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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Retrospective analysis of biochemical limitations to photosynthesis in 49 species: C 4 crops appear still adapted to pre‐industrial atmospheric [ CO 2 ]

Abstract Leaf CO 2 uptake ( A ) in C 4 photosynthesis is limited by the maximum apparent rate of PEPc carboxylation ( V pmax ) at low intercellular [CO 2 ] ( c i ) with a sharp transition to a c i ‐saturated rate ( V max ) due to co‐limitation by ribulose‐1:5‐bisphosphate carboxylase/oxygenase (Rubisco) and regeneration of PEP. The response of A to c i has been widely used to determine these two parameters. V max and V pmax depend on different enzymes but draw on a shared pool of leaf resources, such that resource distribution is optimized, and A maximized, when V max and V pmax are co‐limiting. We collected published A / c i curves in 49 C 4 species and assessed variation in photosynthetic traits between phylogenetic groups, and as a function of atmospheric [CO 2 ]. The balance of V max ‐ V pmax varied among evolutionary lineages and C 4 subtypes. Operating A was strongly V max ‐limited, such that re‐allocation of resources from V pmax towards V max was predicted to improve A by 12% in C 4 crops. This would not require additional inputs but rather altered partitioning of existing leaf nutrients, resulting in increased water and nutrient‐use efficiency. Optimal partitioning was achieved only in plants grown at pre‐industrial atmospheric [CO 2 ], suggesting C 4 crops have not adjusted to the rapid increase in atmospheric [CO 2 ] of the past few decades.

Pignon, Charles P.↗
DOE OSTI2022

Determination of asymptotic normalization coefficients for the channel 16 O→ α+ 12 C: excited state 16 O(0 + ; 6.05 MeV)

Asymptotic normalization coefficients (ANC) determine the overall normalization of cross sections of peripheral radiative capture reactions. In the present paper, we treat the ANC C for the virtual decay 16 O(0 + ; 6.05 MeV)→ α+ 12 C(g.s.), the known values of which are characterized by a large spread (0.29 - 1.65) × 10 3 fm -1/2 . The ANC C is found by analytic continuation in energy of the α 12 C s-wave scattering amplitude, known from the phase-shift analysis of experimental data, to the pole corresponding to the 16O bound state and lying in the unphysical region of negative energies. To determine C, two different methods of analytic continuation are used. In the first method, the scattering data are approximated by the sum of polynomials in energy in the physical region and then extrapolated to the pole. The best way of extrapolation is chosen on the basis of the exactly solvable model. Within the second approach, the ANC C is found by solving the Schrödinger equation for the two-body α 12 C potential, the parameters of which are selected from the requirement of the best description of the phase-shift analysis data at a fixed experimental binding energy of 16 O(0 + ; 6.05 MeV) in the α+ 12 C channel. The values of the ANC C obtained within these two methods lie in the interval (886–1139) fm -1/2 .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Thermodynamically Stable, Plasmonic Transition Metal Oxide Nanoparticle Solar Selective Absorbers towards 95% Optical-to-Thermal Conversion Efficiency at 750 °C

