The Chemistry of Lightning and Life

What chemical effects does lightning have on other planets? How does life affect the atmospheres of other worlds? The ground-breaking experiments of Miller and Urey showed that in some cases, lightning can produce the chemicals necessary for the origin of life. Did lighting succeed in starting off the chemistry that resulted in life on the Early Earth? Does it do so for other planets? These are the questions that a paper by Paul Rimmer & Christiane Helling (2016) wrestle with.

Chemistry leaves a very distinctive footprint on exoplanet atmospheres, thanks to the quantum mechanical precision of spectroscopy. Generally, the spectra of exoplanets can be determined in two ways. The most straightforward way to determine the spectrum of an exoplanet is to look directly at the object, and to observe its emitted light. This can be done only for exoplanets that are bright and far away from their host star, so that the starlight can be blocked out, leaving the planet’s light for astronomers to study. The light from the exoplanet is emitted at characteristic wavelengths, mostly in the infrared. The other way to obtain a spectrum is to look at a transiting planet, a planet that, from our perspective, passes in front of its host star, blocking out the star’s light. At some wavelengths, more light is blocked and the planet looks larger. At other wavelengths, less light is blocked and the planet looks smaller. These wavelengths are determined to exceptional precision by the quantum mechanical properties of the chemical species within the exoplanet’s atmosphere. Physics influences the chemistry, and changing the chemistry changes the light that the exoplanet emits and absorbs. Chemistry gives us a window into the lives of these alien worlds.

Some of the most interesting things in the universe are far outside equilibrium. Equilibrium is a way of describing a system by certain bulk quantities, such as temperature, pressure, volume, and available elements. If you know these properties, you have learnt a lot about the system. You know its chemical composition and its colour. But most of the interesting places in the universe exist outside equilibrium. Take Earth’s atmosphere, for example. It’s comprised of 78% molecular nitrogen, 21% molecular oxygen, and then small amounts of carbon dioxide, methane, hydrogen and water. If the carbon held within the biomass were present in the atmosphere, then our atmosphere would be made up of almost entirely nitrogen and carbon dioxide, with virtually no oxygen or methane. Even if the biomass were not liberated into the atmosphere, all the methane would be destroyed. Methane shouldn’t exist in our atmosphere at all at equilibrium. Life keeps the methane locked out of equilibrium. Additionally, there would be no ozone layer at all. Ozone is produced when molecular oxygen reacts with ultraviolet light from the sun.

Life and light are both written into our planet’s chemistry. And not just our planet’s. Directly imaged planets have chemical features that cannot be explained without invoking strong winds carrying equilibrium mixtures of molecules into places where they are out of equilibrium, and where they are replenished at a rate much faster than they are destroyed. Some hot Jupiters indicate abundances of acetylene and ammonia that are far from equilibrium. The search for life on other worlds has just started, and is focused entirely on the detection of just the kind of non-equilibrium chemistry that indicates the presence of life. There have been a variety of chemical models used to explain this non-equilibrium chemistry, either for Earth and Earth-like planets, or for hot Jupiters or directly imaged exoplanets. The models that work for one object generally cannot be applied to an object with a completely different composition or temperature, and none of these models considers the detailed chemistry of lightning.

Fig. 1. Artistic representation of the types of exoplanets discovered (Credit: Harvard-Smithsonian CfA)

Fig. 1. Artistic representation of the types of exoplanets discovered (Credit: Harvard-Smithsonian CfA)

An object like Jupiter is dominated by hydrogen, with trace amounts of carbon, oxygen and nitrogen, among other elements. Earth, on the other hand, is dominated by nitrogen and oxygen, with trace amounts of carbon in the atmosphere. The exceedingly thin atmosphere of Mars is primarily composed of carbon dioxide and nitrogen. Jupiter, Earth and Mars all would have formed from the same disk of gas and dust, with the gas mostly made of hydrogen. Why do they look so different? Why does Jupiter have so much hydrogen and the Earth and Mars don’t? The most important reason for this is that Mars and Earth are too light to retain hydrogen. They probably did have a hydrogen atmosphere very early in their lifetimes, but lost it long ago. Super-Earths, rocky exoplanets that are more massive than the Earth, have been discovered in abundance, and would have sufficient mass to retain much more hydrogen.

