a range of masses and effective thicknesses up to the infinite thickness for the 185-keV line. These blocks are identically sized aluminum boxes loaded such that a thin, flat face is placed towards the imager, while the back side contains closed cell foam to apply pressure to keep the powder in a fixed position at the front face as the sources are manipulated for measurements. Included is an analysis of the mass estimation using a commercially available Compton imaging instrument where multiple geometries are created showing limitations in current methodologies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Search for Low mass Higgs Portal Scalars at the MicroBooNE Detector in the NuMI Beam

The MicroBooNE experiment exploits Liquid Argon Time Projection Chamber (LArTPC) technology to detect neutrinos from two beams at Fermilab, Chicago: on-axis Booster Neutrino Beam (BNB) and the off-axis Neutrinos at the Main Injector (NuMI) beam. While the aim of the experiment is to study the low-energy excess of electron neutrino events observed by the MiniBooNE experiment, to search for eV-scale sterile neutrinos and to characterise neutrino interactions on argon, it could also be exploited to probe Beyond Standard Model (BSM) Physics. This thesis presents a BSM search for low-mass Higgs Portal Scalars at MicroBooNE in the NuMI beam using data collected during the Run 1 and Run 3 data-taking periods with a total exposure corresponding to $7.01 \times 10^{20}$ protons on target (POT). The Higgs Portal Model is an extension to the Standard Model in which a dark-sector scalar, $S$, mixes with the Higgs boson with mixing angle $\theta$ and acquires a coupling to the Standard Model fermions via the Higgs Yukawa coupling. We search for low-mass Higgs Portal scalars, in the mass range $100-200$ MeV, at MicroBooNE via the production channel $K \rightarrow \pi + S$, where scalars are produced from kaons decaying at rest in the NuMI target and beam dump, as well as kaons decaying in flight in the decay pipe of the NuMI beam. In the MicroBooNE detector, we search for the decay channel $S \rightarrow e^+e^-$, which is the only decay channel available to the scalars in the mass range of our search. The results are expressed as limits, at the 95\% confidence level, on the scalar-Higgs mixing angle $\theta$ for scalars in the mass range $100-200$ MeV.Date of Award1 Aug 2023Original languageEnglishAwarding InstitutionThe University of ManchesterSupervisorStefan Soldner-Rembold (Supervisor) & Justin Evans (Supervisor)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2026

Precision Kinematic Sunyaev--Zel'dovich Measurements Across Halo Mass and Redshift with DESI DR2 and ACT DR6: Part II. Bright Galaxy Survey and Emission-Line Galaxies

We present the first high-significance spectroscopic stacked kinetic Sunyaev-Zel'dovich (kSZ) measurements of circumgalactic gas profiles for both Bright Galaxy Survey (BGS) and Emission Line Galaxy (ELG) tracers, combining DESI Data Release 2 with ACT Data Release 6. Using reconstructed line-of-sight velocities from the DESI galaxies and high-resolution ACT temperature maps, we detect the kSZ signal at high significance, reaching signal-to-noise ratios of up to $\sim$9 for BGS and $\sim$7.5 for ELGs in optimal stellar-mass selections. Together with the LRG measurements presented in Paper I, these constitute the most significant kSZ detections from any spectroscopic survey to date. We perform the analysis in both real and harmonic space, obtaining consistent results. By splitting both tracers into stellar-mass bins, we study the scaling of the kSZ amplitude with galaxy properties. Combining the kSZ measurements with ACT Data Release 6 (DR6) CMB lensing maps enables a joint calibration of the galaxy-halo connection and the gas fractions of host halos. For the BGS galaxies, we observe low gas fractions around the virial radius relative to standard expectations, likely attributable to active galactic nuclei (AGN) activity. We find some evidence for higher-mass halos retaining a larger fraction of their baryons, consistent with more efficient feedback in lower-mass systems. For the ELG sample, dominated by blue, star-forming galaxies, we provide the first detection of the gas distribution in ELG host halos. The ELGs appear to exhibit relatively high gas fractions, which points to the possibility of weaker feedback (due to e.g. low AGN and supernova feedback activity) at their mass scale. Finally, we present generalized Navarro-Frenk-White (GNFW) fits to the harmonic-space measurements, providing a compact parametrization of gas profiles for forward modeling in large-scale structure analyses.