Generation 3 (Gen) concentrating solar power (CSP) systems requires a high operation temperature ≥750°C to increase the power-cycle efficiency towards ≥50%. However, such a high operation temperature poses a notable challenge to high temperature materials. On the receiver side, a critical challenge is the lack of solar selective absorbers that demonstrate both high optical-to-thermal energy conversion efficiency η therm approaching 95% and long-term thermal stability at >750°C in air. Existing solar absorbers either have limited η therm ≤89% or deteriorate significantly within 500 h at 750°C; some of these also require costly vacuum deposition for stringent thickness control. Therefore, it is highly desirable to simultaneously achieve η therm ~95% AND high thermal stability at 750°C for future generations of CSP receivers. This project has investigated and developed low-cost, highly scalable spray-coated transition metal oxide nanoparticle (NP) pigmented solar selective coatings on various types of Inconel alloy tube sections that are thermodynamically stable at 750-800°C in air, maintaining η therm >94.3%(93.2%) under a solar concentration ratio of C=1000 after 60 simulated day-night cycles at 750ºC (800ºC) (1 cycle=12 h at 750 or 800°C and 12h ramping down to 25°C). We have also coated up to 48 inches long receiver tubes for preliminary solar testing under Norwich Technology’s parabolic trough systems, demonstrating notably improved performance in solar heating compared to benchmark Pyromark 2500 coatings. Two key innovations have been developed in this project: (1) We achieved an unprecedented high thermal efficiency >94% by optimizing the d-band optical absorption spectra of transition metal ions, engineering their valences and stoichiometry; (2) We were able to maintain or even slightly increase the efficiency when operating at 750°C in air by engineering the interdiffusion of transition metal ions between the coating and the Inconel substrate to our advantage. Featuring high-temperature solar spectral selectivity and thermodynamic stability in air, as well as low-cost, highly scalable solution-chemical synthesis and spray coating techniques, this innovation in solar selective absorber technology alone accounts for nearly 40% of the targeted reduction in the levelized cost of electricity (LCOE) from the receiver, thermal energy storage, and operation & maintenance combined by 2030, as proposed by the U.S. Department of Energy. For a 110 MWe CSP power plant, this LCOE reduction from the solar selective coating alone transfers to ~$\$ $1.9 M increase in annual profit based on a sales price of 10¢/kWh (or an annual sale of $50 M/year). The high solar absorptance (~98%) NP pigment materials developed in this project are equally applicable to volumetric receivers either as a coating or as bigger ceramic microspheres after sintering, potentially benefiting Gen3 falling particle CSP technologies. All these contributions facilitate the larger scale deployment of CSP systems with energy storage capability to address the intermittency issue of solar energy towards dispatchable solar electricity, bridging the temporal gap between peak solar electricity production and peak electricity consumption. The collaboration with Norwich Technologies and Brayton Energy in this project will also facilitate the future commercialization of this new solar selective coating technology developed in this SIPS project.

14 SOLAR ENERGY↗
DOE OSTI2024

Summary of Structural Alloy Compatibility in Supercritical CO2 at 450°-800°C

Supercritical CO2 (sCO2) is of interest as a working fluid for several concepts including the direct- fired Allam cycle as a low-emission fossil energy power cycle. Over the past 10 years, laboratory exposures at 300 bar sCO2 have found reasonably good compatibility for Ni-based alloys at <800°C, including an assessment of the sCO2 impact on room temperature mechanical properties after 750°C exposures. However, initial screening tests at 1 and 20 bar CO2 at 900°-1100°C showed poor compatibility for Ni-based alloys. In an open cycle, the introduction of 1%O2 and 0.1- 0.25%H2O impurities at 300 bar increased the reaction rates ≥2X at 750°C. At lower temperatures, steels are susceptible to C ingress and embrittlement. Creep-strength enhanced ferritic steels may be limited to <550°C and conventional stainless steels to <600°C. Two strategies to increase those temperatures are higher Ni and Cr alloying additions and Al- or Cr-rich coatings. Alloy 709 (Fe- 20Cr-25Ni) shows some promising results at 650°C in sCO2 but reaction rates were accelerated with the addition of O2 and H2O impurities. Pack aluminized and chromized Gr.91 (Fe-9Cr-1Mo) and type 316H stainless steel show some promise at 600°-650°C but further coating optimization is needed.

Pint, Bruce↗
DOE OSTI2022

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

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

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1981

Surface chemistry and friction behavior of the silicon carbide (0001) surface at temperatures to 1500 deg C

