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From transmission electron microscopy and other laboratory studies of presolar grains, the implicit condensation sequence of carbon-bearing condensates in circumstellar envelopes of carbon stars is (from first to last) TiC-graphite-SiC. We use thermochemical equilibrium condensation calculations and show that the condensation sequence of TiC, graphite, and SiC depends on metallicity in addition to C/O ratio and total pressure. Calculations were performed for a characteristic carbon star ratio of C/O = 1.2 from 1E-10 to 1E-4 bars total pressure and for uniform metallicity variations ranging from 0.01 to 100 times solar elemental abundances. TiC always condenses before SiC, and the carbide condensation temperatures increase with increasing metallicity and total pressure. Graphite, however, can condense in a cooling circumstellar envelope before TiC, between TiC and SiC, or after SiC, depending on the carbon-bearing gas chemistry, which is dependent on metallicity and total pressure. Analytical expressions for the graphite, TiC, and SiC condensation temperatures as functions of metallicity and total pressure are presented. The inferred sequence from laboratory presolar grain studies, TiC-graphite-SiC, is favored under equilibrium conditions at solar and subsolar metallicities between ~1E-5 to 1E-8 bar total pressure within circumstellar envelopes of carbon stars with nominal C/O = 1.2. We also explored the dependence of the sequence at C/O ratios of 1.1 and 3.0 and found that as the C/O ratio increases, the TiC-graphite-SiC region shifts towards higher total pressures and lower metallicities., Comment: 33 pages, 9 figures, 2 tables. Preprint submitted to The Astrophysical Journal, November 2024

This article describes condensation of the elements and use of condensation temperatures (Tcond) to interpret the volatility trend of the Earth. Major points are: (1) a listing of updated 50% Tcond for all natural elements and Pu at 1e-2 to 1e-8 bar pressure for solar composition matter. (2) The Tcond are mainly controlled by the Gibbs energy of condensation reactions and also by the Gibbs energy of ideal mixing if elements (compounds) condense in a solution. The Gibbs energy change of non-ideal solution (activity coefficients not equal to 1) is a secondary effect. (3) The theoretically correct relationship between Tcond and fraction condensed is derived from mass balance and chemical thermodynamic considerations. (4) The maximum amount of element condensed per 1/T, is at the inflection point in the logistic (sigmoid) curve for an element, which is also at (or close to) the 50% Tcond. (5) Plots of normalized elemental abundances versus 50% Tcond (volatility trends) are qualitative indicators of elemental fractionations due to volatility. (6) Volatility trend plots for average elemental abundances in CM, CO, CV, CR, H, L, LL, EH, EL chondrites show different trends for moderately and highly volatile elements, which may be linear, curved, a step function, or plateau. Comparison of three abundance sets for CM and CV chondrites shows trends depend on which elements are plotted, which data sources are used, and which temperature range is considered. (7) Proposed mechanisms for volatile element depletion in carbonaceous chondrites and the Earth are reviewed. (8) Possible implications of volatile element abundances in the bulk silicate Earth are discussed., Comment: 50 pages, 1 table, 15 figures. Preprint submitted to Space Science Reviews October 2024

We review sulfur chemistry of the gas giant planets and their moons where sulfur compounds are observed. The major S-bearing gas in the upper atmospheres of the giant planets is H2S and is removed from their observable atmospheres by condensation into cloud layers (NH4SH on all four planets and additionally H2S ice on Uranus and Neptune). Any remaining H2S at higher altitudes is destroyed photochemically. Among the moons Io is the world dominated by sulfur. We summarize the sulfur cycle on Io and how pyrovolcanism is spreading sulfur across the Jovian system. Implantation of sulfur into icy surfaces of the other Galilean moons via magnetospheric transfer and radiolysis are major processes affecting the sulfur chemistry on their icy surfaces. On the icy worlds, we are literally looking at the top of the icebergs. Subsurface liquid salty bodies reveal themselves through cryovolcanism on Europa, Ganymede, and Enceladus, where salt deposits are indicated. Subsurface oceans are suspected on several other moons. We summarize the sulfur cycle for the icy Galilean moons. The occurrence of sulfates can be explained by salt exchange reactions of radiolytically produced H2SO4 with brine salts (carbonates and halides), or from a subsurface ocean that has become acidified by uptake of H2SO4 leaked from ice. In the primordial oceans of the moons that accreted with high ice rock ratios, sulfur is expected as sulfide and bisulfide anions and H2S in aqueous solution. Cosmochemical constraints suggest that pyrrhotite, tochilinite and green rusts could be important sulfide bearing compounds found with hydrous silicates such as serpentine, and magnetite on the sea floors. In N-C-rich worlds such as Titan, sulfides such as NH4SH and possibly thiazyl compounds could be important, and sulfates are unstable. Nothing is known about the sulfur chemistry on the Uranian and Neptunian moons., Comment: Preprint of chapter for "The Role of Sulfur in Planetary Processes: from Atmospheres to Cores", D. Harlov and G. Pokrovsky (Eds.), Springer Geochemistry. 64 pages, including 4 tables and 3 figures

