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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2

A Fourier transform spectrum of sulfur dioxide 33S16O2 has been recorded in the 18.3 µm spectral region at a resolution of 0.002 cm-1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν2 and 2ν2- ν2 vibrational bands of the 33S16O2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~0.20 x 10-3 cm-1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band centers: ν0 (ν2) =515.659089(50) cm-1, ν0 (2ν2) = 1030.697723(20) cm-1.

Blake, T. A.↗
DOE OSTI2016

Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

We present theoretical calculations for all three isotope ratios of sulfur ( 33 S/ 32 S, 34 S/ 32 S, 36 S/ 32 S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30–40H 2 O clusters spanning the range of sulfur oxidation state (S n , n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34 β values based on major isotope ( 34 S/ 32 S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34 β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values ( x/34 κ = ln( x β)/ln( 34 β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds ( 33/34 κ ≈ 0.5148–0.5159, 36/34 κ ≈ 1.89–1.90 from T ≽ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit ( 33/34 κT→∞= 0.51587 ± 0.00003 and 36/34 κT→∞= 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34 β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO 3 - T(aq)/SO 2(g, aq) , SO 2(aq) /SO 2(g) , H 2 S (aq) /H 2 S (g) , H 2 S (aq) /HS - (aq) , SO 4 2- (aq) /H 2 S T(aq) , S 2 O 3 2- (aq) (intramolecular), and S 2 O 3 2- (aq) /H 2 S T(aq) , and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO 3 - T /SO 3 2- major isotope ( 34 S/ 32 S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O 3 - /SO 3 2- fractionation factor (1000ln 34 α (HS)bisulfite-sulfite = 19.9‰, 25 °C) relative to the (HO)SO 2 - /SO 3 2- fractionation factor (1000ln 34 α (HO)bisulfite–sulfite = -2.2‰, 25 °C), and the increased stability of the (HS)O 3 - isomer with increasing temperature. Finally, we argue that isomerization phenomenon should be considered in models of the sulfur cycle, including models that describe the overall sulfur isotope fractionations associated with microbial metabolism (e.g., microbial sulfate reduction).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanistic Investigation of Dimethylmercury Formation Mediated by a Sulfide Mineral Surface

Mercury (Hg) pollution is a global environmental problem, but many key transformations among 29 various Hg species are not well understood. Although anaerobic microorganisms are the primary 30 producers of monomethylmercury (MMeHg), the abiotic formation of dimethylmercury (DMeHg) 31 from MMeHg have been suggested to account for a large portion of DMeHg in the ocean. It has 32 been shown that abiotic formation of DMeHg from MMeHg can be facilitated by reduced sulfur 33 groups on mineral surfaces. However, a detailed mechanistic understanding of this reaction is 34 lacking. Here we perform density functional theory (DFT) calculations to explore mechanisms of 35 DMeHg formation on the 110 surface of a CdS(s) (hawleyite) nanoparticle. We show that 36 coordination of MMeHg substituents to adjacent reduced sulfur groups protruding from the surface 37 facilitate DMeHg formation and that the reaction proceeds through direct transmethylation from 38 one MMeHg substituent to another. Solvation effects were found to play an important role in the 39 surface reconstruction of the nanoparticle and in decreasing the energetic barrier for DMeHg 40 formation. We also investigate DMeHg formation from MMeHg mediated by organic dithiols and 41 compare the results to those mediated by the mineral surface. In contrast to the surface reaction, 42 the calculations suggest that dithiol-mediated formation of DMeHg instead proceeds through a 43 mechanism in which Hg–Hg interactions activate a methyl group from one MMeHg substituent 44 for intramolecular transfer to the adjacent MMeHg substituent. These findings refine previously 45 proposed mechanisms of abiotic DMeHg formation and fill gaps in our understanding of global 46 Hg cycling in the environment.

