Formation Of Organic Haze Research Articles

Haze Formation in Warm H2-rich Exoplanet Atmospheres

Abstract New observing capabilities coming online over the next few years will provide opportunities for characterization of exoplanet atmospheres. However, clouds/hazes could be present in the atmospheres of many exoplanets, muting the amplitude of spectral features. We use laboratory simulations to explore photochemical haze formation in H2-rich exoplanet atmospheres at 800 K with metallicity either 100 or 1000 times solar. We find that haze particles are produced in both simulated atmospheres with small particle size (20–140 nm) and relatively low production rate (2.4 × 10−5 to 9.7 × 10−5 mg cm−3 hr−1), but the particle size and production rate is dependent on the initial gas mixtures and the energy sources used in the simulation experiments. The gas phase mass spectra show that complex chemical processes happen in these atmospheres and generate new gas products that can further react to form larger molecules and solid haze particles. Two H2-rich atmospheres with similar C/O ratios (∼0.5) yield different haze particle size, haze production rate, and gas products, suggesting that both the elemental abundances and their bonding environments in an atmosphere can significantly affect the photochemistry. There is no methane (CH4) in our initial gas mixtures, although CH4 is often believed to be required to generate organic hazes. However, haze production rates from our experiments with different initial gas mixtures indicate that CH4 is neither required to generate organic hazes nor necessary to promote the organic haze formation. The variety and relative yield of the gas products indicate that CO and N2 enrich chemical reactions in H2-rich atmospheres.

Impact of Hydrogen Sulfide on Photochemical Haze Formation in Methane/Nitrogen Atmospheres

The chemistry of trace sulfur gases in planetary organic haze formation is poorly understood, though both are ubiquitous in planetary atmospheres. Here, we perform laboratory studies to explore how...

The Impact of Molecular Oxygen on Anion Composition in a Hazy Archean Earth Atmosphere.

Atmospheric organic hazes are common in planetary bodies in our solar system and likely exoplanet atmospheres as well. In addition, geochemical data support the existence of an organic haze in the early Earth's atmosphere. Much of what is known about organic haze formation derives from studies of Saturn's moon Titan. It is believed that on Titan ions play an important role in haze formation. It is possible, by using Titan as an analog for the Archean Earth, to consider that an Archean haze could have formed by similar processes. Here, we examine the anion chemistry that occurs during laboratory simulations of early Earth haze formation and measure the composition of gaseous anions as a function of O2 mixing ratio. Gaseous anion composition and relative abundances are measured by an atmospheric pressure interface time-of-flight mass spectrometer and are compared to previous photochemical haze mass loading measurements. Numerous anions are observed spanning from mass-to-charge ratio 26 to 246, with a majority of the identified anions containing carbon, hydrogen, nitrogen, and/or oxygen. A shift in the anion composition occurs with increasing the precursor O2 mixing ratio. With 0-20 ppmv O2 in CH4/CO2/N2 mixtures, ions contain mostly organic nitrogen, with CNO- being the most intense ion peak. As the precursor O2 is increased to 200 and 2000 ppmv, inorganic nitrogen ions become the dominant chemical group, with NO3- having the most intense ion signal. The clear shift in the ionic composition could be indicative of a modification to the gas-phase chemistry that occurs in the transition from an anoxic atmosphere to an oxygen-containing atmosphere, with potential astrobiological significance.

The Influence of Gas-phase Chemistry on Organic Haze Formation

Abstract Although photochemically produced organic hazes are common in planetary atmospheres, there have been few experimental investigations of the gas-phase chemistry leading to organic haze formation. We report a laboratory study of the gas-phase compounds formed by far-ultraviolet irradiation of a CH4/N2 mixture. Using high-resolution chemical ionization mass spectrometry (CIMS) we made in situ measurements of gas-phase products up to m/z 400. Organic nitrogen species dominate the mass spectra with smaller contributions from unsaturated hydrocarbons. Using a structural group method to estimate vapor pressures, we calculate that for compounds detected at m/z > 320, ≥50% of the total compound loading (gas + condensed phase) would be present in the condensed (aerosol) phase at 300 K. Using approximations for changes in vapor pressure with temperature, we estimate that ≥50% of the total loading for species with m/z > 110 would be in the aerosol-phase at 150 K, suggesting that the measured compounds may be important for aerosol composition for a range of temperatures. Finally, we leverage the sensitivity and fast time response of the CIMS measurements to investigate how the gas-phase chemistry evolved over the course of the experiment. This analysis shows that hydrocarbons were the initial products followed by the formation of unsaturated organic nitrogen compounds. Higher molecular weight species and alkylamines appear late in the experiment. Comparison of our measurements to chemical mechanisms used to model planetary haze formation suggests that larger molecular weight compounds need to be considered in haze formation chemistry.