The chemical equilibrium distribution of 69 elements between gas and melt is modeled for bulk silicate Earth (BSE) material from 1000 - 4500 K and 1e-6 to 100 bar. The BSE melt is modeled as a non-ideal solution and the effects of different activity coefficients and ideal solution are studied. Results include 50% condensation temperatures, major gases of each element, and oxygen fugacity (fO2) of dry and wet BSE material. The dry BSE model excludes H, C, N, F, Cl, Br, I, S, Se, Te. The wet BSE model includes H and the other volatiles. Key conclusions are much higher condensation temperatures in silicate vapor than in solar composition gas at the same total P, a different condensation sequence in silicate vapor than in solar composition gas, good agreement between different activity coefficient models except for the alkalis, agreement, where overlap exists, with prior published work, condensation of Re, Mo, W, Ru, Os oxides instead of metals, a stability field for Ni-rich metal as reported by Lock et al. (2018), agreement between ideal solution (from this work and from Lock et al. 2018) and real solution condensation temperatures for elements with minor deviations from ideality in the oxide melt, similar 50% condensation temperatures, within a few degrees, in the dry and wet BSE models for the major elements Al, Ca, Fe, Mg, Si, and the minor elements Co, Cr, Li, Mn, Ti, V, and much lower 50 percent condensation temperatures for elements such as B, Cu, K, Na, Pb, Rb, which form halide, hydroxide, sulfide, selenide, telluride and oxyhalide gases. The latter results are preliminary because the poorly known solubilities and activities of volatile elements in silicate melts must be considered for the correct equilibrium distribution, condensation temperatures and mass balance of F, Cl, Br, I, H, S, Se and Te bearing species between melt and vapor (abridged).

We review a large body of literature for concentrations of halogens in chondrites and stellar halogen data used for solar system abundances (i.e., representative abundances of the solar system at the time of its formation) and associated analytical problems. Claims of lower solar system chlorine, bromine and iodine abundances from recent analyses of CI-chondrites are untenable because of incompatibility of such low values with nuclear abundance systematics and measurements of halogens in the sun and other stars. We suspect analytical problems associated with these peculiar rock types caused lower analytical results in several studies. Mass concentrations in CI-chondrites are F=92+-20 ppm, Cl=717+-110 ppm, Br=3.77+-0.90 ppm, and I=0.77+-0.31 ppm, and abundances normalized to N(Si) =10^6 atoms are N(F)=1270+-270, N(Cl)=5290+-810, N(Br)=12.3+-2.9, and N(I)=1.59+-0.64. Meteoritic values scaled to present-day photospheric abundances with log N(H)=12 are A(F)=4.61+-0.09, A(Cl)=5.23+-0.06, A(Br)=2.60+-0.09, and A(I)=1.71+-0.15. These recommended present-day solar system abundances compare to the sunspot values of N(F)=776+-260, A(F)=4.40+-0.25, and N(Cl)=5500+-810, A(Cl)=5.25+-0.12 and are consistent with F and Cl abundance ratios in other stars and other astronomical environments. The chlorine abundance of 776+-21 ppm by Yokoyama et al. (2022) for the CI-chondrite-like asteroid Ryugu is consistent with the chlorine abundance evaluated for CI-chondrites here. Updated equilibrium 50% condensation temperatures from our previous work (Lodders 2003, Fegley & Schaefer 2010, Fegley & Lodders 2018) considering solid-solution and kinetic inhibition effects are 713K (F), 427K (Cl), 392K (Br) and 312K (I) at 10^-4 bar total pressure. Condensation temperatures computed with lower halogen abundances do not represent the correct condensation temperatures from a solar composition gas. (abridged), Comment: 59 pages, 5 figures, 18 tables

Solar system materials are variably depleted in moderately volatile elements (MVEs) relative to the proto-solar composition. To address the origin of this MVE depletion, we conducted a systematic study of high-precision K isotopic composition on 16 carbonaceous chondrites (CCs) of types CM1-2, CO3, CV3, CR2, CK4-5 and CH3 and 28 ordinary chondrites (OCs) covering petrological types 3 to 6 and chemical groups H, L, and LL. We observed significant overall K isotope (delta41K) variations (-1.54 to 0.70 permil). The K isotope compositions of CCs are largely higher than the Bulk Silicate Earth (BSE) value, whereas OCs show typically lower values than BSE. Neither CCs nor OCs show resolvable correlations between K isotopes and chemical groups, petrological types, shock levels, exposure ages, fall or find occurrence, or terrestrial weathering. The lack of a clear trend between K isotopes and K content indicates that the K isotope fractionations were decoupled from the relative elemental K depletions. The range of K isotope variations in the CCs is consistent with a four-component (chondrule, refractory inclusion, matrix and water) mixing model that is able to explain the bulk elemental and isotopic compositions of the main CC groups, but requires a fractionation in K isotopic compositions in chondrules. We propose that the major control of the isotopic compositions of group averages is condensation or vaporization in nebular environments that is preserved in the compositional variation of chondrules. Parent-body processes (aqueous alteration, thermal metamorphism, and metasomatism) can mobilize K and affect the K isotopes in individual samples. In the case of the OCs, the full range of K isotopic variations can only be explained by the combined effects of the size and relative abundances of chondrules, parent-body aqueous and thermal alteration., Comment: 71 pages, 2 tables, 9 figures

Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass-independent and mass-dependent isotope fractionations. Due to the analytical challenges to obtain high-precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high-precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from -2.34 permil to -0.18 permil). However, K isotopic compositions of nearly all enstatite meteorites scatter around the Bulk Silicate Earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (-0.47 +/- 0.57 permil) is indistinguishable from the BSE value (-0.48 +/- 0.03 permil), thus further corroborating the isotopic similarity between Earth' building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent body processing. Our sample of the main group aubrite MIL 13004 is exceptional and has an extremely light K isotopic composition (delta 41K= -2.34 +/- 0.12 permil). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K-bearing sulfide mineral is predicted to be enriched in 39K during equilibrium exchange with silicates., Comment: 46 pages, 7 figures, 2 tables, published in Meteoritics & Planetary Science

Review of the history of solar system elemental abundances with a new assessment of elemental and isotopic abundances from CI-chondrites and solar data. Solar elemental abundances, or solar system elemental abundances refer to the complement of chemical elements in the entire solar system. The sun contains more than 99-percent of the mass in the solar system and therefore the composition of the sun is a good proxy for the composition of the overall solar system. The solar system composition can be taken as the overall composition of the molecular cloud within the interstellar medium from which the solar system formed 4.567 billion years ago. Active research areas in astronomy and cosmochemistry model collapse of a molecular cloud of solar composition into a star with a planetary system, and the physical and chemical fractionation of the elements during planetary formation and differentiation. The solar system composition is the initial composition from which all solar system objects (the sun, terrestrial planets, gas giant planets, planetary satellites and moons, asteroids, Kuiper-belt objects, and comets) were derived. (Abstract truncated)., Comment: review paper

Presolar grains constitute 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(-3)(+7) ppm in this meteorite. One of the grains (LAP-141) is characterized by an enrichment in 12C and depletions in 33,34S, and contains a small iron sulfide subgrain, representing the first unambiguous identification of presolar iron sulfide. The other grain (LAP-149) is extremely 13C-rich and 15N-poor, with one of the lowest 12C/13C 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., Comment: Accepted for publication in The Astrophysical Journal

Extensive experimental studies show all major rocky elements (Si, Mg, Fe, Ni, Ca, Al, Na, K) dissolve in steam to a greater or lesser extent. We use these results to compute chemical equilibrium abundances of rocky element-bearing gases in steam atmospheres equilibrated with silicate magma oceans. Rocky elements partition into steam atmospheres as volatile hydroxide gases and via reaction with HF or HCl as volatile halide gases in much larger amounts than expected from their vapor pressures over volatile-free solid or molten rock at the same temperature. We compute the extent of fractional vaporization by defining gas to magma partition coefficients and show Earth's sub-solar Si to Mg bulk elemental ratio may be due to loss of a primordial steam atmosphere. We conclude hot rocky exoplanets that are undergoing or have undergone escape of steam atmospheres may experience fractional vaporization and loss of Si, Mg, Fe, Ni, Ca, Al, Na, and K. This loss may modify their bulk composition, density, heat balance, and internal structure., Comment: In press in The Astrophysical Journal, 83 pages text and references, 6 tables, 30 figures

We present new calculations of Rosseland and Planck gaseous mean opacities relevant to the atmospheres of giant planets and ultracool dwarfs. Such calculations are used in modeling the atmospheres, interiors, formation, and evolution of these objects. Our calculations are an expansion of those presented in Freedman et al. (2008) to include lower pressures, finer temperature resolution, and also the higher metallicities most relevant for giant planet atmospheres. Calculations span 1 microbar to 300 bar, and 75 K to 4000 K, in a nearly square grid. Opacities at metallicities from solar to 50 times solar abundances are calculated. We also provide an analytic fit to the Rosseland mean opacities over the grid in pressure, temperature, and metallicity. In addition to computing mean opacities at these local temperatures, we also calculate them with weighting functions up to 7000 K, to simulate the mean opacities for incident stellar intensities, rather than locally thermally emitted intensities. The chemical equilibrium calculations account for the settling of condensates in a gravitational field and are applicable to cloud-free giant planet and ultracool dwarf atmospheres, but not circumstellar disks. We provide our extensive opacity tables for public use., Comment: This version fixes a units description error that was only in the arxiv version, but is correct in the ApJS version. In equations 4 and 5 pressure is in dyne/cm2. Online tables available at the ApJS website: https://iopscience.iop.org/article/10.1088/0067-0049/214/2/25

