This is a repository copy of Stochastic Prebiotic Chemistry within Realistic Geological Systems. White Rose Research Online URL for this paper: http://eprints.whiterose.ac.uk/107200/ Version: Accepted Version Article: Dass, AV, Hickman-Lewis, K, Brack, A et al. (2 more authors) (2016) Stochastic Prebiotic Chemistry within Realistic Geological Systems. ChemistrySelect, 1 (15). pp. 4906-4926. ISSN 2365-6549 https://doi.org/10.1002/slct.201600829 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: A. V. Dass, K. Hickman-Lewis, A. Brack, T. P. Kee, F. Westall, ChemistrySelect 2016, 1, 4906, which has been published in final form at https://doi.org/10.1002/slct.201600829. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Uploaded in accordance with the publisher's self-archiving policy. 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[email protected] https://eprints.whiterose.ac.uk/ Manuscript REVIEW doing science, he performs regular concerts on piano and ‘cello. 1 Stochastic Prebiotic Chemistry 2 within Realistic Geological Dr André Brack is currently Honorary Director of Research at the 3 Centre de Biophysique Moléculaire, CNRS, in Orléans, France, 4 Systems where he founded and headed the astrobiology group. His field 5 of expertise includes the chemistry of the origins of life and the 6 Avinash Vicholous Dassa, Keyron Hickman-Lewisa, Dr. search for extraterrestrial life. He is Fellow of the International 7 André Bracka, Dr. Terence P. Keeb and Dr. Frances Society for the Study of the Origin of Life, which he chaired for a three years, and of the NASA Astrobiology Institute. He is also 8 Westall Honorary President of the European Astrobiology Network and 9 of Centre-Science a center for science popularisation, which he 10 Abstract: This review introduces its readers to a ‘stochastic founded and chaired. 11 approach’ to origins of life research, from the viewpoints of both 12 prebiotic chemistry and geology. The idea of a “primordial soup” has been subject to extensive criticism from thermodynamic, Following BSc (1985) and PhD (1989) degrees in organometallic 13 biochemical and geochemical perspectives, yet recent chemistry at Durham University, Terence Key spent 18 months 14 advancements have made clearer the plausibility of this theory. as an SERC(NATO) Postdoctoral fellow at the Massachusetts 15 Herein, we review the theoretical and experimental approaches Institute of Technology working with Nobel Laureate Professor 16 which have previously been explored, among these modelling, Richard Schrock. He was appointed lecturer at the University of 17 laboratory-confined and geologically motivated experimentation. Leeds in 1990 and subsequently senior lecturer (1997) and 18 Of these, we consider organo-mineral interactions, uniting reader (2010). TPK has been Visiting Professor at the Université aspects of prebiotic chemistry and geology, to be an especially de Cergy-Pontoise, France (1999) and CNRS Centre 19 promising way forward. However, we aim here to advance Biophysique Moléculaire, France (2016) and holds affiliate 20 current approaches by advocating a methodology involving faculty membership in the Department of Astronomy, University 21 chemical systems and their stochastic reactivity on of Florida, Gainesville, USA. He was an STFC-UKSA Aurora 22 heterogeneous geological surfaces. This models the origins of Fellow in Astrobiology (2009-12) and since 2010 has been 23 life as a continuity of chemical reactions in an analogue to the president of the Astrobiology Society of Britain. TPK has 24 early Earth (Hadean) environment. authored or co-authored >100 published journal articles, books 25 chapters and reviews. In 2004, TPK discipline hopped from inorganic chemistry to chemical astrobiology, publishing some 26 Avinash Vicholous Dass completed his bachelor’s degree from 17 papers. He received the Research Award from the 27 Bangalore University, and obtained his master’s degree in Astrobiology Society of Britain in 2008. 