Organic Haze as a Biosignature in Anoxic Earth-like Atmospheres.

Early Earth may have hosted a biologically mediated global organic haze during the Archean eon (3.8–2.5 billion years ago). This haze would have significantly impacted multiple aspects of our planet, including its potential for habitability and its spectral appearance. Here, we model worlds with Archean-like levels of carbon dioxide orbiting the ancient Sun and an M4V dwarf (GJ 876) and show that organic haze formation requires methane fluxes consistent with estimated Earth-like biological production rates. On planets with high fluxes of biogenic organic sulfur gases (CS2, OCS, CH3SH, and CH3SCH3), photochemistry involving these gases can drive haze formation at lower CH4/CO2 ratios than methane photochemistry alone. For a planet orbiting the Sun, at 30× the modern organic sulfur gas flux, haze forms at a CH4/CO2 ratio 20% lower than at 1× the modern organic sulfur flux. For a planet orbiting the M4V star, the impact of organic sulfur gases is more pronounced: at 1× the modern Earth organic sulfur flux, a substantial haze forms at CH4/CO2 ∼ 0.2, but at 30× the organic sulfur flux, the CH4/CO2 ratio needed to form haze decreases by a full order of magnitude. Detection of haze at an anomalously low CH4/CO2 ratio could suggest the influence of these biogenic sulfur gases and therefore imply biological activity on an exoplanet. When these organic sulfur gases are not readily detectable in the spectrum of an Earth-like exoplanet, the thick organic haze they can help produce creates a very strong absorption feature at UV-blue wavelengths detectable in reflected light at a spectral resolution as low as 10. In direct imaging, constraining CH4 and CO2 concentrations will require higher spectral resolution, and R > 170 is needed to accurately resolve the structure of the CO2 feature at 1.57 μm, likely the most accessible CO2 feature on an Archean-like exoplanet. Key Words: Organic haze—Organic sulfur gases—Biosignatures—Archean Earth. Astrobiology 18, 311–329.

Titan's atmosphere and climate

AbstractTitan is the only moon with a substantial atmosphere, the only other thick N2 atmosphere besides Earth's, the site of extraordinarily complex atmospheric chemistry that far surpasses any other solar system atmosphere, and the only other solar system body with stable liquid currently on its surface. The connection between Titan's surface and atmosphere is also unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface‐atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan's atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen‐bearing molecules indicates that Titan's atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. The Cassini‐Huygens mission to the Saturn system has provided a wealth of new information allowing for study of Titan as a complex system. Here I review our current understanding of Titan's atmosphere and climate forged from the powerful combination of Earth‐based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I conclude with some of our remaining unanswered questions as the incredible era of exploration with Cassini‐Huygens comes to an end.

Pale Orange Dots: The Impact of Organic Haze on the Habitability and Detectability of Earthlike Exoplanets

