Titan Tholin Research Articles

Analysis of the Time-Dependent Chemical Evolution of Titan Haze Tholin

Haze particles exert a significant influence over the thermodynamics and radiation absorption properties of the Titan haze, as well as its complex organic chemistry. Characterization of both the molecular and the submicrometer components of the haze is therefore vital for understanding the global properties of Titan. We have carried out a Titan tholin synthesis experiment and measured the time variation of the infrared spectrum of the product as a thin film developed. Also, to examine the possibility of oxygen contamination, we compared the infrared spectrum of the tholin film with that of a tholin film exposed to dry air and laboratory air. The objective of this study is to understand the chemical processes related to how simple organic molecules are processed into more complex haze particles. The progressive development of features characteristic of amines, aromatic and aliphatic hydrocarbons, and nitriles in the experimental mixture is clear. Of particular interest is the formation of aromatic rings after only a few seconds of glow discharge, indicating that these compounds appear to be intermediates between simple haze molecules and microphysical aerosols. The early dominance of aromatic ring structures is accompanied during the later stages of the experiment by the appearance of nitrile and amine compounds. This time-dependent succession of chemical structures provides vital clues to the possible chemical formation pathways of Titan haze aerosols.

Solid organic matter in the atmosphere and on the surface of outer Solar System bodies.

Many bodies in the outer Solar System display the presence of low albedo materials. These materials, evident on the surface of asteroids, comets, Kuiper Belt objects and their intermediate evolutionary step, Centaurs, are related to macromolecular carbon bearing materials such as polycyclic aromatic hydrocarbons and organic materials such as methanol and related light hydrocarbons, embedded in a dark, refractory, photoprocessed matrix. Many planetary rings and satellites around the outer gaseous planets display such component materials. One example, Saturn's largest satellite, Titan, whose atmosphere is comprised of around 90% molecular nitrogen N2 and less than 10% methane CH4, displays this kind of low reflectivity material in its atmospheric haze. These materials were first recorded during the Voyager 1 and 2 flybys of Titan and showed up as an optically thick pinkish orange haze layer. These materials are broadly classified into a chemical group whose laboratory analogs are termed "tholins", after the Greek word for "muddy". Their analogs are produced in the laboratory via the irradiation of gas mixtures and ice mixtures by radiation simulating Solar ultraviolet (UV) photons or keV charged particles simulating particles trapped in Saturn's magnetosphere. Fair analogs of Titan tholin are produced by bombarding a 9:1 mixture of N2:CH4 with charged particles and its match to observations of both the spectrum and scattering properties of the Titan haze is very good over a wide range of wavelengths. In this paper, we describe the historical background of laboratory research on this kind of organic matter and how our laboratory investigations of Titan tholin compare. We comment on the probable existence of polycyclic aromatic hydrocarbons in the Titan Haze and how biological and nonbiological racemic amino acids produced from the acid hydrolysis of Titan tholins make these complex organic compounds prime candidates in the evolution of terrestrial life and extraterrestrial life in our own Solar System and beyond. Finally, we also compare the spectrum and scattering properties of our resulting tholin mixtures with those observed on Centaur 5145 Pholus and the dark hemisphere of Saturn's satellite Iapetus in order to demonstrate the widespread distribution of similar organics throughout the Solar System.

Nature and Source of Organic Matter in the Shoemaker–Levy 9 Jovian Impact Blemishes

The 0.3–1.0 μm optical constants of the aerosols in the dark SL-9 Jupiter impact blemishes are nearly identical to those of the organic residue in the Murchison carbonaceous chondrite. Porous poly-HCN is also a reasonable match. The mass of organics needed to produce a typical blemish is 0.8–8 × 1013g, depending on the aerosol porosity. The 10 μm emission feature seen during the splash-back phase for the impact of fragment R, however, requires ∼1–5 × 1012g of astronomical silicate. The organics from the blemishes cannot be present at this point, or else its greater abundance would dominate the thermal flux, hiding or greatly modifying the 10 μm silicate feature. Furthermore, this mass of silicates, but not the mass of organics in the blemishes, is consistent with the HST reflectances of the impact plumes if the aerosols have radii ∼0.1 μm.In addition to the blemishes, a large expanding ring was observed for the G and K impacts between 3 and 4 μm but was not detected outside that range. Titan tholin has a strong absorption edge near 3 μm which decays by a factor of 8 by 4 μm. Poly-HCN and Murchison organic residue have similar but less extreme behavior. If the radiation from the ring is thermal emission instead of reflected sunlight, this feature is best explained by a very thin cloud of hot Titan tholin-like aerosols at the few microbar level. The rings require ∼1010g of material.The mass of organics required to produce the blemishes is comparable to the organic abundance expected in the ∼1014-g fragments, assuming cometary composition. However, the high temperature of the fireball would likely destroy most, if not all, of the organic matter contained within the fragments. Because of the low abundance of HCN seen at the impact sites, shock synthesis of organics from the jovian atmosphere is an improbable production mechanism. Quench synthesis of organics from cometary dissociation products, though, may satisfy the large mass requirements. The expanding ring requires a low enough mass of tholin that the latter is reasonably the result of shock synthesis, possibly during the splash-back phase.

Spectrophotometry and organic matter on Iapetus. 1. Composition models.

