Earth's Early Reduced Atmospheres

Earths early atmosphere evolved in response to cosmic impacts, photochemistry generated by the copious extreme ultraviolet radiation emitted by the young Sun, hydrogen escape, mineral redox buffering, the evolution of iron in the mantle, and the character of crustal weathering and subduction. No single chemical composition, surface pressure, or temperature was typical. After the biggest impacts the temperature likely rose above 3000 K and the atmosphere held rock vapor. As the atmosphere cooled its constituents rained out: first the silicates, then the geochemical volatiles (such as salt), and last the water. Depending on the size of the impact, cooling took thousands to millions of years. Between impacts the atmosphere was thick with gases like CO2, H2, and CH4 that do not condense at Earth but provide greenhouse warming that could easily have maintained surface temperatures in excess of 500 K. At some point the early atmosphere must have been conducive to the evolution of organic chemistry and the origin of life. It was therefore --- at times --- dominated by reduced gases like hydrogen and methane. Hydrogen-methane atmospheres are easily formed thermochemically after major impacts if H2O and CO2 were present on Earth in quantities consistent with their inventories on Earth today the key is high pressure. Hydrogen-methane atmospheres slowly break down over millions of years by hydrogen escape and photochemistry. At first methane decomposes into tars and nitriles that precipitate, but later as the atmosphere grows more oxidized from hydrogen escape the methane oxidizes to CO and CO2, with a small fraction going to HCN. Impacts can also produce NH3 directly from N2 and H2O, which is expected to rain out with the H2O. As impacts grew infrequent the climate cooled in response to the fixing of CO2 as carbonate and carbonate subduction. Eventually the CO2 was mostly removed to the mantle and the surface mostly frozen

Methane, Carbon Monoxide, and Ammonia in Brown Dwarfs and Self-Luminous Giant Planets

We address disequilibrum abundances of some simple molecules in the atmospheres of solar composition brown dwarfs and self-luminous extrasolar giant planets using a kinetics-based 1D atmospheric chemistry model. Our approach is to use the full kinetics model to survey the parameter space with effective temperatures between 500 K and 1100 K. In all of these worlds equilibrium chemistry favors CH4 over CO in the parts of the atmosphere that can be seen from Earth, but in most disequilibrium favors CO. The small surface gravity of a planet strongly discriminates against CH4 when compared to an otherwise comparable brown dwarf. If vertical mixing is like Jupiter's, the transition from methane to CO occurs at 500 K in a planet. Sluggish vertical mixing can raise this to 600 K; but clouds or more vigorous vertical mixing could lower this to 400 K. The comparable thresholds in brown dwarfs are $1100\pm100$ K. Ammonia is also sensitive to gravity, but unlike CH4/CO, the NH3/N2 ratio is insensitive to mixing, which makes NH3 a potential proxy for gravity. HCN may become interesting in high gravity brown dwarfs with very strong vertical mixing. Detailed analysis of the CO-CH4 reaction network reveals that the bottleneck to CO hydrogenation goes through methanol, in partial agreement with previous work. Simple, easy to use quenching relations are derived by fitting to the complete chemistry of the full ensemble of models. These relations are valid for determining CO, CH4, NH3, HCN, and CO2 abundances in the range of self-luminous worlds we have studied but may not apply if atmospheres are strongly heated at high altitudes by processes not considered here (e.g., wave breaking).Comment: Astrophysical Journal, in press. Clarity improvements throughout and one new figure. 17 figures, 20 page

Environmental Consequences of Big Nasty Impacts on the Early Earth

The geological record of the Archean Earth is spattered with impact spherules from a dozen or so major cosmic collisions involving Earth and asteroids or comets (Lowe, Byerly 1986, 2015). Extrapolation of the documented deposits suggests that most of these impacts were as big or bigger than the Chicxulub event that famously ended the reign of the thunder lizards. As the Archean impacts were greater, the environmental effects were also greater. The number and magnitude of the impacts is bounded by the lunar record. There are no lunar craters bigger than Chicxulub that date to Earth's mid-to-late Archean. Chance dictates that Earth experienced no more than approximately 10 impacts bigger than Chicxulub between 2.5 billion years and 3.5 2.5 billion years, the biggest of which were approximately30-100 times more energetic, comparable to the Orientale impact on the Moon (1x10 (sup 26) joules). To quantify the thermal consequences of big impacts on old Earth, we model the global flow of energy from the impact into the environment. The model presumes that a significant fraction of the impact energy goes into ejecta that interact with the atmosphere. Much of this energy is initially in rock vapor, melt, and high speed particles. (i) The upper atmosphere is heated by ejecta as they reenter the atmosphere. The mix of hot air, rock vapor, and hot silicates cools by thermal radiation. Rock raindrops fall out as the upper atmosphere cools. (ii) The energy balance of the lower atmosphere is set by radiative exchange with the upper atmosphere and with the surface, and by evaporation of seawater. Susequent cooling is governed by condensation of water vapor. (iii) The oceans are heated by thermal radiation and rock rain and cooled by evaporation. Surface waters become hot and salty; if a deep ocean remains it is relatively cool. Subsequently water vapor condenses to replenish the oceans with hot fresh water (how fresh depending on continental weathering, which might be rather rapid under the circumstances). (iv) The surface temperature of dry land is presumed to be the same as the lower atmosphere. A thermal wave propagates into the land at a rate set by conduction. Impacts not greatly larger than Chicxulub can raise the surface temperature by tens, hundreds, or even thousands of degrees, and evaporate meters to hundreds of meters of water. The biggest should have vitrified exposed dry land. More results are for the talk, as here we have run out of space