X-ray photoelectron and Auger electron spectroscopy analyses and friction studies were conducted with a silicon carbide (0001) surface in contact with iron at various temperatures to 1200 or 1500 C in a vacuum of 10 to the minus 8th power Pa. The results indicate that there is a significant temperature influence on both the surface chemistry and friction properties of silicon carbide. The principal contaminant of adsorbed amorphous carbon on the silicon carbide surface in the as received state is removed by simply heating to 400 C. Above 400 C, graphite and carbide type carbine are the primary species on the silicon carbide surface, in addition to silicon. The coefficients of friction of polycrystalline iron sliding against a single crystal silicon carbide (0001) surface were high at temperatures to 800 C. Similar coefficients of friction were obtained at room temperature after the silicon carbide was preheated at various temperatures up 800 C. When the friction experiments were conducted above 800 C or when the specimens were preheated to above 800 C, the coefficients of friction were dramatically lower. At 800 C the silicon and carbide type carbon are at a maximum intensity in the XPS spectra. With increasing temperature above 800 C, the concentration of the graphite increases rapidly on the surface, whereas those of the carbide type carbon and silicon decrease rapidly.

Miyoshi, K.↗
NASA NTRS1994

Factors and processes governing the C-14 content of carbonate in desert soils

A model is presented describing the factors and processes which determine the measured C-14 ages of soil calcium carbonate. Pedogenic carbonate forms in isotopic equilium with soil CO2. Carbon dioxide in soils is a mixture of CO2 derived from two biological sources: respiration by living plant roots and respiration of microorganisms decomposing soil humus. The relative proportion of these two CO2 sources can greatly affect the initial C-14 content of pedogenic carbonate: the greater the contribution of humus-derived CO2, the greater the initial C-14 age of the carbonate mineral. For any given mixture of CO2 sources, the steady-state (14)CO2 distribution vs. soil depth can be described by a production/diffusion model. As a soil ages, the C-14 age of soil humus increases, as does the steady-state C-14 age of soil CO2 and the initial C-14 age of any pedogenic carbonate which forms. The mean C-14 age of a complete pedogenic carbonate coating or nodule will underestimate the true age of the soil carbonate. This discrepancy increases the older a soil becomes. Partial removal of outer (and younger) carbonate coatings greatly improves the relationship between measured C-14 age and true age. Although the production/diffusion model qualitatively explains the C-14 age of pedogenic carbonate vs. soil depth in many soils, other factors, such as climate change, may contribute to the observed trends, particularily in soils older than the Holocene.

Amundson, Ronald↗
NASA NTRS1999

Kinetics of template-directed pyrophosphate-linked dideoxyguanylate synthesis as a function of 2-MeImpdG and poly(C) concentration: insights into the mechanism

Aqueous solutions of deoxyguanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpdG, yield primarily deoxyguanosine 5'-monophosphate, 5'dGMP, and pyrophosphate-linked dideoxyguanylate, dG5'ppdG, abbreviated G2p (see Chart 1). The initial rate of G2p formation, d[G2p]/dt in M h-1, determined at 23 degrees C, pH 7.8, 1.0 M NaCl and 0.2 M Mg2+ by timed high-performance liquid chromatography (HPLC) analysis, exhibits a second-order dependence on 2-MeImpdG concentration, [G]o, indicating a bimolecular mechanism of dimerization in the range 0.02 M < or = [G]o < or = 0.09 M. In the presence of polycytidylate, poly(C), G2p synthesis is accelerated and oligodeoxyguanylate products are formed by incorporation of 2-MeImpdG molecules. The kinetics of G2p formation as a function of both monomer and polymer concentration, expressed in C equivalents, were also determined under the above conditions and exhibited a complex behavior. Specifically, at a constant [poly(C)], values of d[G2p]/dt typically increased with [G]o with a parabolic upward curvature. At a constant [G]o, values of d[G2p]/dt increase with [poly(C)], but level off at the higher poly(C) concentrations. As [G]o increases this saturation occurs at a higher poly(C) concentration, a result opposite to expectation for a simple complexation of two reacting monomers with the catalyst prior to reaction. Nevertheless, these results are shown to be quantitatively consistent with a template-directed (TD) mechanism of dimerization where poly(C) acts as the template to bind 2-MeImpdG in a cooperative manner and lead, for the first time, to the formulation of principles that govern template-directed chemistry. Analysis of the kinetic data via a proposed TD cooperative model provides association constants for the affinity between polymer and monomer and the intrinsic reactivity of 2-MeImpdG toward pyrophosphate synthesis. To the best of our knowledge, poly(C)/2-MeImpdG is the first system that could serve as a textbook example of a TD reaction under conditions such that the template is fully saturated by monomers and under conditions that it is not.

