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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.

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At least 73 records · Page 4

ELT Imaging of MWC 297 from the 23 m LBTI: Complex Disk Structure and a Companion Candidate

Herbig Ae/Be stars represent the early outcomes of star formation and the initial stages of planet formation at intermediate stellar masses. Understanding both of these processes requires detailed characterization of their disk structures and companion frequencies. We present new 3.7 μm imaging of the Herbig Be star MWC 297 from nonredundant masking observations on the phase-controlled, 23 m Large Binocular Telescope Interferometer. The images reveal complex disk structure on the scales of several au, as well as a companion candidate. We discuss physical interpretations for these features and demonstrate that the imaging results are independent of choices such as priors, regularization hyperparameters, and error-bar estimates. With an angular resolution of ∼17 mas, these data provide the first robust Extremely Large Telescope–resolution view of a distant young star.

47 OTHER INSTRUMENTATION↗

New terahertz dielectric spectroscopy for the study of aqueous solutions

We present the development of a high precision, tunable far-infrared (terahertz) frequency-domain dielectric spectrometer for studying the dynamics of biomolecules in aqueous solutions in the gigahertz-to-terahertz frequency. As an important benchmark system, we report on the measurements of the absorption and refractive index for liquid water in the frequency range from 5 GHz to 1.12 THz (0.17–37.36 cm{sup −1} or 0.268–60 mm). The system provides a coherent radiation source with power up to 20 mW in the gigahertz-to-terahertz region. The dynamic range of our instrument reaches 10{sup 12} and the system achieves a spectral resolution of less than 100 Hz. The temperature of samples can be controlled precisely with error bars of ±0.02 °C from 0 °C to 90 °C. Given these attributes, our spectrometer provides unique capabilities for the accurate measurement of even very strongly absorbing materials such as aqueous solutions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Mössbauer parameters of Fe-related defects in group-IV semiconductors: First principles calculations

We employ a combination of pseudopotential and all-electron density functional calculations, to relate the structure of defects in supercells to the isomer shifts and quadrupole splittings observed in Mössbauer spectroscopy experiments. The methodology is comprehensively reviewed and applied to the technologically relevant case of iron-related defects in silicon, and to other group-IV hosts to a lesser degree. Investigated defects include interstitial and substitutional iron, iron-boron pairs, iron-vacancy, and iron-divacancy. We find that, in general, agreement between the calculations and Mössbauer data is within a 10% error bar. Nonetheless, we show that the methodology can be used to make accurate assignments, including to separate peaks of similar defects in slightly different environments.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A fully self-consistent multi-layered model of jupiter

We construct a three-dimensional, fully self-consistent, multi-layered, non-spheroidal model of Jupiter consisting of an inner core, a metallic electrically conducting dynamo region, and an outer molecular electrically insulating envelope. We assume that the Jovian zonal winds are on cylinders parallel to the rotation axis but, due to the effect of magnetic braking, are confined within the outer molecular envelope. We also assume that the location of the molecular-metallic interface is characterized by its equatorial radius HR{sub e}, where R {sub e} is the equatorial radius of Jupiter at the 1 bar pressure level and H is treated as a parameter of the model. We solve the relevant mathematical problem via a perturbation approach. The leading-order problem determines the density, size, and shape of the inner core, the irregular shape of the 1 bar pressure level, and the internal structure of Jupiter that accounts for the full effect of rotational distortion, but without the influence of the zonal winds; the next-order problem determines the variation of the gravitational field solely caused by the effect of the zonal winds on the rotationally distorted non-spheroidal Jupiter. The leading-order solution produces the known mass, the known equatorial and polar radii, and the known zonal gravitational coefficient J {sub 2} of Jupiter within their error bars; it also yields the coefficients J {sub 4} and J {sub 6} within about 5% accuracy, the core equatorial radius 0.09R{sub e} and the core density ρ{sub c}=2.0×10{sup 4} kg m{sup −3} corresponding to 3.73 Earth masses; the next-order solution yields the wind-induced variation of the zonal gravitational coefficients of Jupiter.