Abstract Hazes are common in known planetary atmospheres, and geochemical evidence suggests that early Earth occasionally supported an organic haze with significant environmental and spectral consequences. The UV spectrum of the parent star drives organic haze formation through methane photochemistry. We use a 1D photochemical-climate model to examine production of fractal organic haze on Archean Earth-analogs in the habitable zones of several stellar types: the modern and early Sun, AD Leo (M3.5V), GJ 876 (M4V), ϵ Eridani (K2V), and σ Boötis (F2V). For Archean-like atmospheres, planets orbiting stars with the highest UV fluxes do not form haze because of the formation of photochemical oxygen radicals that destroy haze precursors. Organic hazes impact planetary habitability via UV shielding and surface cooling, but this cooling is minimized around M dwarfs, whose energy is emitted at wavelengths where organic hazes are relatively transparent. We generate spectra to test the detectability of haze. For 10 transits of a planet orbiting GJ 876 observed by the James Webb Space Telescope, haze makes gaseous absorption features at wavelengths < 2.5 μm 2–10σ shallower than a haze-free planet, and methane and carbon dioxide are detectable at >5σ. A haze absorption feature can be detected at 5σ near 6.3 μm, but a higher signal-to-noise ratio is needed to distinguish haze from adjacent absorbers. For direct imaging of a planet at 10 pc using a coronagraphic 10 m class ultraviolet–visible–near-infrared telescope, a UV–blue haze absorption feature would be strongly detectable at >12σ in 200 hr.

3D modeling of organic haze in Pluto’s atmosphere

The New Horizons spacecraft, which flew by Pluto on July 14, 2015, revealed the presence of haze in Pluto’s atmosphere that were formed by CH4/N2 photochemistry at high altitudes in Pluto’s atmosphere, as on Titan and Triton. In order to help the analysis of the observations and further investigate the formation of organic haze and its evolution at global scales, we have implemented a simple parameterization of the formation of organic haze in our Pluto General Circulation Model. The production of haze in our model is based on the different steps of aerosol formation as understood on Titan and Triton: photolysis of CH4 in the upper atmosphere by Lyman-α UV radiation, production of various gaseous species, and conversion into solid particles through accumulation and aggregation processes. The simulations use properties of aerosols similar to those observed in the detached haze layer on Titan. We compared two reference simulations ran with a particle radius of 50 nm: with, and without South Pole N2 condensation. We discuss the impact of the particle radius and the lifetime of the precursors on the haze distribution. We simulate CH4 photolysis and the haze formation up to 600 km above the surface. Results show that CH4 photolysis in Pluto’s atmosphere in 2015 occurred mostly in the sunlit summer hemisphere with a peak at an altitude of 250 km, though the interplanetary source of Lyman-α flux can induce some photolysis even in the Winter hemisphere. We obtained an extensive haze up to altitudes comparable with the observations, and with non-negligible densities up to 500 km altitude. In both reference simulations, the haze density is not strongly impacted by the meridional circulation. With No South Pole N2 condensation, the maximum nadir opacity and haze extent is obtained at the North Pole. With South Pole N2 condensation, the descending parcel of air above the South Pole leads to a latitudinally more homogeneous haze density with a slight density peak at the South Pole. The visible opacities obtained from the computed mass of haze, which is about 2–4×10−7 g cm−2 in the summer hemisphere, are similar for most of the simulation cases and in the range of 0.001-0.01, which is consistent with recent observations of Pluto and their interpretation.

Coupled noble gas–hydrocarbon evolution of the early Earth atmosphere upon solar UV irradiation

Using a new photochemical model of the Earthʼs early atmosphere, the relationship between noble gas photoionization and organic photochemistry has been investigated from the Archean eon to the present day. We have found that the enhanced UV emission of the young Sun triggered a peculiar atmospheric chemistry in a CH4-rich early atmosphere that resulted in the increased formation of an organic haze, similar to the preliminary results of a previous study (Ribas et al., 2010). We have investigated the interaction between this haze and noble gases photoionized by the UV light from the younger Sun. Laboratory experiments have shown indeed that ionized xenon trapping into organics (1) is more efficient that other ionized noble gases trapping and (2) results in a significant enrichment of heavy xenon isotopes relative to the light ones (e.g., Frick et al., 1979; Marrocchi et al., 2011). We find moreover preferential photoionization of xenon that peaks at an altitude range comparable to that of the organic haze formation, in contrast to other noble gases. Trapping and fractioning of ionized xenon in the organic haze could therefore have been far more efficient than for other noble gases, and could have been particularly effective throughout the Archean eon, since the UV irradiation flux from the young Sun was expected to be substantially higher than today (Ribas et al., 2010; Claire et al., 2012). Thus we suspect that the unique isotopic fractionation of atmospheric xenon and its elemental depletion in the atmosphere relative to other noble gases, compared to potential cosmochemical components, could have resulted from a preferential incorporation of the heaviest xenon isotopes into organics. A fraction of atmospheric xenon could have been continuously trapped in the forming haze and enriched in its heavy isotopes, while another fraction would have escaped from the atmosphere to space, with, or without isotope selection of the lightest isotopes. The combination of these two processes over long periods of time provides thereby a key process for explaining the evolution of its isotopic composition in the atmosphere over time that has been observed in Archean archives (Pujol et al., 2011).