Lian, Peng↗
DOE OSTI2011

Nuclear Data Sheets for A = 33

The experimental data are evaluated for known nuclides of mass number A=33 (Ne, Na, Mg, Al, Si, P, S, Cl, Ar, K). Detailed evaluated level properties and related information are presented, including adopted values of level and {gamma}-ray energies, decay data (energies, intensities and placement of radiations), and other spectroscopic data. This work supersedes earlier full evaluations of A=33 published by 1990En08 (also 1998En04 update) and 1978En02. Experimental studies for the identification of the {sup 33}Ne and {sup 33}K nuclides have not met with success as yet. Values of S(n) and S(p) from systematics for {sup 33}Ne and {sup 33}K, respectively suggest that these nuclei are likely to be unstable to particle emission. The radioactive decay schemes of {sup 33}Na and {sup 33}Al seem incomplete in view of large Q values and known excitations much below than allowed by the Q values. The {sup 33}S and {sup 33}Cl nuclides remain as the most extensively studied from many different reactions and decays.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Coordinated analysis of two graphite grains from the CO3.0 LAP 031117 meteorite: first identification of a CO nova graphite and a presolar iron sulfide subgrain

Presolar grains constitute the remnants of stars that existed before the formation of the solar system. In addition to providing direct information on the materials from which the solar system formed, these grains provide ground-truth information for models of stellar evolution and nucleosynthesis. Here we report the in situ identification of two unique presolar graphite grains from the primitive meteorite LaPaz Icefield 031117. Based on these two graphite grains, we estimate a bulk presolar graphite abundance of 5{sub −3}{sup +7} ppm in this meteorite. One of the grains (LAP-141) is characterized by an enrichment in {sup 12}C and depletions in {sup 33,34}S, and contains a small iron sulfide subgrain, representing the first unambiguous identification of presolar iron sulfide. The other grain (LAP-149) is extremely {sup 13}C-rich and {sup 15}N-poor, with one of the lowest {sup 12}C/{sup 13}C ratios observed among presolar grains. Comparison of its isotopic compositions with new stellar nucleosynthesis and dust condensation models indicates an origin in the ejecta of a low-mass CO nova. Grain LAP-149 is the first putative nova grain that quantitatively best matches nova model predictions, providing the first strong evidence for graphite condensation in nova ejecta. Our discovery confirms that CO nova graphite and presolar iron sulfide contributed to the original building blocks of the solar system.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Herschel observations of extra-ordinary sources: H{sub 2}S as a probe of dense gas and possibly hidden luminosity toward the Orion KL hot core

We present Herschel/HIFI observations of the light hydride H{sub 2}S obtained from the full spectral scan of the Orion Kleinmann-Low nebula (Orion KL) taken as part of the Herschel Observations of EXtra-Ordinary Sources GT (guaranteed time) key program. In total, we observe 52, 24, and 8 unblended or slightly blended features from H{sub 2} {sup 32}S, H{sub 2} {sup 34}S, and H{sub 2} {sup 33}S, respectively. We only analyze emission from the so-called hot core, but emission from the plateau, extended ridge, and/or compact ridge are also detected. Rotation diagrams for ortho and para H{sub 2}S follow straight lines given the uncertainties and yield T {sub rot} = 141 ± 12 K. This indicates H{sub 2}S is in local thermodynamic equilibrium and is well characterized by a single kinetic temperature or an intense far-IR radiation field is redistributing the population to produce the observed trend. We argue the latter scenario is more probable and find that the most highly excited states (E {sub up} ≳ 1000 K) are likely populated primarily by radiation pumping. We derive a column density, N {sub tot}(H{sub 2} {sup 32}S) = 9.5 ± 1.9 × 10{sup 17} cm{sup –2}, gas kinetic temperature, T {sub kin} = 120±{sub 10}{sup 13} K, and constrain the H{sub 2} volume density, n{sub H{sub 2}} ≳ 9 × 10 {sup 7} cm{sup –3}, for the H{sub 2}S emitting gas. These results point to an H{sub 2}S origin in markedly dense, heavily embedded gas, possibly in close proximity to a hidden self-luminous source (or sources), which are conceivably responsible for Orion KL's high luminosity. We also derive an H{sub 2}S ortho/para ratio of 1.7 ± 0.8 and set an upper limit for HDS/H{sub 2}S of <4.9 × 10 {sup –3}.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