79 ASTRONOMY AND ASTROPHYSICS↗

Predicting Li-Ion Battery Capacity Fade Using Early-Life Data and a Hybrid Data-Driven Gaussian Process-Bayesian Regression Approach

Accurately predicting Li-ion battery capacity trajectories using early-life data can dramatically improve battery-life understandings and be used to rapidly evaluate design/cost/performance trade-offs when developing new battery materials. Accurate early-life predictions enable researchers to quickly iterate over cell designs and material precursor properties without consistently cycling cells to failure. To this end, we present a toolbox that uses a combined Gaussian Process and Bayesian regression approach that capitalizes on signals other than just capacity (e.g., dQ/dV, voltage drops) to rapidly predict capacity-fade trajectories. The prediction tool uses Bayesian regression to fit functional forms, e.g., power law, sigmoids, etc., to predict capacity-fade dynamics. By fitting functional forms, the capacity fade can be interrogated at any point in the future, allowing for early cell-failure prediction. Additionally, Bayesian regression allows for accurate uncertainty estimates that account for cell-to-cell variability (aleatoric uncertainty) and the lack of observation data (epistemic uncertainty). By only using early cycle data to predict the capacity fade trajectory, uncertainty bounds at end-of-life can be extremely large. The large uncertainty bounds are further exacerbated because there is no systematic way to define the prior distribution of the functional forms' parameters. We improve our the predicted trajectory confidence interval of our predicted trajectory using two methods. First, we shows that a small amount of held-out cycling data is sufficientuse some train cells, that have been cycled to failure to derive information regarding the appropriate prior distributions for the functional forms' parameters of the functional form, effectively leading to data-driven priors.. We propose constructing the data-driven priors by first running a Bayesian regression starting with uninformed priors to generate intermediate cell-specific posterior parameter distributions. These posterior distributions are combined using a Ggaussian mixture model for each parameter to create the data-driven priors. These mixture models serve as the data-driven prior distributions for the parameters for. Second, we derive multiple features, e.g., C_dchg 0.5 DoD 0.5, log (|mean(dQ/dV_(w_3-w_0 ) (V)|), etc., from the train cellsheld-out cycling data, identify which the features are that best predicting capacity at early/mid-life cycles, and then create Ggaussian process regression models that are used for predicting capacity at early/mid-life cycles for the test cells (see blue dots with error bars in Fig 1b). Finally, these predicted data-points are used in addition to the actual early cycle data capacity fade to construct the Bayesian regression trajectory for the test cell s. Notably. We note that these two methods are complementary and can be combined with each other. We evaluate the performance of our proposed method on an testing open-source dataset from Iowa State University and Iowa Lakes Community College (ISU-ILCC). This dataset comprises of 251 nickel-manganese-cobalt/graphite Lithium-ion cells that are cycled under 63 different conditions. We compute the mean average percentage error (MAPE) and negative log predictive density (NLPD) to quantify the efficacy of our method. Our initial findings suggest that, when only few observations are available, for test cells, when using only Bayesian regression with uninformed priors, a power law functional provides the most accurate predictions. with very few data points. However, asHowever, a the number of data points increases, a twin sigmoidal function becomes more accurate as the number of observations further increases. We also find that using as little as 10% of the data set towards generating data-driven priors can lead to significant improvement in prediction accuracy when using early cycle data. Lastly, we found that augmenting early-cycle data with Gaussian process-predicted capacity data for Bayesian regression greatly improves the prediction accuracy. We will present a comprehensive comparison of our methods to other methods available in the literature and apply this method to additional battery datasets.