The formation of clouds affects brown dwarf and planetary atmospheres of nearly all effective temperatures. Iron and silicate condense in L dwarf atmospheres and dissipate at the L/T transition. Minor species such as sulfides and salts condense in mid-late T dwarfs. For brown dwarfs below Teff=450 K, water condenses in the upper atmosphere to form ice clouds. Currently over a dozen objects in this temperature range have been discovered, and few previous theoretical studies have addressed the effect of water clouds on brown dwarf or exoplanetary spectra. Here we present a new grid of models that include the effect of water cloud opacity. We find that they become optically thick in objects below Teff=350-375 K. Unlike refractory cloud materials, water ice particles are significantly non-gray absorbers; they predominantly scatter at optical wavelengths through J band and absorb in the infrared with prominent features, the strongest of which is at 2.8 microns. H2O, NH3, CH4, and H2 CIA are dominant opacity sources; less abundant species such as may also be detectable, including the alkalis, H2S, and PH3. PH3, which has been detected in Jupiter, is expected to have a strong signature in the mid-infrared at 4.3 microns in Y dwarfs around Teff=450 K; if disequilibrium chemistry increases the abundance of PH3, it may be detectable over a wider effective temperature range than models predict. We show results incorporating disequilibrium nitrogen and carbon chemistry and predict signatures of low gravity in planetary- mass objects. Lastly, we make predictions for the observability of Y dwarfs and planets with existing and future instruments including the James Webb Space Telescope and Gemini Planet Imager., Comment: 23 pages, 20 figures, Revised for ApJ

Currently, there are about 3 dozen known super-Earth (M < 10 MEarth), of which 8 are transiting planets suitable for atmospheric follow-up observations. Some of the planets are exposed to extreme temperatures as they orbit close to their host stars, e.g., CoRot-7b, and all of these planets have equilibrium temperatures significantly hotter than the Earth. Such planets can develop atmospheres through (partial) vaporization of their crustal and/or mantle silicates. We investigated the chemical equilibrium composition of such heated systems from 500 - 4000 K and total pressures from 10-6 to 10+2 bars. The major gases are H2O and CO2 over broad temperature and pressure ranges, and Na, K, O2, SiO, and O at high temperatures and low pressures. We discuss the differences in atmospheric composition arising from vaporization of SiO2-rich (i.e., felsic) silicates (like Earth's continental crust) and MgO-, FeO-rich (i.e., mafic) silicates like the bulk silicate Earth. The computational results will be useful in planning spectroscopic studies of the atmospheres of Earth-like exoplanets., Comment: 50 pages, 11 figures, 4 tables, ApJ (in press)

Representative abundances of the chemical elements for use as a solar abundance standard in astronomical and planetary studies are summarized. Updated abundance tables for solar system abundances based on meteorites and photospheric measurements are presented., Comment: 46 pages; 5 figures; 8 tables; In: Principles and Perspectives in Cosmochemistry.Lecture Notes of the Kodai School on 'Synthesis of Elements in Stars' held at Kodaikanal Observatory, India, April 29 - May 13, 2008 (Aruna Goswami and B. Eswar Reddy eds.) Astrophysics and Space Science Proceedings, Springer-Verlag Berlin Heidelberg, 2010, p. 379-417 (ISBN 978-3-642-10351-3), 2010

GJ436b is a unique member of the transiting extrasolar planet population being one of the smallest and least irradiated and possessing an eccentric orbit. Because of its size, mass and density, GJ436b could plausibly have an atmospheric metallicity similar to Neptune (20-60 times solar abundances), which makes it an ideal target to study the effects of atmospheric metallicity on dynamics and radiative transfer in an extrasolar planetary atmosphere. We present three-dimensional atmospheric circulation models that include realistic non-gray radiative transfer for 1, 3, 10, 30, and 50 times solar atmospheric metallicity cases of GJ436b. Low metallicity models (1 and 3 times solar) show little day/night temperature variation and strong high-latitude jets. In contrast, higher metallicity models (30 and 50 times solar) exhibit day/night temperature variations and a strong equatorial jet. Spectra and light curves produced from these simulations show strong orbital phase dependencies in the 50 times solar case and negligible variations with orbital phase in the 1 times solar case. Comparisons between the predicted planet/star flux ratio from these models and current secondary eclipse measurements support a high metallicity atmosphere (30-50 times solar abundances) with disequilibrium carbon chemistry at play for GJ436b. Regardless of the actual atmospheric composition of GJ436b, our models serve to illuminate how metallicity influences the atmospheric circulation for a broad range of warm extrasolar planets., Comment: 25 pages, 13 figures