Paul Rimmer and Christiane Helling have developed a comprehensive chemical network called STAND, that incorporates hydrogen, carbon, nitrogen and oxygen chemistry, complete up to glycine, as well as simple chemistries for a variety of other species, including titanium, silicon, sodium, calcium, and potassium. It is robust for a wide range of temperatures and compositions, so that it can be applied to both hot Jupiter planets and directly imaged planets far from their host star, to rocky planets like Mars, Earth, or even to moons like Titan. Additionally, it includes UV and X-ray photochemistry, and chemistry induced by cosmic ray ionization or by interaction with other charged particles. The combination of these tools makes it so STAND can model in detail the chemistry of lightning, to determine both what observational effect it might have on exoplanet atmospheres and to determine whether lighting on different worlds might effectively open up the pathways to prebiotic chemistry.

In combination with ARGO, a photochemistry and diffusion model, STAND has been tested against various planets and exoplanets to find out whether it achieves results consistent with observation and with other models. STAND itself was also tested against laboratory tests similar to those of the Miller experiment, and found the same general trend concerning the hydrogen bonds of carbon and nitrogen, measured in the paper by a quantity called Rr. When they form mostly hydrogen bonds (Rr is small), they produce significant concentrations of glycine; and when carbon and nitrogen are bonded to oxygen or to each other instead of hydrogen (Rr is big), they produce small concentrations of glycine. This is true up until a certain point, when virtually all the nitrogen and carbon share hydrogen bonds, and none are bound to oxygen (when oxygen is bound either to itself as molecular oxygen or is in the form of water). In this case, interestingly, virtually no glycine is formed at all. This result from the paper is shown here in colour (Fig. 2)

Fig. 2. Mixing ratio of glycine as a function of time, for five lab simulations (Rimmer & Helling 2015)

Fig. 2. Mixing ratio of glycine as a function of time, for five lab simulations (Rimmer & Helling 2016)

The STAND network is now being compared to work from leading origin of life research groups, and is also being applied to explain the observed chemical impact of aurorae on brown dwarfs. Rimmer & Helling’s 2015 paper show how important it is to understand the connection between physics and chemistry in exoplanet atmospheres, because often chemistry is the only thing that can be determined very precisely or in much detail. They also provide the community with a new tool to model this chemistry at its most interesting, when it’s far from equilibrium.

For more details check out the original paper on ADS:

 Paul Rimmer & Christiane Helling 2016, ApJS, 224, 9R

The LEAP Group can be found here:

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Cosmic Rays enhance Prebiotic Chemistry on Sunless Worlds

In the International Journal of Astrobiology, Camille Bilger, Christiane Helling and Paul Rimmer (2014) presented a proof-of-concept on the potential effect of cosmic rays in the upper atmospheres of exoplanets (atmospheric pressures between 0.000001 bar and 0.000000001 bar, where 1 bar is the pressure of Earth’s atmosphere at sea level). We model the cosmic ray transport through the atmosphere of a planet with elemental composition and surface gravity similar to (but not the same as) Jupiter, if Jupiter were much farther away from the sun. This model atmosphere was produced using the Drift-Phoenix code (an upcoming post will be available soon on the Drift-Phoenix code).

Cosmic rays are charged particles (electrons, protons, bare nuclei) hurled through our galaxy at relativistic speeds by supernovae. When they strike the upper atmosphere of a planet, found to change its chemistry.

Cosmic Ray air shower

Figure 1. Cosmic Ray air shower

The combination of ultraviolet light from a star and cosmic ray ionization involves a delicate interplay between physics and chemistry, and is a hard problem to solve. It is simpler to consider cosmic ray chemistry on planets without daylight. These planets are often gas giants far from their host star, or rogue planets without a host star at all. These gas giants, like Jupiter, have an atmosphere made up not of mostly oxygen and nitrogen, but of mostly hydrogen, with a significant amount of nacient atomic hydrogen.

This is therefore a reducing atmosphere, and provides an ideal environment for making molecules believed to be important for the origin of life. Cosmic rays would ionize the molecular hydrogen, and this would make the atmosphere even more reducing.

Artistic impression of cosmic rays entering Earth's atmosphere. (Credit: Asimmetrie/Infn via CERN).

Figure 2. Artistic impression of cosmic rays entering Earth’s atmosphere. (Credit: Asimmetrie/Infn via CERN).