{sup 33}S for Neutron Capture Therapy: Nuclear Data for Monte Carlo Calculations

A study of the nuclear data required for the Monte Carlo simulation of boron neutron capture therapy including the {sup 33}S isotope as an enhancer of the dose at small depths has been performed. In particular, the controversy on the available data for the {sup 33}S(n, α) cross section will be shown, which motivates new measurements. In addition to this, kerma factors for the main components of tissue are calculated with the use of fitting functions. Finally, we have applied these data to a potential neutron capture treatment with boron and sulfur addition to tissue in which part of the hydrogen atoms are replaced by deuterium, which improves the procedure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2011

Fock-space multireference coupled-cluster calculations of the hyperfine structure of isoelectronic {sup 33}S{sup -} and {sup 35,37}Cl

Due to its flexibility and possible systematic improvement, the Fock-space (FS) multireference coupled-cluster (MRCC) method remains a very important tool for the computation of energy differences of spectroscopic interest. In the present work, the FS MRCC method for the electron detachment process has been applied to determine the magnetic hyperfine constant A{sub J} and nuclear quadrupole moments Q (related to electric hyperfine constant B{sub J}) for the lowest multiplets of {sup 33}S{sup -}, {sup 35}Cl, and {sup 37}Cl with Dirac-Fock orbitals. In addition, we also report {sup 2}P{sub 3/2}([Ne]3s{sup 2}3p{sup 5}) {yields} {sup 2}P{sub 1/2}([Ne]3s{sup 2}3p{sup 5}) magnetic dipole transition matrix element and electron affinity of {sup 35}Cl (i.e., ionization energy of Cl{sup -}). Calculated properties are in very good agreement with the available new standard or reference values.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2011

Branches of {sup 33}S(p,{gamma}){sup 34}Cl at oxygen-neon nova temperatures

Recent simulations of classical novae on oxygen-neon white-dwarf stars indicate that the isotopic ratio {sup 32}S/{sup 33}S has the potential to be a remarkable indicator of presolar grains of nova origin. The {sup 33}S(p,{gamma}){sup 34}Cl reaction influences this ratio directly by destroying {sup 33}S in novae. Additionally, {beta}-delayed {gamma} rays from the metastable state of {sup 34}Cl (t{sub 1/2}=32 min) have been suggested to be potential nova observables. We have measured the branches for known {sup 33}S(p,{gamma}){sup 34}Cl resonances that are activated at temperatures relevant to oxygen-neon novae. We provide the first reliable uncertainties on these branches and the first upper limits for several previously unmeasured branches.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2011

Improving the {sup 33}S(p,{gamma}){sup 34}Cl Reaction Rate for Models of Classical Nova Explosions

Reduced uncertainty in the thermonuclear rate of the {sup 33}S(p,{gamma}){sup 34}Cl reaction would help to improve our understanding of nucleosynthesis in classical nova explosions. At present, models are generally in concordance with observations that nuclei up to roughly the calcium region may be produced in these explosive phenomena; better knowledge of this rate would help with the quantitative interpretation of nova observations over the S-Ca mass region, and contribute towards the firm establishment of a nucleosynthetic endpoint. As well, models find that the ejecta of nova explosions on massive oxygen-neon white dwarfs may contain as much as 150 times the solar abundance of {sup 33}S. This characteristic isotopic signature of a nova explosion could possibly be observed through the analysis of microscopic grains formed in the environment surrounding a nova and later embedded within primitive meteorites. An improved {sup 33}S(p,{gamma}){sup 34}Cl rate (the principal destruction mechanism for {sup 33}S in novae) would help to ensure a robust model prediction for the amount of {sup 33}S that may be produced. Finally, constraining this rate could confirm or rule out the decay of an isomeric state of {sup 34}Cl(E{sub x} = 146 keV, t{sub 1/2} = 32 m) as a source for observable gamma-rays from novae. We have performed several complementary experiments dedicated to improving our knowledge of the {sup 33}S(p,{gamma}){sup 34}Cl rate, using both indirect methods (measurement of the {sup 34}S({sup 3}He,t){sup 34}Cl and {sup 33}S({sup 3}He,d){sup 34}Cl reactions with the Munich Q3D spectrograph) and direct methods (in normal kinematics at CENPA, University of Washington, and in inverse kinematics with the DRAGON recoil mass separator at TRIUMF). Our results will be used with nova models to facilitate comparisons of model predictions with present and future nova observables.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2013