THE ATMOSPHERIC CHEMISTRY OF GJ 1214b: PHOTOCHEMISTRY AND CLOUDS

Recent observations of the transiting super-Earth GJ 1214b reveal that its atmosphere may be hydrogen-rich or water-rich in nature, with clouds or hazes potentially affecting its transmission spectrum in the optical and very-near-IR. Here we further examine the possibility that GJ 1214b does indeed possess a hydrogen-dominated atmosphere, which is the hypothesis that is favored by models of the bulk composition of the planet. We study the effects of non-equilibrium chemistry (photochemistry, thermal chemistry, and mixing) on the planet's transmission spectrum. We furthermore examine the possibility that clouds could play a significant role in attenuating GJ 1214b's transmission spectrum at short wavelengths. We find that non-equilibrium chemistry can have a large effect on the overall chemical composition of GJ 1214b's atmosphere, however these changes mostly take place above the height in the atmosphere that is probed by transmission spectroscopy. The effects of non-equilibrium chemistry on GJ 1214b's transmission spectrum are therefore minimal, with the largest effects taking place if the planet's atmosphere has super-solar metallicity and a low rate of vertical mixing. Interestingly, we find that the best fit to the observations of GJ 1214b's atmosphere in transmission occur if the planet's atmosphere is deficient in CH4, and possesses a cloud layer at a pressure of ~200 mbar. This is consistent with a picture of efficient methane photolysis, accompanied by formation of organic haze that obscures the lower atmosphere of GJ 1214b at optical wavelengths. However, for methane to be absent from GJ 1214b's transmission spectrum, UV photolysis of this molecule must be efficient at pressures of greater than ~1 mbar, whereas we find that methane only photolyzes to pressures less than 0.1 mbar, even under the most optimistic assumptions. (Abridged)

Geologic evidence for Archean atmospheric and climatic evolution: Fluctuating levels of CO2, CH4, and O2 with an overriding tectonic control

The 3.5-3.2 Ga sedimentary record shows evidence of surface temperatures of 70 ′ 15 °C, nahcolite (NaHCO 3 ) as a primary evaporitic mineral, and an aggressive weathering regime even in the absence of land vegetation. These features are best explained by a mixed CH 4 and CO 2 atmospheric greenhouse in which CH 4 /CO 2 ratios were «1 and pCO 2 was at least 100-1000 times the present value and perhaps as high as several bars. The formation of large areas of continental crust at 3.2-3.0 Ga, including the Kaapvaal and Pilbara cratons, resulted in the gradual depletion of atmospheric CO 2 through weathering. By 2.9-2.7 Ga, declining pCO 2 was associated with climatic cooling and siderite-free soils. Transitory CH 4 /CO 2 ratios of ∼1 may have resulted in the sporadic formation of organic haze from atmospheric CH 4 , reflected in one or more isotopic excursions involving global deposition of abnormally 1 3 C-depleted organic C. Surface temperatures of <60 °C after 2.9 Ga may have also increased the distribution and productivity of oxygenic photosynthetic microbes. Eventual lowering of new continental blocks by erosion, reduced loss of atmospheric CO 2 due to weathering, and continued long-term tectonic recycling of CO 2 resulted in rising pCO 2 and decreasing CH 4 /CO 2 ratios in the later Archean and eventual reestablishment of a mainly CO 2 greenhouse. Similar events may have been repeated in the latest Archean and earliest Proterozoic, but gradually rising production of O 2 effectively kept CH 4 /CO 2 ratios to «1 at this time.