A reducing atmosphere is the standard initial chemical environment used in “origin-of-life” experiments, such as the Urey-Miller experiment. In the Urey-Miller experiment, an ionizing source in the form of an electrical discharge is initiated in a molecular gas, and so long as the atmosphere is reducing, prebiotic molecules are formed, including the twenty common amino acids found in living systems. If a reducing atmosphere, such as one dominated by oxygen and nitrogen, is used, the experiment produces no organic compounds.

The ion-neutral reactions made possible by cosmic ray ionization allow more of the hydrogen to be liberated from its molecular form, and increases the rate of reducing reactions. These reactions are found to be responsible for much of the prebiotic chemistry. Specifically, cosmic rays help to make biologically important molecules such as ammonia and acetylene. How much do cosmic rays help? They increase the abundance of some of these species by 10x or 100x in some cases.

Figure 3. Volume fraction of various species as a function of the gas pressure, p [bar] for the model atmosphere of a free-floating giant gas planet. The results assuming chemical quenching of C2H2 and C2H4 at height at ∼10−3 (dashed), and the results with cosmic ray ionization (solid) are all presented in this plot. A thick black horizontal line indicates the pressure above which termolecular (??) reactions may dominate.

Figure 3. Volume fraction of various species as a function of the gas pressure, p [bar] for the model atmosphere of a free-floating giant gas planet. The results assuming chemical quenching of C2H2 and C2H4 at height at ∼10−3 (dashed), and the results with cosmic ray ionization (solid) are all presented in this plot. A thick black horizontal line indicates the pressure above which termolecular reactions may dominate. (Rimmer et al. 2014, Fig. 4.)

The third picture in this article is from our paper, showing how much various molecules are enhanced or reduced because of cosmic rays. Some of the molecules that are enhanced, like ammonia, are key ingredients in the formation of the amino acid Glycine. These ingredients often must overcome a reactive barrier in order to form the amino acid, and overcoming this barrier may be made possible by electrostatic activation of ammonia (see our previous post here).

An image of the HR8799 planetary system from the December 2010 press release.

Figure 4. An image of the HR8799 planetary system from the December 2010 press release. (Credit: NRC-HIA, C. Marois, and Keck Observatory)

Our work may be relevant for directly imaged exoplanets orbiting HR 8799. Since these planets are ten times farther from their host star than Jupiter is from the sun, they are forever shrouded in the dark of night. It will be good to see how a star would change the chemistry, but this is a difficult problem. In order to find out what a star does in the upper atmosphere, it will be necessary to consider how the starlight passes through the atmosphere, and how that will affect thetemperature. The temperature will change the chemistry, and the chemistry will in turn affect how the starlight passes through theatmosphere. Much work still needs to be done to solve the problem for planets closer to their sun.

For more details check out the original paper on arXiv:

P. B. Rimmer, Ch. Helling and C. Bilger 2014, IntJAstrobio, 13, 173

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Electrostatic activation of prebiotic chemistry in substellar atmospheres

How do prebiotic molecules, necessary to the origin of life, form? What energies are needed for the formation of e.g. formaldehyde, ammonia or glycine? Do dust grains of exoplanetary atmospheres have a key role in these processes? These and similar questions were investigated by Dr. Craig Stark and his collaborators.

Dust is present all over the Universe, growing in a variety of diverse environments, for example in the atmospheres of gas giant exoplanets, where mineral dust clouds form, as earlier works of our group have demonstrated. In this atmospheric plasma the dust grains become charged and attract positive ions accelerated from the plasma. “The energy of the ions upon reaching the grain surface may be sufficient to overcome the activation energy of particular chemical reactions that would be unattainable via ion and neutral bombardment from classical, thermal excitation. As a result, prebiotic molecules or their precursors could be synthesized on the surface of dust grains that form clouds in exoplanetary atmospheres.”


Figure 1. Miller-Urey experiment

The famous experiment of Stanley Miller and Harold Urey was one of the first to show how important electricity is in the synthesis of prebiotic molecules. (Fig. 1.) They showed that in a planetary atmosphere composed of H2, CH4, NH3 and H2O it is possible to form prebiotic amino acids and other biological molecules important for life if electrical discharge is present. However nowadays scientists believe that the atmospheric composition used in the above mentioned experiment does not correspond to the one existed on the young Earth, although a recent study showed that during volcano outbursts, where reduced gases and lightning processes are also present, it is possible to produce prebiotic molecules. As our paper says: “For atmospheres more representative of primitive Earth, no significant organic molecules are produced using electrical (sparking) discharges. However, the presence of hydroxy-acids in the famous Murchison meteorite indicate that the so-called Strecker amino-acid synthesizing mechanism (triggered by a Miller-Urey-type electrical discharge) may be responsible for the extraterrestrial synthesis of amino acids.”