42 ENGINEERING↗

Constraining transfer cross sections using Bayes' theorem

Background: Being able to rigorously quantify the uncertainties in reaction models is crucial to moving this field forward. Even though Bayesian methods are becoming increasingly popular in nuclear theory, they have yet to be implemented and applied in reaction theory problems. Purpose: The purpose of this work is to investigate, using Bayesian methods, the uncertainties in the optical potentials generated from fits to elastic-scattering data and the subsequent uncertainties in the transfer predictions. We also study the differences in two reaction models where the parameters are constrained in a similar manner, as well as the impact of reducing the experimental error bars on the data used to constrain the parameters. Method: We use Bayes' theorem combined with a Markov chain Monte Carlo to determine posterior distributions for the parameters of the optical model, constrained by neutron-, proton-, and/or deuteron-target elastic scattering. These potentials are then used to predict transfer cross sections within the adiabatic wave approximation or the distorted-wave Born approximation. Results: We study a number of reactions involving deuteron projectiles with energies in the range 10–25 MeV/nucleon on targets with mass A = 48–208. The case of 48 Ca(d,p) 49 Ca transfer to the ground state is described in detail. A comparative study of the effect of the size of experimental errors is also performed. Five transfer reactions are studied, and their results are then compiled in order to systematically identify trends.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Evaluation of COTS Rad Detection Apps

Mobile applications are currently under distribution to smart phones utilizing the built-in charge coupled-device (CCD) camera as a radiation detector. The CCD detector has a very low but measurable gamma interaction cross section so the mechanism is feasible, especially for higher dose rate environments. Given that in a large release of radioactive material these ‘crowd sourced’ measurements will be put forth for consideration, a testing and evaluation of the accuracy and uncertainty of the Apps is a critical endeavor. Not only is the accuracy of the reported measurement of concern to the immediate user’s safety, a quantitative uncertainty is required for a government response such as the Federal Radiological Monitoring and Assessment Center (FRMAC) to accept the values for consideration in the determination of regions exceeding protective action guidelines. Already, prompted by the Fukushima nuclear material releases, several repositories of this crowd-sourced data have been created (http://japan.failedrobot.com, http://www.stubbytour.com/nuc/index_en.asp, and http://www.rdtn.org) although the question remains as to the reliability of measurements incorporated into these repositories. In cases of conflict between the real-time published crowd-sourced data and governmental protective actions prepared literature should be on-hand documenting why the difference, if any, exists. Four applications for iOS devices were obtained along with hardware to benchmark their performance. Gamma/X-Ray Detector by Stephan Hotto, Geiger Camera by Senscare, and RadioactivityCounter App by Hotray LTD are all the applications available for distribution within the US that utilize the CCD camera sensor for detection of radiation levels. The CellRad app under development by Idaho National Laboratory for the Android platform was evaluated. In addition, iRad Geiger with the associated hardware accessory was also benchmarked. Radiation fields were generated in a Cs-137 JL Shepherd Model 89 shielded calibration range. The accuracy of the exposure rate within the box calibrator is +/- 5% of the system settings and NIST traceable. This is the same calibration unit utilized for calibration of US DOE exposure rate meters. Measurements were performed from 0.2 to 40,000 mR/hr. Included in the following sections are discussions on each of the evaluated applications and their performance in reporting radiation field measurements. Unfortunately the applications do not provide a readily identifiable quality of the measurement in order to produce error bars or even out of range conditions. In general all the CCD based applications had issues detecting consistent measurements in radiation fields less than 5 mR/hr. This is most likely attributable to the electronic noise level on the CCD’s becoming comparable to the signal level due to the ionizing radiation photons.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Oscillation degeneracy in non-standard neutrino interactions

The standard theory describing neutrino oscillations only uses the interactions predicted by the Standard Model of particle physics. However, there is plenty of room for non-standard interactions (NSI) to exist. This is because extra interactions are allowed by experimental error bars and even expected at some level from effective theory arguments. This research is focused on examining the phenomenological consequences of the new physics of NSI at large atmospheric neutrino detectors like IceCube DeepCore. Of particular focus are the degeneracies between and within the standard neutrino oscillation parameters and the NSI parameters. These degeneracies will be explored both analytically and numerically, and strategies to lift them will also be discussed. This research is largely based on [1].

