An analytical formulation of isotope fractionation due to self-shielding.

Isotope fractionation due to photochemical self-shielding is believed to be responsible for the enrichment of inner solar system planetary materials in the rare isotopes of carbon, nitrogen, and oxygen relative to the Sun. Self-shielding may also contribute to sulfur isotope mass-independent fractionation in modern atmospheric sulfates, although its role in the early Earth atmosphere has not yet been convincingly established. Here, I present an analytical formulation of isotopic photodissociation rate coefficients that describe self-shielding isotope signatures for 3 and 4-isotope systems broadly representative of O and S isotopes. The analytic equations are derived for idealized molecular spectra, making an analytic formulation tractable. The idealized spectra characterize key features of actual isotopologue spectra, particularly for CO and SO2, but are applicable to many small molecules and their isotopologues. The analytic expressions are convenient for evaluating the magnitude of isotope effects without having to pursue involved numerical solutions. More importantly, the analytic expressions illustrate the origin of particular isotope signatures, such as the previously unexplained large mass-dependent fractionation associated with photodissociation of optically-thick SO2. The formulation presented here elucidates the origin of some of these important isotopic fractionation processes.

Fourier-transform-spectroscopic photoabsorption cross sections and oscillator strengths for the S2 BΣu-3-XΣg-3 system.

Photoabsorption cross sections and oscillator strengths for the strong, predissociating vibrational bands, v ≥ 11, in the S2 BΣu-3-XΣg-3(v,0) system are reported. Absorption measurements were undertaken on S2 vapor produced by a radio-frequency discharge through H2S seeded in helium, and also in a two-temperature sulfur furnace, at temperatures of 370 K and 823 K, respectively. S2 column densities were determined in each source by combining experimental line strengths in low-v non-predissociating B - X bands (v < 7) with calculated line f-values based on measured radiative lifetimes and calculated branching ratios. The broad-band capabilities of two vacuum-ultraviolet Fourier-transform spectrometers, used with instrumental resolutions of 0.22 cm-1 and 0.12 cm-1, respectively, allowed for simultaneous recordings of both non-predissociating and predissociating bands, thus placing the predissociating-band cross sections on a common absolute scale. Uncertainties in the final cross section datasets are estimated to be 15% for the 370-K vapor and 10% for the 823-K vapor. The experimental cross sections are used to inform a detailed predissociation model of the B(v) levels in Paper II [Lewis et al., J. Chem. Phys. 148, 244303 (2018)]. For astrophysical and other applications, this model can be adjusted simply to provide isotopologue-specific cross sections for a range of relevant temperatures.

Observation of a new electronic state of CO perturbing W ¹Π(v=1).

We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation.

Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

Flash heating on the early Earth.

It has been suggested that very large impact events (approximately 500 km diameter impactors) sterilized the surface of the young Earth by producing enough rock vapor to boil the oceans. Here, we consider surface heating due to smaller impactors, and demonstrate that surface temperatures conductive to organic synthesis resulted. In particular, we focus on the synthesis of thermal peptides. Previously, laboratory experiments have demonstrated that dry heating a mixture of amino acids containing excess Asp, Glu, or Lys to temperatures approximately 170 degrees C for approximately 2 hours yields polypeptides. It has been argued that such temperature conditions would not have been available on the early Earth. Here we demonstrate, by analogy with the K/T impact, that the requisite temperatures are achieved on sand surfaces during the atmospheric reentry of fine ejecta particles produced by impacts of bolides approximately 10-20 km in diameter, assuming approximately 1-100 PAL CO2. Impactors of this size struck the Earth with a frequency of approximately 1 per 10(4)-10(5) y at 4.2 Ga. Smaller bolides produced negligible global surface heating, whereas bolides > 30 km in diameter yielded solid surface temperatures > 1000 K, high enough to pyrolyze amino acids and other organic compounds. Thus, peptide formation would have occurred globally for a relatively narrow range of bolide sizes.

Metal ions in the atmosphere of Neptune.

Microwave propagation experiments performed with Voyager 2 at Neptune revealed sharp layers of electrons in Neptune's lower ionosphere with densities of approximately 10(4) per cubic centimeter. These layers are reminiscent of the sporadic-E layers in the Earth's ionosphere, and when taken together with data from the other giant planets, these data confirm the importance of the magnetic field in layer formation. A photochemical model that incorporates species produced by meteoroid ablation predicts that singly ionized magnesium is the most likely metal to be found in the layers, although laboratory data on the kinetics of metallic atoms and ions in a reducing environment are lacking. The metal chemistry discussed here is directly relevant to the abundant metals observed at the impact site of the G fragment of comet Shoemaker Levy 9 on Jupiter.

Solar control of the upper atmosphere of Triton.