Iapetus shows a greater hemispheric albedo asymmetry than any other body in the solar system. Hapke scattering theory and optical constants measured in the laboratory are used to identify possible compositions for the dark material on the leading hemisphere of Iapetus. The materials considered are poly-HCN, kerogen, Murchison organic residue, Titan tholin, ice tholin, and water ice. Three-component mixtures of these materials are modeled in intraparticle, particle, and areal mixtures. In a computer grid search of approximately 2 x 10(7) models, an intraparticle mixture of 25% poly-HCN, 10% Murchison residue, and 65% water ice is found to best fit the spectrum, albedo, and phase behavior of the dark material. The Murchison residue and/or water ice can be replaced by kerogen and ice tholin, respectively, and still produce very good fits. Areal and particle mixtures of poly-HCN, Titan tholin, and either ice tholin or Murchison residue are also possible models. Poly-HCN is a necessary component in almost all good models. The presence of poly-HCN can be further tested by high-resolution observations near 4.5 micrometers.

The Titan Haze Revisited: Magnetospheric Energy Sources and Quantitative Tholin Yields

We present laboratory measurements of the radiation yields of complex organic solids produced from N 2/CH 4 gas mixtures containing 10 or 0.1% CH 4. These tholins are thought to resemble organic aerosols produced in the atmospheres of Titan, Pluto, and Triton. The tholin yields are large compared to the total yield of gaseous products: nominally, 13 (C + N)/100 eV for Titan tholin and 2.1 (C + N)/100 eV for Triton tholin. High-energy magnetospheric electrons responsible for tholin production represent a class distinct from the plasma electrons considered in models of Titan's airglow. Electrons with E > 20 keV provide an energy flux ∼1 × 10 -2 erg cm -2 sec -1, implying from our measured tholin yields a mass flux of 0.5 to 4.0 × 10 -14 g cm -2 sec -1 of tholin. (The corresponding thickness of the tholin sedimentary column accumulated over 4 Gyr on Titan's surface is 4 to 30 m.) This figure is in agreement with required mass fluxes computed from recent radiative transfer and sedimentation models. If, however, these results, derived from experiments at ∼2 mb, are applied to lower pressure levels toward peak auroral electron energy deposition and scaled with pressure as the gas-phase organic yields, the derived tholin mass flux is at least an order of magnitude less. We attribute this difference to the fact that tholin synthesis occurs well below the level of maximum electron energy deposition and to possible contributions to tholins from UV-derived C 2-hydrocarbons. We conclude that Titan tholin, produced by magnetospheric electrons, is alone sufficient to supply at least a significant fraction of Titan's haze—a result consistent with the fact that the optical properties of Titan tholin, among all proposed materials, are best at reproducing Titan's geometric albedo spectrum from near UV to mid-IR in light-scattering models.

Chemical Investigation of Titan and Triton Tholins

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N 2/CH 4 gas mixtures, respectively. The lower CH 4 mixing ratio leads to a nitrogen-richer tholin (N/C > 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H 2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H 2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H 2O-soluble fractions of both tholins are mainly molecules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H 2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

The Organic Surface of 5145 Pholus: Constraints Set by Scattering Theory

No known body in the Solar System has a spectrum redder than that of object 5145 Pholus. We use Hapke scattering theory and optical constants measured in this laboratory to examine the ability of mixtures of a number of organic solids and ices to reproduce the observed spectrum and phase variation. The primary materials considered are poly-HCN, kerogen, Murchison organic extract, Titan tholin, ice tholin, and water ice. In a computer grid search of over 10 million models, we find an intraparticle mixture of 15% Titan tholin, 10% poly-HCN, and 75% water ice with 10-μm particles to provide an excellent fit. Replacing water ice with ammonia ice improves the fits significantly while using a pure hydrocarbon tholin, Tholin α, instead of Titan tholin makes only modest improvements. All acceptable fits require Titan tholin or some comparable material to provide the steep slope in the visible, and poly-HCN or some comparable material to provide strong absorption in the near-infrared. A pure Titan tholin surface with 16-μm particles, as well as all acceptable Pholus models, fit the present spectrophotometric data for the transplutonian object 1992 QB 1. The feasibility of gas-phase chemistry to generate material like Titan tholin on such small objects is examined. An irradiated transient atmosphere arising from sublimating ices may generate at most a few centimeters of tholin over the lifetime of the Solar System, but this is insignificant compared to the expected lag deposit of primordial contaminants left behind by the sublimating ice. Irradiation of subsurface N 2/CH 4 ice by cosmic rays may generate ∼20 cm of tholin in the upper 10 m of regolith in the some time scale but the identity of this tholin to its gasphase equivalent has not been demonstrated.

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter.

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.

Amino acids derived from Titan Tholins

An organic heteropolymer(Titan tholin) was produced by continuous dc discharge through a 0.9 N 2/0.1 CH 4 gas mixture at 0.2 mbar pressure, roughly simulating the cloudtop atmosphere of Titan. Treatment of this tholin with 6 N HCI yielded 16 amino acids by gas chromatography after derivazation to N-trifluroacetyl isopropyl esters on two different capillary columns. Identifications were confirmed by GC/MS. Glycine, aspartic acid, and α- and β-alanine were produced in greatest abundance; the total yield of amino acids was ∼ 10 −2, approximately equal to the yield of urea. The presence of “nonbiological” amino acids, the absence of serine, and the fact that the amino acids are racemic within experimental error together indicate that these molecules are not due to microbial or other contamination, but are derived from the tholin. In addition to the HCN, HC 2CN, and (CN) 2 found by Voyager, nitriles and aminonitriles should be sought in the Titanian atmosphere and, eventually, amino acids on the surface. These results suggest that episodes of liquid water in the past or future of Titan might lead to major further steps in prebiological organic chemistry on that body.

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N 2/0.1 CH 4 gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n ( ⋍1.65) and k ( ⋍0.004 to 0.08 ) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k(λ), including the 4.6 μm nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.