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

CALIBRATING STELLAR POPULATION MODELS WITH MAGELLANIC CLOUD STAR CLUSTERS

Stellar population models are commonly calculated using star clusters as calibrators for those evolutionary stages that depend on free parameters. However, discrepancies exist among different models, even if similar sets of calibration clusters are used. With the aim of understanding these discrepancies, and of improving the calibration procedure, we consider a set of 43 Magellanic Cloud (MC) clusters, taking age and photometric information from the literature. We carefully assign ages to each cluster based on up-to-date determinations, ensuring that these are as homogeneous as possible. To cope with statistical fluctuations, we stack the clusters in five age bins, deriving for each of them integrated luminosities and colors. We find that clusters become abruptly red in optical and optical-infrared colors as they age from {approx}0.6 to {approx}1 Gyr, which we interpret as due to the development of a well-populated thermally pulsing asymptotic giant branch (TP-AGB). We argue that other studies missed this detection because of coarser age binnings. Maraston and Girardi et al. models predict the presence of a populated TP-AGB at {approx}0.6 Gyr, with a correspondingly very red integrated color, at variance with the data; Bruzual and Charlot and Conroy models run within the error bars at all ages. The discrepancy between the synthetic colors of Maraston models and the average colors of MC clusters results from the now obsolete age scale adopted. Finally, our finding that the TP-AGB phase appears to develop between {approx}0.6 and 1 Gyr is dependent on the adopted age scale for the clusters and may have important implications for stellar evolution.

79 ASTRONOMY AND ASTROPHYSICS↗

Signatures of anisotropic sources in the trispectrum of the cosmic microwave background

Soft limits of N-point correlation functions, in which one wavenumber is much smaller than the others, play a special role in constraining the physics of inflation. Anisotropic sources such as a vector field during inflation generate distinct angular dependence in all these correlators, and introduce a fix privileged direction in our sky. In this paper we focus on the four-point correlator (the trispectrum T). We adopt a parametrization motivated by models in which the inflaton φ is coupled to a vector field through a I{sup 2}(φ)F{sup 2} interaction, namely T{sub ζ}(k{sub 1},k{sub 2},k{sub 3},k{sub 4})≡∑{sub n}d{sub n}[P{sub n}( k-circumflex {sub 1}⋅ k-circumflex {sub 3})+P{sub n}( k-circumflex {sub 1}⋅ k-circumflex {sub 12})+P{sub n}( k-circumflex {sub 3}⋅ k-circumflex {sub 12})]P{sub ζ}(k{sub 1})P{sub ζ}(k{sub 3})P{sub ζ}(k{sub 12})+(23perm), where P{sub n} denotes the Legendre polynomials. This shape is enhanced when the wavenumbers of the diagonals of the quadrilateral are much smaller than the sides, k{sub i}. The coefficient of the isotropic part, d{sub 0}, is equal to τ{sub NL}/6 discussed in the literature. A I{sup 2}(φ)F{sup 2} interaction generates d{sub 2} = 2d{sub 0} which is, in turn, related to the quadrupole modulation parameter of the power spectrum, g{sub *}, as d{sub 2} ≈ 14|g{sub *}|N{sup 2} with N ≈ 60. We show that d{sub 0} and d{sub 2} can be equally well-constrained: the expected 68% CL error bars on these coefficients from a cosmic-variance-limited experiment measuring temperature anisotropy of the cosmic microwave background up to ℓ{sub max} = 2000 are δd{sub 2} ≈ 4δd{sub 0} = 105. Therefore, we can reach |g{sub *}| = 10{sup −3} by measuring the angle-dependent trispectrum. The current upper limit on τ{sub NL} from the Planck temperature maps yields |g{sub *}| < 0.02 (95% CL)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