NASA Discipline Exobiology↗
NASA NTRS2006

Static and Switching Characteristics of a 4H-SiC Based BJT to 200 C

Static curves and resistive load switching characteristics of a 600 V, 4 A rated, SiC-based NPN bipolar power transistor (BJT) were observed at selected temperatures from 23 to 200 C. All testing was done in a pulse mode at low duty cycle (approx. 0.1 percent). Turn-on was driven by an adjustable base current pulse and turn-off was accelerated by a negative base voltage pulse of either 7 or 0.6 V. Switching observations were done at base drive currents (I(sub B)) up to 400 mA and collector currents (I(sub C)) up to 4 A, using a 100 OMEGA non-inductive load. At I(sub B) = 400 mA and I(sub C) = 4 A, turn-on times typically varied from 81 to 97 ns, over temperatures from 23 to 200 C. As expected, lowering the base drive greatly extended the turn-on time. Similarly, decreasing the load current to I(sub C) = 1 A with I(sub B) = 400 mA produced turn-on times as short as 30 ns. Over the 23 to 200 C range, with I(sub B) = 400 mA and I(sub C) = 4 A, turn-off times were in the range of 61 to 77 ns with the 7 V sweep-out and 130 to 150 ns with the 0.6 V sweep-out. At a fixed temperature and I(sub C), the turn-off time decreased slightly with decreasing I(sub B), for I(sub B) sufficient to still provide full turn-on. The ratio of conduction to switching losses is estimated, based on the observed I(sub C) transition times and static curves. An estimate at 200 kHz and a 50 percent duty cycle shows that under practicable conditions the two losses can be comparable. Hence the evidence obtained does not support the occasionally voiced concern of necessarily unacceptably high conduction losses in SiC-based BJTs.

Niedra, Janis M.↗
NASA NTRS2016

Phase Equilibria of a S- and C-Poor Lunar Core

The composition of the lunar core can have a large impact on its thermal evolution, possible early dynamo creation, and physical state. Geochemical measurements have placed better constraints on the S and C content of the lunar mantle. In this study we have carried out phase equilibrium studies of geochemically plausible S- and C-poor lunar core compositions in the Fe-Ni-S-C system, and apply them to the early history of the Moon. We chose two bulk core compositions, with differing S and C content based on geochemical analyses of S and C trapped melts in Apollo samples, and on the partitioning of S and C between metal and silicate. This approach allowed calculation of core S and C contents - 90% Fe, 9% Ni, 0.5% C, and 0.375% S by weight; a second composition contained 1% each of S and C. Experiments were carried out from 1473K to 1973K and 1 GPa to 5 GPa, in piston cylinder and multi- anvil apparatuses. Combination of the thermal model of with our results, shows that a solid inner core (and therefore initiation of a dynamo) may have been possible in the earliest history of the Moon (approximately 4.2 Ga ago), in agreement with. Thus a volatile poor lunar core may explain the thermal and magnetic history of the Moon.

Righter, K.↗
NASA NTRS2021

Additional Characterization of Dome-C to Improve its Use as an Invariant Visible Calibration Target

Dome-C is a recommended CEOS invariant target that has been utilized by the calibration community for several decades for monitoring onboard sensor calibration systems as well radiometric inter-comparisons. Dome-C is a high-altitude Earth target located on the East Antarctic interior plateau, which has a permanent bright, flat, and homogeneous snow-covered surface with little aerosol, cloud cover, snowfall, and water vapor burden. This paper describes angular directional models for characterizing the Dome-C top-of-atmosphere (TOA)radiances as a function of cosine solar zenith angle for pre-solstice and post-solstice conditions. The 0.86-μm channel Dome-C reflectance decreases over the summer due to snow metamorphosisis not observed by the visible channels. Coinciding Terra and AquaMODIS Dome-C reflectance showed occasional inter-annual anomalies when compared against the deep convective cloud and Libya-4 invariant targets observations. Further characterization of the Dome-C reflectances with the Dome-C surface broadband albedo, Antarctic Oscillation(AAO) index, and ozone concentration values were evaluated. A strong correlation with ozone was found for the 0.55-μm and 0.65-μm MODIS channels. The monthly Dome-C reflectances were linearly regressed with ozone to derive the ozone correction coefficients. The uncertainty in the Aqua-and Terra-MODIS Dome-C trends was reduced by half after applying ozone corrections to both the 0.55-μm and 0.65-μm channelTOA observations.