Why may dust grains have a significant role in the occurrence of particular chemical reactions? Because in a plasma containing dust particles the absorption of different kind of species is electrostatically driven, which means that energies can easily exceed the activation energy required for the formation of prebiotic molecules.

“Consider a dusty plasma in the atmosphere of a substellar object such as a giant gas exoplanet. The dust particles will be negatively charged and as a result a plasma sheath (an electron depleted region) forms around the particle. As a consequence, the ionic flux at the grain surface increases as the plasma ions are attracted to and are accelerated towards the grain surface. Upon reaching the surface the ions have fallen through an electrostatic potential and have been energized. In comparison to the neutral case, the ionic flux is enhanced and the ionic energy amplified, increasing the probability that chemical reactions will occur and that reactions with higher activation energies are accessible. In this way, charged particle surfaces help catalyze chemical reactions otherwise inaccessible at such low-temperatures present in planetary atmospheres.”

In this paper we investigated the energization of ions as they are accelerated to the surface of a charged dust grain. We were mainly interested in the electrostatic activation of particular chemical reactions in the atmospheres of exoplanets.

Simulations were made using an example substellar atmosphere, which was created by the Drif-Phoenix atmosphere and cloud formation code. The atmosphere was defined by the following parameters: Surface gravity (log(g)) = 3.0; effective temperature (Teff) = 1500 K and solar metalicity ([M/H]=0.0).

Figure 2. was taken from the paper. As it says, the figure “shows the mean grain size  as a function of atmospheric pressure pgas. In the nucleation-dominated upper atmosphere (pgas ≈ 10-11 bar) seed particles form with a mean grain size <a> ≈ 10-7  cm. The dust particles gravitationally settle and grow as they fall, increasing in size. In the lower atmosphere (pgas ≈ 1 bar) the mean particle size is <a> ≈ 10-5 cm.”

Figure 2.  Mean grain particle size  as a function of gas pressure.

Figure 2. Mean grain particle size as a function of gas pressure (Stark et al. 2013)

As the electron temperature increases the local electrostatic field will rise as well which will result in that the ions accelerated by this field gain more energy. The more energy the ions gain the more likely to form molecules with higher activation energies.

We used the formation of glycine (NH2CH2COOH) to give an example “of the electrostatic activation of prebiotic chemistry on the surface of a charged dust grain.” The following chemical sequence shows the individual steps, which lead to the formation of glycine, with the formation energies (an indicator of the activation energy of the chemical reaction)

Screen Shot 2014-01-28 at 14.24.12

Figure 3. Synthesis of glycine

Figure 3. Synthesis of glycine

As our results show, “high in the atmosphere where pgas ≈ 10-15 bar, the ion temperature is ≈ 600 K and the resulting thermal energy of an ion is ≈ 0.08 eV, which is lower than the energies required to form the reaction products above. However when the electron temperature Te = 1 eV the ions are accelerated to Etot ≈ 7.8 eV which surpasses the required formation energies, increasing the likelihood that these reactions will occur. At lower atmospheric pressures where it is hotter, the thermal energy can reach ≈ 0.45 eV (≈ 5200 K) and there will exist a population of higher energy ions that, once neutralized on the surface, may be energetic enough to activate the required chemical reactions to form glycine.”

We showed in our paper that in atmospheric plasma where dust grains become negatively charged, ions can be accelerated to energies high enough to produce chemical reactions which would be inaccessible via classical thermal ion and neutral fluxes. As a consequence the creation of prebiotic molecules on grain surfaces may increase significantly.

The importance of this paper is that it “establishes the feasibility of the electrostatic activation of prebiotic chemistry. This idea can be developed to explicitly model the surface chemical kinetics, describing the incoming accelerated ions interacting with the grain surface. In this way, the effect of the plasma ionic species, the composition of the grain surface and the effect of the grain charge on the resulting surface chemical reactions can be quantified.”

For more details check out the original paper on arXiv:

C. R. Stark, Ch. Helling, D. A. Diver, and P. B. Rimmer 2013, IntJAstrobio 13, 165

Also look at the press release of the paper:,233471,en.php