GLEAM: Galaxy Line Emission & Absorption Modeling

We present Galaxy Line Emission & Absorption Modeling (gleam), a Python tool for fitting Gaussian models to emission and absorption lines in large samples of 1D extragalactic spectra. gleam is tailored to work well in batch mode without much human interaction. With gleam, users can uniformly process a variety of spectra, including galaxies and active galactic nuclei, in a wide range of instrument setups and signal-to-noise regimes. gleam also takes advantage of multiprocessing capabilities to process spectra in parallel. With the goal of enabling reproducible workflows for its users, gleam employs a small number of input files, including a central, user-friendly configuration in which fitting constraints can be defined for groups of spectra and overrides can be specified for edge cases. For each spectrum, gleam produces a table containing measurements and error bars for the detected spectral lines and continuum and upper limits for nondetections. For visual inspection and publishing, gleam can also produce plots of the data with fitted lines overlaid. In the present paper, we describe gleam’s main features, the necessary inputs, expected outputs, and some example applications, including thorough tests on a large sample of optical/infrared multi-object spectroscopic observations and integral field spectroscopic data. gleam is developed as an open-source project hosted at https://github.com/multiwavelength/gleam and welcomes community contributions.

79 ASTRONOMY AND ASTROPHYSICS↗

The optical, ultraviolet, and X-ray structure of the quasar HE 0435–1223

Microlensing has proved an effective probe of the structure of the innermost regions of quasars and an important test of accretion disk models. We present light curves of the lensed quasar HE 0435–1223 in the R band and in the ultraviolet (UV), and consider them together with X-ray light curves in two energy bands that are presented in a companion paper. Using a Bayesian Monte Carlo method, we constrain the size of the accretion disk in the rest-frame near- and far-UV, and constrain for the first time the size of the X-ray emission regions in two X-ray energy bands. The R-band scale size of the accretion disk is about 10{sup 15.23} cm (∼23r{sub g}), slightly smaller than previous estimates, but larger than would be predicted from the quasar flux. In the UV, the source size is weakly constrained, with a strong prior dependence. The UV to R-band size ratio is consistent with the thin disk model prediction, with large error bars. In soft and hard X-rays, the source size is smaller than ∼10{sup 14.8} cm (∼10r{sub g} ) at 95% confidence. We do not find evidence of structure in the X-ray emission region, as the most likely value for the ratio of the hard X-ray size to the soft X-ray size is unity. Finally, we find that the most likely value for the mean mass of stars in the lens galaxy is ∼0.3 M{sub ☉}, consistent with other studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Beyond H {sub 0} and q {sub 0}: Cosmology is no longer just two numbers

For decades, H {sub 0} and q {sub 0} were the quest of cosmology, as they promised to characterize our 'world model' without reference to a specific cosmological framework. Using Monte Carlo simulations, we show that q {sub 0} cannot be directly measured using distance indicators with both accuracy (without offset away from its true value) and precision (small error bar). While H {sub 0} can be measured with accuracy and precision, to avoid a small bias in its direct measurement (of order 5%) we demonstrate that the pair H {sub 0} and Ω {sub M} (assuming flatness and w = –1) is a better choice of two parameters, even if our world model is not precisely ΛCDM. We illustrate this with analysis of the Constitution set of supernovae and indirectly infer q {sub 0} = –0.57 ± –0.04. Finally, we show that it may be possible to directly determine q {sub 0} with both accuracy and precision using the time dependence of redshifts ('redshift drift').