David R Doelling↗
DOE OSTI2020

First Measurement of Λ c Baryon Production in Au + Au Collisions at s N N = 200 GeV

Herein we report on the first measurement of the charmed baryon Λ c ± production at midrapidity ( | y | < 1 ) in Au + Au collisions at s NN = 200 GeV collected by the STAR experiment at the Relativistic Heavy Ion Collider. The Λ c / D 0 [denoting ( Λ c + + Λ c - ) / ( D 0 + D ¯ 0 ) ] yield ratio is measured to be 1.08 ± 0.16 ( stat ) ± 0.26 ( sys ) in the 0%–20% most central Au + Au collisions for the transverse momentum ( p T ) range 3 < p T < 6 GeV / c . This is significantly larger than the pythia model calculations for p + p collisions. The measured Λ c / D 0 ratio, as a function of p T and collision centrality, is comparable to the baryon-to-meson ratios for light and strange hadrons in Au + Au collisions. Model calculations including coalescence hadronization for charmed baryon and meson formation reproduce the features of our measured Λ c / D 0 ratio.

13000 GeV-cms/nucleon↗
DOE OSTI2021

Mechanical Characterization of Low Modulus Polymer-Modified Calcium-Silicate-Hydrate (C-S-H) Binder

Calcium-silicate-hydrate (C-S-H) represents a key microstructural phase that governs the mechanical properties of concrete at a large scale. Defects in the C-S-H phase are also responsible for the poor ductility and low tensile strength of concrete. Manipulating the microstructure of C-S-H can lead to new cementitious materials with improved structural performance. This paper presents an experimental investigation aiming to characterize a new synthetic polymer-modified synthetic calcium-silicate-hydrate (C-S-H)/styrene-butadiene rubber (SBR) binder. The new C-S-H/SBR binder is produced by calcining calcium carbonate and mixing this with fumed silica (SiO 2 ), deionized water and SBR. Mechanical, physical, chemical and microstructural characterization was conducted to measure the properties of new hardened C-S-H binder. Results from the experimental investigation demonstrate the ability to engineer a new C-S-H binder with low elastic modulus and improved toughness and bond strength by controlling the SBR content and method of C-S-H synthesis. The new binder suggests the possible development of a new family of low-modulus silica-polymer binders that might fit many engineering applications such as cementing oil and gas wells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Constraining low redshift [C II ] emission by cross-correlating FIRAS and BOSS data

ABSTRACT We perform a tomographic cross-correlation analysis of archival FIRAS data and the BOSS galaxy redshift survey to constrain the amplitude of [C II] 2P3/2 → 2P1/2 fine structure emission. Our analysis employs spherical harmonic tomography (SHT), which is based on the angular cross-power spectrum between FIRAS maps and BOSS galaxy over-densities at each pair of redshift bins, over a redshift range of 0.24 < z < 0.69. We develop the SHT approach for intensity mapping, where it has several advantages over existing power spectral estimators. Our analysis constrains the product of the [C II] bias and [C II] specific intensity, $b_{\rm [C \small{\rm II}]}I_{\rm [C \small{\rm II}]}$, to be <0.31 MJy/sr at z ≈ 0.35 and <0.28 MJy/sr at z ≈ 0.57 at $95{{\ \rm per\ cent}}$ confidence. These limits are consistent with most current models of the [C II] signal, as well as with higher-redshift [C II] cross-power spectrum measurements from the Planck satellite and BOSS quasars. We also show that our analysis, if applied to data from a more sensitive instrument such as the proposed PIXIE satellite, can detect pessimistic [C II] models at high significance.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

