Given the role of HCN as a reactant in RNA building block production (e.g. nucleobases, ribose, and 2-aminooxazole), we propose that an atmosphere rich in hydrogen cyanide (HCN) is a distinguishing feature of what we term biogenic worlds. These are worlds that can produce key biomolecules for the emergence of life in situ rather than requiring they be delivered, e.g., by meteorites. To attack the question of whether early Earth was biogenic, we develop a series of new capabilities including the calculation of missing/unknown HCN reaction rate coefficients, the simulation of HCN chemistry in planetary atmospheres, and the coupling of atmospheric HCN chemistry and rain-out to the production and evolution of RNA building blocks in warm little ponds (WLPs). We make a major leap in understanding the origin of RNA on a biogenic early Earth by building a comprehensive model that couples terrestrial geochemistry, radiative transfer, atmospheric photochemistry, lightning chemistry, and aqueous pond chemistry.
We begin by developing an accurate and feasible method to calculate missing reaction rate coefficients related to HCN chemistry in planetary atmospheres. We use density functional theory simulations to solve the transition states for various reactions, and use the simulated energies and partition functions to calculate the corresponding rate coefficients using the principles of statistical mechanics. We initially explore and calculate rate coefficients for a total of 110 reactions present in reducing atmospheres dominated by N2, CH4, and H2, including 48 reactions that were previously unknown in the literature. Our rate coefficients are most commonly within a factor of two of experimental values, and generally always within an order of magnitude of these values. This accuracy is consistent with the typical uncertainties assigned in large-scale kinetic data evaluations.
Next, we develop a consistent reduced atmospheric hybrid chemical network (CRAHCN) containing experimental values when available (32%) and our calculated rate coefficients otherwise (68%). To validate our chemistry, we couple CRAHCN to a 1D disequilibrium chemical kinetic model (ChemKM) to compute HCN production in the reducing atmosphere of Saturn's moon Titan. Our calculated atmospheric HCN profile agrees very well with the measurements performed by instruments aboard the Cassini spacecraft, suggesting our chemical network is accurate for modeling HCN production in reducing environments. We also perform sensitivity analyses on this chemistry and find HCN production and destruction on Titan can be understood in terms of only 19 dominant reactions. The process begins with UV photodissociation of N2 and CH4 in the upper atmosphere, and galactic cosmic ray dissociation of these species in the lower atmosphere. The dissociation radicals then proceed to react along four main channels to produce HCN. It is of particular excitement that one of these channels was newly discovered in this work.
Moving forward to modeling early Earth, we expand upon CRAHCN by exploring and calculating rate coefficients related to HCN and H2CO chemistry in atmospheres with oxidizing conditions. We calculate the rate coefficients for 126 new reactions, including 45 reactions that were first discovered in this work. We find the accuracy of our method continues to produce most commonly factor of two agreement with respect to experimental values. Next, we develop the oxygen extension to CRAHCN (CRAHCN-O), containing a total of 259 reactions for computing HCN and H2CO production in atmospheres dominated by N2, CO2, H2, CH4, and H2O. Again, experimental rate coefficients are used when available (43%), and our calculated values are used otherwise (57%).
We then build a comprehensive model with a unique coupling of early Earth geochemistry, radiative transfer, atmospheric UV and lightning chemistry, and aqueous chemistry in WLPs. We calculate self-consistent pressure-temperature profiles using a 1D radiative transfer code called petitRADTRANS, and couple these to CRAHCN-O and ChemKM to simulate HCN and H2CO production on early Earth. We model two epochs, at 4.4 and 4.0 billion years ago (bya), which differ in atmospheric composition, luminosity, UV intensity, radical production from lightning, and impact bombardment rate. The respective reducing and oxidizing atmospheric compositions of the 4.4 and 4.0 bya epochs are mainly driven by the balance of H2 impact degassing and CO2 outgassing from volcanoes. We then couple the rain-out of HCN with a comprehensive WLP model to compute the in situ production of RNA building blocks for each epoch. HCN pond concentrations are multiplied by experimental yields to calculate biomolecule production, and there are various biomolecule sinks present including UV photodissociation, hydrolysis and seepage.
At 4.4 bya, we find that HCN rain-out leads to peak adenine production of 2.8μM (378 ppb) for maximum lightning conditions. These concentrations are comparable to the peak adenine concentrations delivered by carbon-rich meteorites (10.6μM); however, the concentrations from in situ production persist for > 100 million years in contrast to ~days for meteoritic concentrations. Guanine, cytosine, uracil and thymine concentrations from in situ production at this time peak in the 0.19–3.2μM range, and ribose and 2-aminooxazole peak in the nM range. We note that cytosine and thymine are not present in meteorites, suggesting this biogenic pathway may be one of the only plausible origins of these RNA and DNA building blocks. We find that the high mixing ratio of HCN near the surface of our 4.4 bya model is mainly driven by lightning chemistry rather than UV chemistry. Our results show that HCN production at the surface is linearly dependent on lightning flash density. This result supports a lightning-based Miller-Urey scenario for the origin of RNA building blocks. At 4.0 bya, HCN production and rain-out is 2–3 orders of magnitude less abundant than it is at 4.4 bya, leading to negligible concentrations of RNA building blocks in WLPs during this late oxidizing phase. Similar to HCN production in Titan's atmosphere, HCN production in early Earth's atmosphere is strongly correlated with CH4 content. Reducing (H2-dominant) conditions sustain CH4 levels at a roughly constant ppm-level over 100 million years, which is favourable for HCN production. In oxidizing conditions, CH4 is readily oxidized into CO2, leading to less HCN. These results suggest that early Earth was biogenic at 4.4 bya, and remained so for at least ~100 million years, but was over by 4.0 bya due to oxidation of the atmosphere.
This thesis provides a firm theoretical foundation for an origin of RNA in WLPs on a biogenic early Earth within about 200 million years after the Moon-forming impact and the cooling of the magma ocean. / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/26775 |
| Date | January 2021 |
| Creators | Pearce, Ben K. D. |
| Contributors | Pudritz, Ralph E., Physics and Astronomy |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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