Massively parallel implementations of coupled-cluster methods for electron spin resonance spectra. I. Isotropic hyperfine coupling tensors in large radicals

Coupled cluster (CC) methods provide highly accurate predictions of molecular properties, but their high computational cost has precluded their routine application to large systems. Fortunately, recent computational developments in the ACES III program by the Bartlett group [the OED/ERD atomic integral package, the super instruction processor, and the super instruction architecture language] permit overcoming that limitation by providing a framework for massively parallel CC implementations. In that scheme, we are further extending those parallel CC efforts to systematically predict the three main electron spin resonance (ESR) tensors (A-, g-, and D-tensors) to be reported in a series of papers. In this paper inaugurating that series, we report our new ACES III parallel capabilities that calculate isotropic hyperfine coupling constants in 38 neutral, cationic, and anionic radicals that include the {sup 11}B, {sup 17}O, {sup 9}Be, {sup 19}F, {sup 1}H, {sup 13}C, {sup 35}Cl, {sup 33}S,{sup 14}N, {sup 31}P, and {sup 67}Zn nuclei. Present parallel calculations are conducted at the Hartree-Fock (HF), second-order many-body perturbation theory [MBPT(2)], CC singles and doubles (CCSD), and CCSD with perturbative triples [CCSD(T)] levels using Roos augmented double- and triple-zeta atomic natural orbitals basis sets. HF results consistently overestimate isotropic hyperfine coupling constants. However, inclusion of electron correlation effects in the simplest way via MBPT(2) provides significant improvements in the predictions, but not without occasional failures. In contrast, CCSD results are consistently in very good agreement with experimental results. Inclusion of perturbative triples to CCSD via CCSD(T) leads to small improvements in the predictions, which might not compensate for the extra computational effort at a non-iterative N{sup 7}-scaling in CCSD(T). The importance of these accurate computations of isotropic hyperfine coupling constants to elucidate experimental ESR spectra, to interpret spin-density distributions, and to characterize and identify radical species is illustrated with our results from large organic radicals. Those include species relevant for organic chemistry, petroleum industry, and biochemistry, such as the cyclo-hexyl, 1-adamatyl, and Zn-porphycene anion radicals, inter alia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Experimental study of Cl 35 excited states via S 32 ( α , p )