Limits to Creation of Oxygen-Rich Atmospheres on Planets in the Outer Reaches of the Conventional Habitable Zone

Abundant free oxygen appears to be a requirement for macroflora and macrofauna. To the best of our knowledge, a general discussion of which habitable planets are conducive to oxygen has not taken place. Theories for the rise of oxygen fall into 4 categories: (i) It is governed by an intrinsic rate of biological innovation, independent of environmental factors. (ii) It is caused by mantle evolution, probably consequent to secular cooling. (iii) It is caused by hydrogen escape, which irreversibly oxidizes the Earth. (iv) It is Gaia's response to the brightening Sun, its rise prevented until reduced greenhouse gases were no longer needed to maintain a clement climate. All but the first of these make implicit astronomical predictions that can be quantified and made explicit. Here we address the third hypothesis. In this hypothesis hydrogen escape acts like an hourglass that continues until all relevant reduced mineral buffers have been oxidized (titrated, as it were) and the surface made safe for O2. The hypothesis predicts that abundant free O2 will be absent from habitable planets that have not experienced significant hydrogen escape. Where hydrogen escape is modest or insignificant, the atmosphere can be approximated as hydrostatic, which makes assessing radiative cooling by embedded molecules, atoms, and ions such as CO2 and H3+ straightforward. In particular, H2 is efficient at exciting non-LTE CO2 15 micron emission, which makes radiative cooling very effective when H2 is abundant. We can therefore map out the region of phase space in which habitable planets do not lose hydrogen, and therefore do not develop O2 atmospheres. A related matter is the power of radiative cooling by embedded molecules to enforce the diffusion limit to hydrogen escape. This matter in particular is relevant to addressing the empirical observation that rocky planets with thin or negligible atmospheres are rarely or never bigger than approx.1.6 Earth radii

Impact-Induced Climate Change on Titan

Titan's thick atmosphere and volatile surface cause it to respond to big impacts like the one that produced the prominent Menrva impact basin in a somewhat Earth-like manner. Menrva was big enough to raise the surface temperature by 100 K. If methane in the regolith is generally as abundant as it was at the Huygens landing site, Menrva would have been big enough to double the amount of methane in the atmosphere. The extra methane would have drizzled out of the atmosphere over hundreds of years. Conditions may have been favorable for clathrating volatiles such as ethane. Impacts can also create local crater lakes set in warm ice but these quickly sink below the warm ice; whether the cryptic waters quickly freeze by mixing with the ice crust or whether they long endure under the ice remains a open question. Bigger impacts can create shallow liquid water oceans at the surface. If Titan's crust is made of water ice, the putative Hotei impact (a possible 800-1200 km diameter basin, Soderblom et al 2009) would have raised the average surface temperature to 350-400 K. Water rain would have fallen and global meltwaters would have averaged 50 m to as much as 500 m deep. The meltwaters may not have lasted more than a few decades or centuries at most, but are interesting to consider given Titan's organic wealth

The Atmospheres of Directly Imaged Planets: Where Has All the Methane Gone?

Methane and ammonia both first appear at lower effective temperatures in brown dwarf atmospheres than equilibrium chemistry models would suggest. This has traditionally been understood as a consequence of vertical mixing timescales being shorter than chemical equilibration timescales in brown dwarf photospheres. Indeed the eddy diffusivity, a variable accounting for the vigor of vertical mixing, has become a standard part of the description of brown dwarf atmosphere models, along with Teff and log g. While some models have suggested that methane is less favored at lower gravity, the almost complete absence of methane in the atmospheres of directly imaged planets, such as those orbiting HR 8799, even at effective temperatures where methane is readily apparent in brown dwarf spectra, has been puzzling. To better understand the paucity of methane in low gravity atmospheres we have revisited the problem of methane chemistry and mixing. We employed a 1-D atmospheric chemistry code augmented with an updated and complete network of the chemical reactions that link CO to CH4. We find the methane abundance at altitudes at or above the effective photosphere is a strong function of surface gravity because higher g shifts the p-T structure to higher pressures (i.e., a given optical depth is proportional to p/g, a relation mitigated somewhat by pressure broadening). Thus quenching in more massive brown dwarfs occurs at a lower temperature and higher pressure, both favoring CH4. We predict that in the lowest mass young giant planets, methane will appear very late, at effective temperatures as low as 600 K rather than the 1200 K seen among field brown dwarfs. This methane deficiency has important implications for the interpretation of spectra as well as methane-based planetary companion searches, such as the NICI survey. The GPI and SPHERE surveys will test these ideas and probe atmospheric chemistry and composition in an entire new range of parameter space. A caveat is that these calculations presume that the C to O ratio is comfortably less than one; the behavior is quite different if C and O are equally abundant, and of course CH4 is always present if C exceeds O

Photolytic Hazes in the Atmosphere of 51 Eri b

We use a 1D model to address photochemistry and possible haze formation in the irradiated warm Jupiter, 51 Eridani b. The intended focus was to be carbon, but sulfur photochemistry turns out to be important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If organic hazes form, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the altitudes where methane and water are photolyzed. The more novel result is that photochemistry turns H$_2$S into elemental sulfur, here treated as S$_8$. In the cooler models, S$_8$ is predicted to condense in optically thick clouds of solid sulfur particles, whilst in the warmer models S$_8$ remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we have discussed is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650-750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.Comment: 24 pages including 11 figures and a tabl