First Evidence of Solar Neutrino Interactions on 13 C

The SNO+ Collaboration reports the first evidence of 8 B solar neutrinos interacting on 13 C nuclei. The charged current interaction proceeds through 13 C +𝜈 𝑒 → 13 N+𝑒 − which is followed, with a 10 minute half life, by 13 N → 13 C +𝑒 + +𝜈 𝑒 . The detection strategy is based on the delayed coincidence between the electron and the positron. Evidence for the charged current signal is presented with a significance of 4.2⁢𝜎. Using the natural abundance of 13 C present in the scintillator, 5.7 metric tons of 13 C over 231 days of data were used in this analysis. The 5.6$^{+3.0}_{−2.3}$ observed events in the data set are consistent with the expectation of 4.7$^{+0.6}_{−1.3}$ events. This result is the second real-time measurement of CC interactions of 8 B neutrinos with nuclei and constitutes the lowest energy observation of neutrino interactions on 13 C generally. This enables the first direct measurement of the CC 𝜈 𝑒 reaction to the ground state of 13 N , yielding an average cross section of (16.1$^{+8.5}_{−6.7}$⁢(stat.)$^{+1.6}_{−2.7}$⁢(syst.))×10 −43 cm 2 over the relevant 8 B solar neutrino energies.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Observation of time-dependent C P violation and measurement of the branching fraction of B 0 → J / ψ π 0 decays

We present a measurement of the branching fraction and time-dependent charge-parity ( C P ) decay-rate asymmetries in B 0 → J / ψ π 0 decays. The data sample was collected with the Belle II detector at the SuperKEKB asymmetric e + e − collider in 2019–2022 and contains ( 387 ± 6 ) × 10 6 B B ¯ meson pairs from ϒ ( 4 S ) decays. We reconstruct 392 ± 24 signal decays and fit the C P parameters from the distribution of the proper-decay-time difference of the two B mesons. We measure the branching fraction to be ( B 0 → J / ψ π 0 ) = ( 2.00 ± 0.12 ± 0.09 ) × 10 − 5 and the direct and mixing-induced C P asymmetries to be C C P = 0.13 ± 0.12 ± 0.03 and S C P = − 0.88 ± 0.17 ± 0.03 , respectively, where the first uncertainties are statistical and the second are systematic. We observe mixing-induced C P violation with a significance of 5.0 standard deviations for the first time in this mode. Published by the American Physical Society 2025

Adachi, I. (ORCID:0000000322870173)↗
DOE OSTI2021

Benzo[a]pyrene (BaP) metabolites predominant in human plasma following escalating oral micro-dosing with [ 14 C]-BaP

Benzo[a]pyrene (BaP) is formed by incomplete combustion of organic materials (petroleum, coal, tobacco, etc.). BaP is designated by the International Agency for Research on Cancer as a group 1 known human carcinogen; a classification supported by numerous studies in preclinical models and epidemiology studies of exposed populations. Risk assessment relies on toxicokinetic and cancer studies in rodents at doses 5–6 orders of magnitude greater than average human uptake. Using a dose–response design at environmentally relevant concentrations, this study follows uptake, metabolism, and elimination of [ 14 C]-BaP in human plasma by employing UPLC - accelerator mass spectrometry (UPLC-AMS). Volunteers were administered 25, 50, 100, and 250 ng (2.7–27 nCi) of [ 14 C]-BaP (with interceding minimum 3-week washout periods) with quantification of parent [ 14 C]-BaP and metabolites in plasma measured over 48 h. [ 14 C]-BaP median T max was 30 min with C max and area under the curve (AUC) approximating dose-dependency. Marked inter-individual variability in plasma pharmacokinetics following a 250 ng dose was seen with 7 volunteers as measured by the C max (8.99 ± 7.08 ng × mL -1 ) and AUC0-48hr (68.6 ± 64.0 fg × hr -1 × mL -1 ). Approximately 3–6% of the [ 14 C] recovered (AUC 0-48 hr ) was parent compound, demonstrating extensive metabolism following oral dosing. Metabolite profiles showed that, even at the earliest time-point (30 min), a substantial percentage of [ 14 C] in plasma was polar BaP metabolites. The best fit modeling approach identified non-compartmental apparent volume of distribution of BaP as significantly increasing as a function of dose (p = 0.004). Bay region tetrols and dihydrodiols predominated, suggesting not only was there extensive first pass metabolism but also potentially bioactivation. AMS enables the study of environmental carcinogens in humans with de minimus risk, allowing for important testing and validation of physiologically based pharmacokinetic models derived from animal data, risk assessment, and the interpretation of data from high-risk occupationally exposed populations.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Experimental and theoretical determinations of hydrogen isotopic equilibrium in the system CH 4 —H 2 —H 2 O from 3 to 200°C

