Tholin

Tholins (after the Greek θολός (tholós) "hazy" or "muddy"; from the ancient Greek word meaning "sepia ink") are a wide variety of organic compounds formed by solar ultraviolet or cosmic ray irradiation of simple carbon-containing compounds such as carbon dioxide (CO2), methane (CH4) or ethane (C2H6), often in combination with nitrogen (N2) or water (H2O). Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups, typically nitriles and hydrocarbons, and their degraded forms such as amines and phenyls. Tholins do not form naturally on modern-day Earth, but they are found in great abundance on the surfaces of icy bodies in the outer Solar System, and as reddish aerosols in the atmospheres of outer Solar System planets and moons. In the presence of water, tholins could be raw materials for prebiotic chemistry (i.e., the non-living chemistry that forms the basic chemicals of which life is made). Their existence has implications for the origins of life on Earth and possibly on other planets. As particles in an atmosphere, tholins scatter light, and can affect habitability. Tholins may be produced in a laboratory, and are usually studied as a heterogeneous mixture of many chemicals with many different structures and properties. Using techniques including thermogravimetric analysis, astrochemists analyze the composition of laboratory-produced tholin mixtures and the exact character of the individual chemicals within them.

Overview

The term "tholin" was coined by astronomer Carl Sagan and his colleague Bishun Khare to describe the difficult-to-characterize substances they obtained in his Miller–Urey-type experiments on the methane-containing gas mixtures such as those found in Titan's atmosphere. Their paper proposing the name "tholin" said:

For the past decade we have been producing in our laboratory a variety of complex organic solids from mixtures of the cosmically abundant gases CH4, C2H6, NH3, H2O, HCHO, and H2S. The product, synthesized by ultraviolet (UV) light or spark discharge, is a brown, sometimes sticky, residue, which has been called, because of its resistance to conventional analytical chemistry, "intractable polymer". [...] We propose, as a model-free descriptive term, 'tholins' (Greek Θολός, muddy; but also Θόλος, vault or dome), although we were tempted by the phrase 'star-tar'. Tholins are not one specific compound but rather are descriptive of a spectrum of molecules, including heteropolymers, that give a reddish, organic surface covering on certain planetary surfaces. Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups. Sagan and Khare note "The properties of tholins will depend on the energy source used and the initial abundances of precursors, but a general physical and chemical similarity among the various tholins is evident." Some researchers in the field prefer a narrowed definition of tholins, for example, S. Hörst wrote: "Personally, I try to use the word 'tholins' only when describing the laboratory-produced samples, in part because we do not really know yet how similar the material we produce in the lab is to the material found on places like Titan or Triton (or Pluto!)." French researchers also use the term tholins only when describing the laboratory-produced samples as analogues. NASA scientists also prefer the word 'tholin' for the products of laboratory simulations, and use the term 'refractory residues' for actual observations on astronomical bodies.

Formation

Artificially The key elements of tholins are carbon, nitrogen, and hydrogen. Laboratory infrared spectroscopy analysis of experimentally synthesized tholins has confirmed earlier identifications of chemical groups present, including primary amines, nitriles, and alkyl portions such as CH2/CH3 forming complex disordered macromolecular solids. Laboratory tests generated complex solids formed from exposure of N2:CH4 gaseous mixtures to electrical discharge in cold plasma conditions, reminiscent of the famous Miller–Urey experiment conducted in 1952.

Naturally As illustrated, tholins are thought to form in nature through a chain of chemical reactions known as pyrolysis and radiolysis. This begins with the dissociation and ionization of molecular nitrogen (N2) and methane (CH4) by energetic particles and solar radiation. This is followed by the formation of ethylene, ethane, acetylene, hydrogen cyanide, and other small simple molecules and small positive ions. Further reactions form benzene and other organic molecules, and their polymerization leads to the formation of an aerosol of heavier molecules, which then condense and precipitate on the planetary surface below. Tholins formed at low pressure tend to contain nitrogen atoms in the interior of their molecules, while tholins formed at high pressure are more likely to have nitrogen atoms located in terminal positions. Tholins may be a major constituent of the interstellar medium. On Titan, their chemistry is initiated at high altitudes and participates in the formation of solid organic particles. These atmospherically derived substances are distinct from ice tholin II, which are formed instead by irradiation (radiolysis) of clathrates of water and organic compounds such as methane (CH4) or ethane (C2H6). The radiation-induced synthesis on ice are independent of temperature. Models show that, even when far from UV radiation of a star, cosmic ray doses may be fully sufficient to convert carbon-containing ice grains entirely to complex organics in less than the lifetime of the typical interstellar cloud.

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