We use thermochemical equilibrium calculations to model iron, magnesium, and silicon chemistry in the atmospheres of giant planets, brown dwarfs, extrasolar giant planets (EGPs), and low-mass stars. The behavior of individual Fe-, Mg-, and Si-bearing gases and condensates is determined as a function of temperature, pressure, and metallicity. Our results are thus independent of any particular model atmosphere. The condensation of Fe metal strongly affects iron chemistry by efficiently removing Fe-bearing species from the gas phase. Monatomic Fe is the most abundant Fe-bearing gas throughout the atmospheres of EGPs and L dwarfs and in the deep atmospheres of giant planets and T dwarfs. Mg- and Si-bearing gases are effectively removed from the atmosphere by forsterite (Mg2SiO4) and enstatite (MgSiO3) cloud formation. Monatomic Mg is the dominant magnesium gas throughout the atmospheres of EGPs and L dwarfs and in the deep atmospheres of giant planets and T dwarfs. Silicon monoxide (SiO) is the most abundant Si-bearing gas in the deep atmospheres of brown dwarfs and EGPs, whereas SiH4 is dominant in the deep atmosphere of Jupiter and other gas giant planets. Several other Fe-, Mg-, and Si-bearing gases become increasingly important with decreasing effective temperature. In principle, a number of Fe, Mg, and Si gases are potential tracers of weather or diagnostic of temperature in substellar atmospheres., Comment: 42 pages, 15 figures, submitted to the Astrophysical Journal

The terrestrial and gas-giant planets in our solar system may represent some prototypes for planets around other stars; the exoplanets because most stars have similar overall elemental abundances as our sun. The solar system planets represent at least four chemical planet types, depending on the phases that make them: Terrestrial-like planets made of rock (metal plus silicates), Plutonian planets made of rock and ice, Neptunian giant planets of rocky, icy with low H and He contents, and Jovian gas-giant planets of rocky, icy planets with near-solar H and He contents. The planetary compositions are linked to the chemical fractionation in the planetary accretion disks. Chemical tracers of these fractionations are described. Many known exoplanets are gas-giant planets with up to several Jupiter-masses and their atmospheric chemistry is compared to that of brown dwarfs. Exoplanets in close orbits around their host stars may resemble hot brown dwarfs (L-dwarfs). Planets receiving less radiation form their host may compare more to the methane-rich T dwarfs. The cloud layers resulting from condensation of oxides, metal, sulfides, and salts in these hot and cool gas giant planets and their chemical tracers are described., Comment: 33 pages, 8 figures, 2 tables, in: Formation and Evolution of Exoplanets, R. Barnes (ed.), Wiley, Berlin, in press

This White Paper to the National Academy of Sciences Astro2010 Decadal Review Committee highlights cross-disciplinary science opportunities over the next decade with cold brown dwarfs, sources defined here as having photospheric temperatures less than ~1000 K., Comment: 8 pages, 3 figures, Astro2010 Science White Paper; v2 has a generally printable font

We examine the spectra and infrared colors of the cool methane-dominated atmospheres at Teff < 1400 K expected for young gas giant planets. We couple these spectral calculations to an updated version of the Marley et al. (2007) giant planet thermal evolution models that include formation by core accretion-gas capture. These relatively cool "young Jupiters" can be 1-6 magnitudes fainter than predicted by standard cooling tracks that include a traditional initial condition, which may provide a diagnostic of formation. If correct, this would make true Jupiter-like planets much more difficult to detect at young ages than previously thought. Since Jupiter and Saturn are of distinctly super-solar composition, we examine emitted spectra for model planets at both solar metallicity and a metallicity of 5 times solar. These metal-enhanced young Jupiters have lower pressure photospheres than field brown dwarfs of the same effective temperatures arising from both lower surface gravities and enhanced atmospheric opacity. We highlight several diagnostics for enhanced metallicity. A stronger CO absorption band at 4.5 $\mu$m for the warmest objects is predicted. At all temperatures, enhanced flux in $K$ band is expected due to reduced collisional induced absorption by H$_2$. This leads to correspondingly redder near infrared colors, which are redder than solar metallicity models with the same surface gravity by up to 0.7 in $J-K$ and 1.5 in $H-K$. Molecular absorption band depths increase as well, most significantly for the coolest objects. We also qualitatively assess the changes to emitted spectra due to nonequilibrium chemistry., Comment: Accepted to ApJ. Most figures in color