The stable isotopic composition of methane (CH 4 ) is commonly used to fingerprint natural gas origins. Over the past 50 years, there have been numerous proposals that both microbial and thermogenic CH 4 can form in or later attain hydrogen isotopic equilibrium with water (H 2 O) and carbon isotopic equilibrium with carbon dioxide (CO 2 ). Evaluation of such proposals requires knowledge of the equilibrium fractionation factors between CH 4 and H 2 O or CO 2 at the temperatures where microbial and thermogenic CH 4 form in or are found in the environment, which is generally less than 200°C. Experimental determinations of these fractionation factors are only available above 200°C, requiring extrapolation of these results beyond the calibrated range or the use of theoretical calculations at lower temperatures. Here, we provide a calibration of the equilibrium hydrogen isotopic fractionation factor for CH 4 and hydrogen gas (H 2 ) ( D α CH4(g)–H2(g) ) based on experiments using γ-Al 2 O 3 and Ni catalysts from 3 to 200°C. Results were regressed as a 2 nd order polynomial of 1000 × ln D α CH4(g)–H2(g) vs. 1/T (K -1 ) yielding: 1000 × l n D α C H 4 ( g ) - H 2 ( g ) = 3.5317 × 10 7 T 2 + 2.7749 × 10 5 T - 179.48 We combine this calibration with previous experimental determinations of hydrogen isotope equilibrium between H 2 , H 2 O(g), and H 2 O(l) and we provide an interpolatable experimental calibration of 1000 × ln D α CH4(g)–H2O(l) from 3 to 200°C. Our resulting 4th order polynomial is the following equation: 1000 × l n D α C H 4 ( g ) - H 2 O l = - 7.9443 × 10 12 T 4 + 8.7772 × 10 10 T 3 - 3.4973 × 10 8 T 2 + 5.4398 × 10 5 T - 382.05 At 3°C, the value from our calibration differs by 93‰ relative to what would be calculated based on the extrapolation of the only experimental calibration currently available to temperatures below its calibrated range (lowest temperature of 200°C; Horibe and Craig, 1995). We additionally provide new theoretical estimates of hydrogen isotopic equilibrium between CH 4 (g), H 2 (g), and H 2 O(g) and carbon isotopic equilibrium between CH 4 (g) and CO 2 (g) using Path Integral Monte Carlo (PIMC) calculations. Our PIMC calculations for hydrogen isotopic equilibrium between CH 4 and H 2 agree 1:1 with our experiments. Finally, we compile carbon and hydrogen isotopic measurements of CH 4 , CO 2 , and H 2 O from various environmental systems and compare observed differences between carbon and hydrogen isotopes to those expected based on isotopic equilibrium. We find that isotopic compositions of some microbial gases from marine sedimentary, coalbed, and shale environments are consistent with those expected for CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. In contrast, microbial terrestrial and pure culture gases are not consistent with both CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. Overall, these results are explained qualitatively using previously developed conceptual models that link free energy gradients available to microorganisms to the degree that their enzymes can promote isotope-exchange reactions between CH 4 , CO 2 , and H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