Hadzhiyska, B. [Cambridge U.; Cambridge U., Inst. ↗

DOE OSTI2023

A Dual-Gated Structures for Lossless Ion Manipulations-Ion Mobility Orbitrap Mass Spectrometry Platform for Combined Ultra-High-Resolution Molecular Analysis

High-resolution ion mobility spectrometry-mass spectrometry (HR-IMS-MS) instruments have enormously advanced the ability to characterize complex biological mixtures. Unfortunately, HR-IMS and HR-MS measurements are typically performed independently due to mismatches in analysis time scales. Here we overcome this limitation by using a dual-gated ion injection approach to couple an 11-meter path length structures for lossless ion manipulations (SLIM) module to a Q-Exactive Plus Orbitrap MS. The dual-gate setup was implemented by placing one ion gate before the SLIM module and a second ion gate after. The dual-gated ion injection approach allowed the new SLIM-Orbitrap platform to simultaneously perform an 11-meter SLIM separation, Orbitrap mass analysis using the highest selectable mass resolution setting (up to 140k), and high-energy collision induced dissociation (HCD) in ~25 minutes over an $m/z$ range of ~1500 amu. The SLIM-Orbitrap was initially characterized using a mixture of standard phosphazene cations and demonstrated an average SLIM CCS resolving power (Rp CCS ) of ~218 and SLIM peak capacity of ~156 while simultaneously obtaining high mass resolutions. SLIM-Orbitrap analysis with fragmentation was then performed on mixtures of standard peptides and two reverse peptides (SDGRG 1+ , GRGDS 1+ , Rp CCS = 305) to demonstrate the utility of combined HR-IMS-MS/MS measurements for peptide identification. Our new HR-IMS-MS/MS capability was further demonstrated by analyzing a complex lipid mixture and showcasing SLIM separations on isobaric lipids. In conclusion, this new SLIM-Orbitrap platform demonstrates a critical new capability for proteomics and lipidomics applications, and the high-resolution multimodal data obtainable with this system establishes the foundation for reference-free identification of unknown ion structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Data and scripts associated with a manuscript investigating impacts of solid phase extraction on freshwater organic matter optical signatures and mass spectrometry pairing