We present an analysis of the 0.95-14.5 micron spectral energy distributions of nine field ultracool dwarfs with spectral types ranging from L1 to T4.5. Effective temperatures, gravities, and condensate cloud sedimentation efficiencies are derived by comparing the data to synthetic spectra computed from atmospheric models that self-consistently include the formation of condensate clouds. Derived effective temperatures decrease steadily through the L1 to T4.5 spectral types and we confirm that the effective temperatures of ultracool dwarfs at the L/T transition are nearly constant, decreasing by only ~200 K from spectral types L7.5 to T4.5. The two objects in our sample with very red J-Ks colors are best fitted with synthetic spectra that have thick clouds which hints at a possible correlation between the near-infrared colors of L dwarfs and the condensate cloud properties. The fits to the two T dwarfs in our sample (T2 and T4.5) also suggest that the clouds become thinner in this spectral class, in agreement with previous studies. Restricting the fits to narrower wavelength ranges (i.e., individual photometric bands) almost always yields excellent agreement between the data and models. Limitations in our knowledge of the opacities of key absorbers such as FeH, VO, and CH4 at certain wavelengths remain obvious, however. The effective temperatures obtained by fitting the narrower wavelength ranges can show a large scatter compared to the values derived by fitting the full spectral energy distributions; deviations are typically ~200 K and in the worst cases, up to 700 K., Comment: 44 pages, 24 figures, accepted to ApJ on 2007 Nov 5

The solar argon abundance cannot be directly derived by spectroscopic observations of the solar photosphere. The solar Ar abundance is evaluated from solar wind measurements, nucleosynthetic arguments, observations of B stars, HII regions, planetary nebulae, and noble gas abundances measured in Jupiter's atmosphere. These data lead to a recommended argon abundance of N(Ar) = 91,200(+/-)23,700 (on a scale where Si = 10^6 atoms). The recommended abundance for the solar photosphere (on a scale where log N(H) = 12) is A(Ar)photo = 6.50(+/-)0.10, and taking element settling into account, the solar system (protosolar) abundance is A(Ar)solsys = 6.57(+/-)0.10., Comment: 14 pages, 1 figure, 1 table; submitted to Astrophysical Journal

We highlight the importance of gaseous TiO and VO opacity on the highly irradiated close-in giant planets. The atmospheres of these planets naturally fall into two classes that are somewhat analogous to the M- and L-type dwarfs. Those that are warm enough to have appreciable opacity due to TiO and VO gases we term the ``pM Class'' planets, and those that are cooler we term ``pL Class'' planets. We calculate model atmospheres for these planets, including pressure-temperature profiles, spectra, and characteristic radiative time constants. We show that pM Class planets have hot stratospheres $\sim$2000 K and appear ``anomalously'' bright in the mid infrared secondary eclipse, as was recently found for planets HD 149026b and HD 209458b. This class of planets absorbs incident flux and emits thermal flux from high in their atmospheres. Consequently, they will have large day/night temperature contrasts and negligible phase shifts between orbital phase and thermal emission light curves, because radiative timescales are much shorter than possible dynamical timescales. The pL Class planets absorb incident flux deeper in the atmosphere where atmospheric dynamics will more readily redistribute absorbed energy. This will lead to cooler day sides, warmer night sides, and larger phase shifts in thermal emission light curves. Around a Sun-like primary this boundary occurs at $\sim$0.04-0.05 AU. The eccentric transiting planets HD 147506b and HD 17156b alternate between the classes. Thermal emission in the optical from pM Class planets is significant red-ward of 400 nm, making these planets attractive targets for optical detection. The difference in the observed day/night contrast between ups Andromeda b (pM Class) and HD 189733b (pL Class) is naturally explained in this scenario. (Abridged.), Comment: Accepted to the Astrophysical Journal

Opacities and chemical abundance data are crucial ingredients of ultracool dwarf and extrasolar giant planet atmosphere models. We report here on the detailed sources of molecular opacity data employed by our group for this application. We also present tables of Rosseland and Planck mean opacities which are of use in some studies of the atmospheres, interiors, and evolution of planets and brown dwarfs. For the tables presented here we have included the opacities of important atomic and molecular species, including the alkali elements, pressure induced absorption by hydrogen, and other significant opacity sources but neglect opacity from condensates. We report for each species how we have assembled molecular line data from a combination of public databases, laboratory data that is not yet in the public databases, and our own numerical calculations. We combine these opacities with abundances computed from a chemical equilibrium model using recently revised solar abundances to compute mean opacities. The chemical equilibrium calculation accounts for the settling of condensates in a gravitational field, and is applicable to ultracool dwarf and extrasolar planetary atmospheres, but not circumstellar disks. We find that the inclusion of alkali atomic opacity substantially increases the mean opacities over those currently in the literature at densities relevant to the atmospheres and interiors of giant planets and brown dwarfs. We provide our opacity tables for public use and discuss their limitations., Comment: 32 pages, 6 figures, accepted for publication in Astrphysical Journal Supplement, units revised, now includes on-line only data files (available in "source" package from "other formats" link)