79 ASTRONOMY AND ASTROPHYSICS↗

Phase-curve Pollution of Exoplanet Transmission Spectra

The occurrence of a planet transiting in front of its host star offers the opportunity to observe the planet’s atmosphere filtering starlight. The fraction of occulted stellar flux is roughly proportional to the optically thick area of the planet, the extent of which depends on the opacity of the planet’s gaseous envelope at the observed wavelengths. Chemical species, haze, and clouds are now routinely detected in exoplanet atmospheres through rather small features in transmission spectra, i.e., collections of planet-to-star area ratios across multiple spectral bins and/or photometric bands. Technological advances have led to a shrinking of the error bars down to a few tens of parts per million (ppm) per spectral point for the brightest targets. The upcoming James Webb Space Telescope (JWST) is anticipated to deliver transmission spectra with precision down to 10 ppm. The increasing precision of measurements requires a reassessment of the approximations hitherto adopted in astrophysical models, including transit light-curve models. Recently, it has been shown that neglecting the planet’s thermal emission can introduce significant biases in the transit depth measured with the JWST/Mid-InfraRed Instrument, integrated between 5 and 12 μm. In this paper, we take a step forward by analyzing the effects of the approximation on transmission spectra over the 0.6–12 μm wavelength range covered by various JWST instruments. We present open-source software to predict the spectral bias, showing that, if not corrected, it may affect the inferred molecular abundances and thermal structure of some exoplanet atmospheres.

47 OTHER INSTRUMENTATION↗

Constraining neutrino properties with a Euclid-like galaxy cluster survey

We perform a forecast analysis on how well a Euclid-like photometric galaxy cluster survey will constrain the total neutrino mass and effective number of neutrino species. We base our analysis on the Monte Carlo Markov Chains technique by combining information from cluster number counts and cluster power spectrum. We find that combining cluster data with Cosmic Microwave Background (CMB) measurements from Planck improves by more than an order of magnitude the constraint on neutrino masses compared to each probe used independently. For the ΛCDM+m{sub ν} model the 2σ upper limit on total neutrino mass shifts from Σm{sub ν} < 0.35 eV using cluster data alone to Σm{sub ν} < 0.031 eV when combined with Planck data. When a non-standard scenario with N{sub eff}≠3.046 number of neutrino species is considered, we estimate an upper limit of N{sub eff} < 3.14 (95%CL), while the bounds on neutrino mass are relaxed to Σm{sub ν} < 0.040 eV. This accuracy would be sufficient for a 2σ detection of neutrino mass even in the minimal normal hierarchy scenario (Σm{sub ν} ≅ 0.05 eV). In addition to the extended ΛCDM+m{sub ν}+N{sub eff} model we also consider scenarios with a constant dark energy equation of state and a non-vanishing curvature. When these models are considered the error on Σm{sub ν} is only slightly affected, while there is a larger impact of the order of ∼ 15% and ∼ 20% respectively on the 2σ error bar of N{sub eff} with respect to the standard case. To assess the effect of an uncertain knowledge of the relation between cluster mass and optical richness, we also treat the ΛCDM+m{sub ν}+N{sub eff} case with free nuisance parameters, which parameterize the uncertainties on the cluster mass determination. Adopting the over-conservative assumption of no prior knowledge on the nuisance parameter the loss of information from cluster number counts leads to a large degradation of neutrino constraints. In particular, the upper bounds for Σm{sub ν} are relaxed by a factor larger than two, Σm{sub ν} < 0.083 eV (95%CL), hence compromising the possibility of detecting the total neutrino mass with good significance. We thus confirm the potential that a large optical/near-IR cluster survey, like that to be carried out by Euclid, could have in constraining neutrino properties, and we stress the importance of a robust measurement of masses, e.g. from weak lensing within the Euclid survey, in order to full exploit the cosmological information carried by such survey.