If the upper atmosphere and ionosphere of Triton are controlled by precipitation of electrons from Neptune's magnetosphere as previously proposed, Triton could have the only ionosphere in the solar system not controlled by solar radiation. However, a new model of Triton's atmosphere, in which only solar radiation is present, predicts a large column of carbon atoms. With an assumed, but reasonable, rate of charge transfer between N2(+) and C, a peak C+ abundance results that is close to the peak electron densities measured by Voyager in Triton's ionosphere. These results suggest that Triton's upper atmospheric chemistry may thus be solar-controlled. Measurement of key reaction rate constants, currently unknown or highly uncertain at Triton's low temperatures, would help to clarify the chemical and physical processes occurring in Triton's atmosphere.

Triton: topside ionosphere and nitrogen escape.

The principal ion in the ionosphere of Triton is N+. Energetic electrons of magnetospheric origin are the primary source of ionization, with a smaller contribution due to photoionization. To explain the topside plasma scale height, we postulate that N+ ions escape from Triton. The loss rate is 3.4 x 10(7) cm-2 s-1 or 7.9 x 10(24) ions s-1. Dissociative recombination of N2+ produces neutral exothermic fragments that can escape from Triton. The rate is estimated to be 8.6 x 10(6) N cm-2 s-1 or 2.0 x 10(24) atoms s-1. Implications for the magnetosphere of Neptune and Triton's evolution are discussed.

Voyager radio science observations of neptune and triton.

The Voyager 2 encounter with the Neptune system included radio science investigations of the masses and densities of Neptune and Triton, the low-order gravitational harmonics of Neptune, the vertical structures of the atmospheres and ionospheres of Neptune and Triton, the composition of the atmosphere of Neptune, and characteristics of ring material. Demanding experimental requirements were met successfully, and study of the large store of collected data has begun. The initial search of the data revealed no detectable effects of ring material with optical depth tau [unknown] 0.01. Preliminary representative results include the following: 1.0243 x 10(26) and 2.141 x 10(22) kilograms for the masses of Neptune and Triton; 1640 and 2054 kilograms per cubic meter for their respective densities; 1355 +/- 7 kilometers, provisionally, for the radius of Triton; and J(2) = 3411 +/- 10(x 10(-6)) and J(4) = -26(+12)(-20)(x10(-6)) for Neptune's gravity field (J>(2) and J(4) are harmonic coefficients of the gravity field). The equatorial and polar radii of Neptune are 24,764 +/- 20 and 24,340 +/- 30 kllometers, respectively, at the 10(5)-pascal (1 bar) pressure level. Neptune's atmosphere was probed to a pressure level of about 5 x 10(5) pascals, and effects of a methane cloud region and probable ammonia absorption below the cloud are evident in the data. Results for the mixing ratios of helium and ammonia are still being investigated; the methane abundance below the clouds is at least 1 percent by volume. Derived temperature-pressure profiles to 1.2 x 10(5) pascals and 78 kelvins (K) show a lapse rate corresponding to "frozen" equilibrium of the para- and ortho-hydrogen states. Neptune's ionosphere exhibits an extended topside at a temperature of 950 +/- 160 K if H(+) is the dominant ion, and narrow ionization layers of the type previously seen at the other three giant planets. Triton has a dense ionosphere with a peak electron concentration of 46 x 10(9) per cubic meter at an altitude of 340 kilometers measured during occultation egress. Its topside plasma temperature is about 80 +/- 16 K if N(2)(+) is the principal ion. The tenuous neutral atmosphere of Triton produced distinct signatures in the occultation data; however, the accuracy of the measurements is limited by uncertainties in the frequency of the spacecraft reference oscillator. Preliminary values for the surface pressure of 1.6 +/- 0.3 pascals and an equivalent isothermal temperature of 48 +/- 5 K are suggested, on the assumption that molecular nitrogen dominates the atmosphere. The radio data may be showing the effects of a thermal inversion near the surface; this and other evidence imply that the Triton atmosphere is controlled by vapor-pressure equilibrium with surface ices, at a temperature of 38 K and a methane mixing ratio of about 10(-4).

The lateral pectoral composite flap in one-stage reconstruction of the irradiated mandible.

We present a composite flap based on the musculature of the anterolateral thorax that allows immediate reconstruction of the mandible through the interposition of vascularized bony fifth rib. While the vascular pedicle remains the pectoral branch of the thoracoacromial artery, the pectoralis major muscle can be spared largely intact. The lateral position of the composite rib segment ensures a purely bony composition, while the lateral skin island remains largely hairless. Despite the unfavorable conditions of massive tumor size and prior irradiation attending the clinical cases presented, the complication rate was acceptable, with only one flap loss, and this followed technical error.