A new formation scenario for TiC and Fe,Ni-metal inclusions in presolar graphite grains of supernova origin is described. The mineralogy and chemistry require condensation of (Fe,Ni)-titanides from Fe, Ni, and Ti-rich gaseous ejecta, subsequent carburization to make TiC and metal, and encapsulation into graphite. Titanides only condense if Si is depleted relative to heavier mass elements, which requires alpha-rich freeze-out and a deep mass-cut for the supernova ejecta. This Si-poor core material must remain unmixed with other supernova zones until the titanides condensed. This can be accomplished by transport of core ejecta in bipolar jets through the major expanding supernova zone ejecta. If the jets stall in regions dominated by C-rich ejecta such as C-He zone where graphite condenses, thermochemically favored in situ carburization of the titanides - either before or during encapsulation into condensing graphite - leads to a TiC and metal composite. This scenario agrees with theoretical models and observations of asymmetric core collapse in supernovae that are associated with bipolar jets loaded with iron-peak elements., Comment: 8 pages, 2 tables, 2 figures; Astrophysical Journal, in press

"Brown dwarfs" is the collective name for objects more massive than giant planets such as Jupiter but less massive than M dwarf stars. This review gives a brief description of the classification and chemistry of low mass dwarfs. The current spectral classification of stars includes L and T dwarfs that encompass the coolest known stars and substellar objects. The relatively low atmospheric temperatures and high total pressures in substellar dwarfs lead to molecular gas and condensate chemistry. The chemistry of elements such as C, N, O, Ti, V, Fe, Cr, and the alkali elements play a dominant role in shaping the optical and infrared spectra of the "failed" stars. Chemical diagnostics for the subclassifications are described., Comment: review article: 30 pages, 3 figures, 2 tables; Astrophysics Update v. 2 (in press)

Thermochemical equilibrium and kinetic calculations are used to model sulfur and phosphorus chemistry in giant planets, brown dwarfs, and extrasolar giant planets (EGPs). The chemical behavior of individual S- and P-bearing gases and condensates is determined as a function of pressure, temperature, and metallicity. The results are independent of particular model atmospheres and, in principle, the equilibrium composition along the pressure-temperature profile of any object can be determined. Hydrogen sulfide (H2S) is the dominant S-bearing gas throughout substellar atmospheres and approximately represents the atmospheric sulfur inventory. Silicon sulfide (SiS) is a potential tracer of weather in substellar atmospheres. Disequilibrium abundances of phosphine (PH3) approximately representative of the total atmospheric phosphorus inventory are expected to be mixed upward into the observable atmospheres of giant planets and T dwarfs. In hotter objects, several P-bearing gases (e.g., P2, PH3, PH2, PH, HCP) become increasingly important at high temperatures., Comment: 38 pages, 8 figures, accepted for Astrophysical Journal

This review provides an introduction to presolar grains - preserved stardust from the interstellar molecular cloud from which our solar system formed - found in primitive meteorites. We describe the search for the presolar components, the currently known presolar mineral populations, and the chemical and isotopic characteristics of the grains and dust-forming stars to identify the grains' most probable stellar sources. Keywords: presolar grains, interstellar dust, asymptotic giant branch (AGB) stars, novae, supernovae, nucleosynthesis, isotopic ratios, meteorites, Comment: 71 pages, 24 figures, 9 tables. Invited review. to appear in Chemie der Erde

Infrared and ultraviolet observations of nova light curves have confirmed grain formation in their expanding shells that are ejected into the interstellar medium by a thermonuclear runaway. In this paper, we present isotopic ratios of intermediate-mass elements up to silicon for the ejecta of CO and ONe novae, based on 20 hydrodynamic models of nova explosions. These theoretical estimates will help to properly identify nova grains in primitive meteorites. In addition, equilibrium condensation calculations are used to predict the types of grains that can be expected in the nova ejecta, providing some hints on the puzzling formation of C-rich dust in O>C environments. These results show that SiC grains can condense in ONe novae, in concert with an inferred (ONe) nova origin for several presolar SiC grains., Comment: 42 pages. Accepted for publication in The Astrophysical Journal

We report on the results of an I-band photometric variability survey of eighteen L dwarfs. We find that seven exhibit statistically significant variations above the 95.4% confidence level with root-mean-square scatter (including photometric errors) between 0.010 and 0.083 mag. Another five targets have variability probabilities ~80%, suggesting that these are likely variable objects. Three of the variable objects display significant peaks in a CLEAN periodogram that are several times higher than the noise. The period for 2MASS 0345+25 is clearly not intrinsic to the object and can be dismissed. The periods found for 2MASS 0746+20AB and 2MASS 1300+19 are unique but longer than those periods likely from rotation velocity measurements and they do not represent periodic behavior in the light curve that persists through the entire data set. These observations suggest that we are not observing the rotation modulation of a long-lived albedo feature. Instead, rapid evolution of atmospheric features is likely causing the non-periodic variability. The remaining variable objects show no prominent features in their light curves, suggesting even more rapid evolution of atmospheric features. We argue against the existence of magnetic spots in these atmospheres and favor the idea that non-uniform condensate coverage is responsible for these variations. The magnetic Reynolds number in the atmosphere of L dwarfs is too small to support the formation of magnetic spots. In contrast, silicate and iron clouds are expected to form in the photospheres of L dwarfs. Inhomogeneities in such cloud decks and the evolution of the inhomogeneities can plausibly produce the observed photometric variations., Comment: 42 pages, 14 figures, minor corrections for typos and Figure 12, to appear in ApJ, v577, September 20, 2002