79 ASTRONOMY AND ASTROPHYSICS↗

Wet scavenging of soluble gases in DC3 deep convective storms using WRF-Chem simulations and aircraft observations

In this work, we examine wet scavenging of soluble trace gases in storms observed during the Deep Convective Clouds and Chemistry (DC3) field campaign. We conduct high-resolution simulations with the Weather Research and Forecasting model with Chemistry (WRF-Chem) of a severe storm in Oklahoma. The model represents well the storm location, size, and structure as compared with Next Generation Weather Radar reflectivity, and simulated CO transport is consistent with aircraft observations. Scavenging efficiencies (SEs) between inflow and outflow of soluble species are calculated from aircraft measurements and model simulations. Using a simple wet scavenging scheme, we simulate the SE of each soluble species within the error bars of the observations. The simulated SEs of all species except nitric acid (HNO 3 ) are highly sensitive to the values specified for the fractions retained in ice when cloud water freezes. To reproduce the observations, we must assume zero ice retention for formaldehyde (CH 2 O) and hydrogen peroxide (H 2 O 2 ) and complete retention for methyl hydrogen peroxide (CH 3 OOH) and sulfur dioxide (SO 2 ), likely to compensate for the lack of aqueous chemistry in the model. We then compare scavenging efficiencies among storms that formed in Alabama and northeast Colorado and the Oklahoma storm. Significant differences in SEs are seen among storms and species. More scavenging of HNO 3 and less removal of CH 3 OOH are seen in storms with higher maximum flash rates, an indication of more graupel mass. Graupel is associated with mixed-phase scavenging and lightning production of nitrogen oxides (NOx ), processes that may explain the observed differences in HNO 3 and CH 3 OOH scavenging.

54 ENVIRONMENTAL SCIENCES↗

Data free inference with processed data products

Here, we consider the context of probabilistic inference of model parameters given error bars or confidence intervals on model output values, when the data is unavailable. We introduce a class of algorithms in a Bayesian framework, relying on maximum entropy arguments and approximate Bayesian computation methods, to generate consistent data with the given summary statistics. Once we obtain consistent data sets, we pool the respective posteriors, to arrive at a single, averaged density on the parameters. This approach allows us to perform accurate forward uncertainty propagation consistent with the reported statistics.

97 MATHEMATICS AND COMPUTING↗

High-dimensional isotomics, part 2: Observations of over 100 constraints on methionine's isotome

The abundances of different isotopic forms of a compound, or isotopologues, will vary based on its physical and chemical history. The number of isotopologues increases combinatorically with the size of a molecule, and even small molecules such as amino acids have thousands of potentially observable isotopic variants. However, due to the analytical challenges of separating and observing isotopologues, only a few dimensions of isotopic diversity are routinely measured. Overcoming these challenges requires both an experimental method to observe many isotopic properties and a theoretical framework for interpreting these experiments. In Part 1, we presented such a theoretical framework; here, we demonstrate an experimental method, which we apply to methionine. Our approach uses a Q Exactive HF Orbitrap to perform several “M + N experiments”, where a sample is ionized, a subset of its isotopologues with cardinal mass N daltons greater than the unsubstituted isotopologue is selected and fragmented, and the proportions of all detectable isotopic forms of those fragment ions are quantified. We perform M + 1, M + 2, M + 3, and M + 4 experiments of a methionine sample and standard where the sample has a 100 ‰ enrichment of 13C at the methyl carbon relative to the natural 13C abundance at that position in the standard, and is otherwise identical to the standard. We observe isotopic forms of 8 fragment ion species for each version of the M + N experiment. With the assistance of a forward model of expected mass spectra, we identify isotopic peaks for each fragment ion based on observed mass and abundance, screen these for data quality, and quantify abundances for 146 unique isotopic peaks at precisions of ≈ 0.3–3 ‰. We present our direct observations and use them to reconstruct the concentrations of 19 individual singly, doubly, and triply-substituted isotopologues; doing so gives fewer constraints and broader error bars than working with the direct observations, but may be more interpretable for some applications. We also examine possibilities for measuring additional peaks, which are primarily limited by the detection limit of the Orbitrap-IRMS method. We then suggest some possible uses of our direct measurements for chemical forensics and hypothesis testing. Furthermore, our results demonstrate the diversity of isotopic constraints currently observable and interpretable for organic molecules.

58 GEOSCIENCES↗