The presolar grains originating in oxygen-neon novae may be identified more easily than those of other stellar sources if their sulfur isotopic ratios ($^{33}\mathrm{S}/^{32}\mathrm{S}$ and $^{34}\mathrm{S}/^{32}\mathrm{S}$) are compared with the theoretical ones. The accuracy of such a comparison depends on reliable $^{33}\mathrm{S}(p,{\gamma})^{34}\mathrm{Cl}$ and $^{34}\mathrm{S}(p,{\gamma})^{35}\mathrm{Cl}$ reaction rates at the nova temperature regime. The latter rate has recently been computed based on experimental input, and many new excited states in $^{35}\mathrm{Cl}$ were discovered above the proton threshold. As a result, the experimental $^{34}\mathrm{S}(p,{\gamma})^{35}\mathrm{Cl}$ rate was found to be less uncertain and 2–5 times smaller than the theoretical one. Consequently, the simulated $^{34}\mathrm{S}/^{32}\mathrm{S}$ isotopic ratio for nova presolar grains was predicted to be smaller than that of type II supernova grains by a factor of 1.5 to 3.7. The present study was performed to confirm the existence of these new resonances, and to improve the remaining uncertainties in the S 34 ( p , γ ) Cl 35 reaction rate. Energies and spin-parities of the Cl 35 excited levels were investigated via high-resolution charged-particle spectroscopy with an Enge split-pole spectrograph using the S 32 ( α , p ) Cl 35 reaction. Differential cross sections of the outgoing protons were measured at E α = 21 MeV. Distorted-wave Born approximation calculations were carried out to constrain the spin-parity assignments of observed levels, with special attention to those significant in determination of the S 34 ( p , γ ) Cl 35 reaction rate over the nova temperature regime. The existence of these newly discovered states are largely confirmed, although a few states were not observed in this study. The spins and parities of a few Cl 35 states were assigned tentatively for the first time. The present S 34 ( p , γ ) Cl 35 experimental thermonuclear reaction rate at 0.1–0.4 GK is consistent within 1 σ with the previous evaluation. However, our rate uncertainty is larger than before due to a more realistic treatment of the uncertainties in the rate input. In comparison with the previous rate evaluation, where the high and low rates differed by less than a factor of 2 over the nova temperature regime, the ratio of the present limit rates is at most a factor of 3.5 at 0.12 GK. At temperatures above 0.2 GK, we recommend the future work to focus on determination of the unknown properties of four excited states of Cl 35 : 6643, 6761, 6780, and 6800 keV.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2018

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this ‘mass-independent’ fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative Δ(exp 33)S values and positive Δ(exp 33)S values in elemental sulfur—just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive Δ(exp 33)S and negative Δ(exp 33)S. Positive Δ(exp 33)S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

C. E. Harman↗
NASA NTRSDate not supplied

Identifying Sources of Sulfate Preserved in High Elevation Lava Tubes From Mauna Loa, Hawaii

Volcanic sulfates record a history of their formation pathways in their triple oxygen isotope compositions, making them a powerful target for understanding atmospheric chemistry. To understand how these isotopic signals may be preserved in sulfate minerals, we investigate multiple O and S isotopes of thenardite, mirabilite, and gypsum from in a Mars analog environment: a pair of lava tubes near the summit of Mauna Loa, Hawaii. Based on 16 O-, 17 O- 18 O compositions, the primary oxygen sources for sulfates in the lava tube are atmospheric oxygen (O 2 ), peroxide (H 2 O 2 ), and ozone (O 3 ). We suggest the isotopic signature of O 2 originates from combustion of reduced sulfur gases and/or elemental sulfur at the eruptive source or within the lava tube soon after skylight collapse. Sulfate with isotopic signatures of peroxide and ozone are typically expected from aqueous reactions in cloud droplets. Chemical modeling indicates the observed proportion of ozone sourced sulfate requires pH greater than ~5.4, higher than measured cloud water pH, instead suggesting the observed O 3 signature could not have formed in cloud water droplets. We interpret that sulfate possessing an ozone signature in the lava tube sulfates formed on wetted surfaces of the lava tubes with alkalinity from alteration of basaltic glass. Furthermore, the oxygen and sulfur isotopes of the sulfate are uncorrelated. Multiple sulfur isotopes ( 32 S- 33 S- 34 S- 36 S) from the Mauna Loa sulfates are consistent with ocean island basalt from Pitcairn, suggesting the sulfate-sulfur has not been modified compared to its volcanic source. The findings of this study indicate that oxidation by ozone plays a key role in the formation of sulfate within lava tubes. We also find that combustion is a significant pathway toward sulfuric acid formation in volcanic environments. Similar signatures should be expected on other planets if volcanism is a significant sulfate source, as has been suggested for Mars. If true, sulfates in returned samples from Mars may hold key information on pO 2 , pCO 2 and planetary scale oxygen fluxes at the time of sulfate formation.