28 Organic Chemistry from Vellore Institute of Technology. During 29 his master’s, he worked on organocatalytic Michael addition 30 reaction using polyionic liquids. Currently a doctoral student at Frances Westall is a geologist now working in the very broad CNRS Centre de Biophysique Moléculaire, Orléans, his discipline of astrobiology, the study of the origins of life and its 31 research focusses on prebiotic chemistry on mineral surfaces, destiny in the Universe. After a PhD in marine geology at the 32 and he is also working on the analysis of the Photochemistry on University of Cape Town in South Africa, she worked in various 33 the Space Station (PSS) samples from the Expose R2 research institutes around the world: the Alfred Wegener 34 experiment. Institute for Polar and Marine Research in Bremerhaven in 35 Germany, the University of Nantes in France, the University of 36 Bologna in Italy, the Johnson Space Center and Lunar and Keyron Hickman-Lewis read for his degree in Earth Sciences at Planetary Institute in Houston, USA and, for the last 15 years, 37 St Edmund Hall, The University of Oxford, graduating in 2015. she is Director of Research at the CNRS-Orléans in France 38 Presently a doctoral student at CNRS Centre de Biophysique where she heads the astrobiology group. Her research interests 39 Moléculaire, Orléans, his research concerns assessing and activities cover study of the earliest traces of life on Earth 40 enigmatic chemotrophic biosignatures from the Early Archaean, and the geological environment in which they lived, the artifical 41 decoding the surface environments of the early Earth, and using fossilisation of bacteria, the search for life on Mars, especially these discoveries to inform on the search for biosignatures in a 42 with the ESA/Russian ExoMars 2020 mission, and prebiotic potential Martian biosphere. He has also conducted research chemistry and the origin of life. 43 using novel techniques to unveil the three-dimensional character 44 of Archaean microfossils and microbial structures. When not 45 46 47 48 49 [a] A.V. Dass, K. Hickman-Lewis, Dr. A. Brack, Dr. F. Westall CNRS Centre de Biophysique Moléculaire 50 Rue Charles Sadron 51 45071 Orléans, France [email protected] 52 53 [email protected] 54 55 56 [b] T.P. Kee 57 School of Chemistry, University of Leeds Leeds LS2 9JT, UK 58 59 60 61 62 63 64 65 REVIEW 1 2 3 4 Table of Contents: 5 6 7 8 9 10 1 Introduction 11 1.1. Rationale 12 1.2. Ingredients for Life 13 1.2.1. Endogneous organic molecules 14 15 1.2.2. Exogenous organic molecules 16 17 2 Contemporary prebiotic chemistry approaches 18 2.1. Theoretical models for primitive life 19 20 2.1.1. Chemoton model 21 2.1.2. Autopoesis 22 2.1.3. Computer modelling 23 2.2. A cellular origin of Life 24 2.3. Hydrothermal vents 25 26 2.4. A vesicular origin for life 27 2.5. The RNA World Hypothesis 28 2.6. Self organisation and autocatalysis 29 2.7. An autotrophic origin of life 30 31 32 3 Contemporary geological approaches 33 34 4 A new paradigm: stochastic chemistry on mineral surfaces 35 4.1. Introduction 36 37 4.2. The virtues of mineral surfaces 38 4.2.1. The advantages of minerals 39 4.2.2. Mineral surface specificities 40 4.3. Realistic scenarios 41 42 43 5 Conclusion 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 REVIEW 1. Introduction studies to further elucidate the importance of mineral surfaces at 1 the prebiotic-biotic transition. 2 1.1. Rationale Herein, we complement and advance contemporary approaches 3 by not limiting our scope to a single mineral, but by considering 4 What is our origin? When a graduate student by the name of the situation inherent within heterogeneous geological 5 Stanley Miller published his experimental results in 1953, many substrates i.e., rocks, which was certainly the setting for 6 believed that mankind was very close to uncovering this mystery. aqueous chemistry on the primitive Hadean Earth. We therefore By demonstrating that it was possible to form amino acids from promote an approach of stochastic chemistry on the surfaces of 7 methane, a simple organic molecule containing only one carbon 8 diverse mineral faces, within a unified geological-chemical atom, Miller set in motion the ambitious hope that chemists system. 9 would be able to create life in a test tube, i.e., an organised 10 molecular system capable both of self-replication and of evolving. 1.2. Ingredients of life 11 It is now the year 2016, i.e. 63 years have passed since that 12 famous experiment. Despite tremendous efforts by chemists to The building blocks of life that we observe today on Earth are tackle the problem, the dream has not yet been accomplished: mainly composed of organic molecules; life, at least as we 13 although there have been many technological breakthroughs 14 recognise it, may not have existed without such molecules.