This data package is associated with the publication “Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high-resolution mass spectrometry data in a freshwater system” submitted to “Limnology and Oceanography: Methods.” This data is an extension of the River Corridor and Watershed Biogeochemistry SFA’s Spatial Study 2021 (https://doi.org/10.15485/1898914). Other associated data and field metadata can be found at the link provided. The goal of this manuscript is to assess the impact of solid phase extraction (SPE) on the ability to pair ultra-high resolution mass spectrometry data collected from SPE extracts with optical properties collected on ambient stream samples. Forty-seven samples collected from within the Yakima River Basin, Washington were analyzed dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), absorbance, and fluorescence. Samples were subsequently concentrated with SPE and reanalyzed for each measurement. The extraction efficiency for the DOC and common optical indices were calculated. In addition, SPE samples were subject to ultra-high resolution mass spectrometry and compared with the ambient and SPE generated optical data. Finally, in addition to this cross-platform inter-comparison, we further performed and intra-comparison among the high-resolution mass spectrometry data to determine the impact of sample preparation on the interpretability of results. Here, the SPE samples were prepared at 40 milligrams per liter (mg/L) based on the known DOC extraction efficiency of the samples (ranging from ~30 to ~75%) compared to the common practice of assuming the DOC extraction efficiency of freshwater samples at 60%. This data package folder consists of one main data folder with one subfolder (Data_Input). The main data folder contains (1) readme; (2) data dictionary (dd); (3) file-level metadata (flmd); (4) final data summary output from processing script; and (5) the processing script. The R-markdown processing script (SPE_Manuscript_Rmarkdown_Data_Package.rmd) contains all code needed to reproduce manuscript statistics and figures (with the exception of that stated below). The Data_Input folder has two subfolders: (1) FTICR and (2) Optics. Additionally, the Data_Input folder contains dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data (SPS_NPOC_Summary.csv) and relevant supporting Solid Phase Extraction Volume information (SPS_SPE_Volumes.csv). Methods information for the optical and FTICR data is embedded in the header rows of SPS_EEMs_Methods.csv and SPS_FTICR_Methods.csv, respectively. In addition, the data dictionary (SPS_SPE_dd.csv), file level metadata (SPS_SPE_flmd.csv), and methods codes (SPS_SPE_Methods_codes.csv) are provided. The FTICR subfolder contains all raw FTICR data as well as instructions for processing. In addition, post processed FTICR molecular information (Processed_FTICRMS_Mol.csv) and sample data (Processed_FTICRMS_Data.csv) is provided that can be directly read into R with the associated R-markdown file. The Optics subfolder contains all Absorbance and Fluorescence Spectra. Fluorescence spectra have been blank corrected, inner filter corrected, and undergone scatter removal. In addition, this folder contains Matlab code used to make a portion of Figure 1 within the manuscript, derive various spectral parameters used within the manuscript, and used for parallel factor analysis (PARAFAC) modeling. Spectral indices (SPS_SpectralIndices.csv) and PARAFAC outputs (SPS_PARAFAC_Model_Loadings.csv and SPS_PARAFAC_Sample_Scores.csv) are directly read into the associated R-markdown file. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected some of these data. We thank the Confederated Tribes and Bands of 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.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Statistically-driven Experimental Design to Improve Reference-free Quantification of Small Molecules by Liquid Chromatography-Mass Spectrometry

Non-targeted analysis of small molecules and metabolites in unknown, complex samples using liquid chromatography-tandem mass spectrometry remains challenging. One of the main bottlenecks is the extensive unannotated regions of metabolomics mass spectrometry data, resulting in knowledge gaps. Small molecule annotation in mass spectrometry data has conventionally relied on reference standards and libraries for compound identification and confirmation, which can constrain compound identification to those molecules already known, thus limiting the ability to discover new knowledge and new markers. Retention time prediction can facilitate and expedite unknown compound identification in non-targeted analysis of complex metabolomics samples. Additionally, accurate retention time predictions can also inform sample mixture design for LC-MS/MS analyses. However, current machine learning-based methods for retention time prediction are typically developed for specific chromatographic platforms and are not generalizable across scales. And while technologies and methods to improve reference-free metabolite identification for more comprehensive annotation of unknowns has received much attention, development of the same for quantitation without reference standards has been much more limited, despite its importance in toxicological, environmental, food safety, forensics, and clinical applications. We believe that a reference-free quantitation strategy that exploits mass spectrometry data already collected for reference-free identification can provide much more insight on unknowns, and move the metabolomics field for more complete unknowns characterization. As such, we pursue two efforts to improve upon current state-of-the-art methods in non-targeted analysis: (1) machine learning-based retention time prediction and (2) statistical design of experiments framework for reference-free quantitation. In this work, we develop and demonstrate (1) a generalizable retention time prediction capability across chromatographic conditions and scales, and (2) a statistical design-based framework for response factor contribution elucidation and reference-free quantitation. Evaluation of our retention time prediction model, PrediToR, showed approximately 24% improvement over current models, and we observed approximately 10X improvement in concentration estimation accuracy from our statistical design-based response factor model over a primarily ionization efficiency-based model. We expect that future efforts to improve upon these new capabilities will further advance non-targeted analysis of small molecules towards truly reference-free metabolomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