Justin Hayles↗
DOE OSTI2013

{sup 33}S hyperfine interactions in H{sub 2}S and SO{sub 2} and revision of the sulfur nuclear magnetic shielding scale

Using the Lamb-dip technique, the hyperfine structure in the rotational spectra of H{sub 2}{sup 33}S and {sup 33}SO{sub 2} has been resolved and the corresponding parameters—that is, the sulfur quadrupole-coupling and spin–rotation tensors—were determined. The experimental parameters are in good agreement with results from high-level coupled-cluster calculations, provided that up to quadruple excitations are considered in the cluster operator, sufficiently large basis sets are used, and vibrational corrections are accounted for. The {sup 33}S spin-rotation tensor for H{sub 2}S has been used to establish a new sulfur nuclear magnetic shielding scale, combining the paramagnetic part of the shielding as obtained from the spin–rotation tensor with a calculated value for the diamagnetic part as well as computed vibrational and temperature corrections. The value of 716(5) ppm obtained in this way for the sulfur shielding of H{sub 2}S is in good agreement with results from high-accuracy quantum-chemical calculations but leads to a shielding scale that is about 28 ppm lower than the one suggested previously in the literature, based on the {sup 33}S spin-rotation constant of OCS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A COMPLETE SPECTROSCOPIC CHARACTERIZATION OF SO AND ITS ISOTOPOLOGUES UP TO THE TERAHERTZ DOMAIN

In order to obtain accurate terahertz center frequencies for SO and its isotopologues, we have studied the absorption spectrum of SO, {sup 34}SO, and {sup 33}SO up to 2.5 THz using continuous-wave terahertz photomixing based on a frequency comb providing an accuracy down to 10 kHz. Sulfur monoxide was produced in a radio frequency discharge of air in a cell containing pure sulfur. Together with the strong absorption signal of the main isotopologue, transitions of {sup 34}SO ({sup 34}S: 4.21%) and {sup 33}SO ({sup 33}S: 0.75%) were observed in natural abundance. The newly observed transitions constitute an extension of the observed rotational quantum numbers of the molecule toward higher N values, allowing an improvement of the molecular parameters for the three species. An isotopically invariant fit has been performed based on pure rotational and ro-vibrational transitions of all SO isotopologues, enabling their accurate line position prediction at higher frequencies. Thanks to this new set of parameters, it is now possible to predict with very high accuracy the frequencies of the ro-vibrational lines. This should enable the research of SO in the mid-IR using ground-based IR telescopes, space-based telescope archives (Infrared Space Observatory, Spitzer), and future space missions such as the James Webb Space Telescope. This set of parameters is particularly well adapted for the detection of SO lines in O-rich evolved stars or in molecular clouds in absorption against bright IR sources.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Evidence of both molecular cloud and fluid chemistry in Ryugu regolith

The sulfur chemistry of (162173) Ryugu particles can be a powerful tracer of molecular cloud chemistry and small body processes, but it has not been well explored. We report identification of organosulfurs and a sulfate grain in two Ryugu particles, A0070 and A0093. The sulfate grain shows oxygen isotope ratios (δ 17 O = -11.0 ± 4.3 per mil, δ 18 O = -7.8 ± 2.3 per mil) that are akin to silicates in Ryugu but exhibit mass-independent sulfur isotopic fractionation (Δ 33 S = +5 ± 2 per mil). A methionine-like coating on the sulfate grain is isotopically anomalous (δ 15 N = +62 ± 2 per mil). Both the sulfate and organosulfurs can simultaneously form and survive during aqueous alteration within Ryugu’s parent body, under reduced conditions, low temperature, and a pH >7 in the presence of N-rich organic molecules. This work extends the heliocentric zone where anomalous sulfur, formed by selective photodissociation of H 2 S gas in the molecular cloud, is found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Williford, K. H.↗