Clouds of metal-bearing condensates play a critical role in shaping the emergent spectral energy distributions of the coolest classes of low-mass stars and brown dwarfs, L and T dwarfs. Because condensate clouds in planetary atmospheres show distinct horizontal structure, we have explored a model for partly cloudy atmospheres in brown dwarfs. Our model successfully reproduces the colors and magnitudes of both L and T dwarfs for the first time, including the unexpected brightning of the early- and mid-type T dwarfs at J-band, provided that clouds are rapidly removed from the photosphere at T_eff ~ 1200 K. The clearing of cloud layers also explains the surprising persistence and strengthening of gaseous FeH bands in early- and mid-type T dwarfs. The breakup of cloud layers is likely driven by convection in the troposphere, analogous to phenomena observed on Jupiter. Our results demonstrate that planetary-like atmospheric dynamics must be considered when examining the evolution of free-floating brown dwarfs., Comment: 12 pages, 3 figures, accepted to ApJ Letters for June 2002

The recent discovery of photometric variations in L dwarfs has opened a discussion on the cause of the variations. We argue against the existence of magnetic spots in these atmospheres and favor the idea that non-uniform condensate coverage (i.e. clouds) is responsible for the variations. The magnetic Reynolds number (Rm) in the atmosphere of L dwarfs, which describes how well the gas couples with the magnetic field, is too small (<<1) to support the formation of magnetic spots. In constrast silicate and iron clouds form in the photospheres of L dwarfs. Inhomogeneities in such cloud decks can plausibly produce the observed photometric variations. Further evidence in support of clouds is the tendency for variable L dwarfs to be bluer in J-Ks than the average L dwarf of a given spectral type. This color effect is expected if clear holes appear in an otherwise uniform cloud layer., Comment: submitted to ApJL, 13 pages, 2 figures

A curious and unexpected result of the impact of P/Shoemaker Levy 9 with Jupiter was the production of enormous amounts of molecular sulfur (S2). Here we show that S2 is the natural product of disequilibrium chemistry at low pressures in shocked Jovian air, its formation a byproduct of hydrogen recombination. The species observed by the Hubble Space Telescope (HST) - S2, CS2, and H2S - imply that the G fragment penetrated the NH4SH cloud but did not reach the water table. A typical impact within or below the NH4SH clouds produces about 0.03 - 0.1 impactor masses of S2. Because comets are relatively hydrogen-poor, SO2, not S2, is the major product of shocking a water-rich comet, while S2, CS2 and OCS are major products of a dessicated comet. In all cases we find that as the gas cools, S2 converts to the stable low temperature allotrope S8, although other chemical fates not modeled here might intervene first.

New and updated chemical kinetic data, elemental abundances, and thermodynamic data are used for thermochemical equilibrium and, where relevant, thermochemical kinetic calculations of gas abundances and condensate stability in the hot, deep atmospheres of Jupiter and Saturn. Over 2000 compounds of all naturally occurring elements in the periodic table are considered. The calculations range from 298 to 2000 K and are done for adiabatic models of the two planetary atmospheres. The results predict the abundances of many gases which are potentially observable by the Galileo probe to Jupiter, by the Cassini mission to Saturn, and by Earth-based and Earth-orbital telescopes. In addition, the results also predict many new species which are potentially observable by a new generation of entry probes capable of penetrating deeper into the atmospheres of Jupiter and Saturn.

Chemical equilibrium calculations were performed to study the condensation chemistry of the REE and actinides under the highly reducing conditions which are necessary for the formation of the enstatite chondrites. Our calculations confirm that the REE and actinides condensed into oldhamite (CaS), the major REE and actinide host phase in enstatite chondrites, at a carbon-oxygen (C/O) ratio not less than 1 in an otherwise solar gas. Five basic types of REE abundance patterns, several of which are analogous to REE abundance patterns observed in the Ca, Al-rich inclusions in carbonaceous chondrites, are predicted to occur in meteoritic oldhamites. All of the reported REE patterns in oldhamites in enstatite chondrites can be interpreted in terms of our condensation calculations. The observed patterns fall into three of the five predicted categories. The reported Th and U enrichments and ratios in meteoritic oldhamites are also consistent with predictions of the condensation calculations. Pure REE sulfides are predicted to condense in the 10 exp -6 to 10 exp -9 bar range and may be found in enstatite chondrites if they formed in this pressure range.