ELSI	
  4th	
  international	
  symposium	
  “Three	  experiments	
  in	
  biological	
  origins:	
  early	
  Earth,	
  Venus	
  and	
  Mars”	
  
	
  
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  Abstracts	  for	
  oral	  presentaions	  -­‐	
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	  Introductory day (Tue 12th)
Kei Hirose, George Helffrich (ELSI, Japan)
Welcome and Introduction
Shigeru Ida (ELSI, Japan)
Introduction to day 1 topics: Planet formation and volatile delivery to terrestrial planets (p. 3)
Dave Stevenson (Caltech, USA)
Introduction to day 2 topics: The Nature of Planets (p. 4)
Norm Sleep (Stanford, USA)
Introduction to day 3 topics: Disequilibria and the requirements for (successful) pre-biotic
chemistry (p. 5)
Instructions to poster presenters
Coffee and poster viewing
Public lecture: “Does water define a planet's habitability?”
Victoria Meadows (University of Washington/NASA Astrobiology Institute)
Tomohiro Usui (Tokyo Tech)
Day 1 (Wed 13th) - The Formation of Venus, Earth and Mars
Colette Salyk (Vassar College, USA)
Chemistry in terrestrial planet forming regions of protoplanetary disks (p. 6)
Hal Levison (SwRI, USA)The Formation of Terrestrial Planets from the Direct Accretion of Pebbles (p. 7)
CoffeeFrancis Albarede (ENS Lyon, France)
Volatility scale, gravitational escape, and abundance of water and volatiles in the Moon andEarth (p. 8)
Q&A and discussion
Discussion leaders: Shigeru Ida
Lunch
Bernard Marty (CRPG Nancy, France)
Origins and timing of volatile elements on Earth and Mars in view of the results of the
Rosetta mission (p. 10)
Hidenori Genda (ELSI, Japan)
Giant impacts and early evolution of terrestrial planets (p. 11)
CoffeeKosuke Kurosawa (Chiba Tech, Japan)
An atmospheric response against from impact bombardments on Earth and Venus: The roleof impact ejecta (p. 12)
Patrick McGovern (LPI, USA)
The Martian Crustal Dichotomy: an Ancient and Fundamental Feature (p. 13)
Q&A and discussion
Discussion leaders: Steve Mojzsis
Poster viewing1	
  09:00 - 09:40
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15:20 - 16:00
16:00 - 17:15
17:15 - 18:30

09:00 - 09:40
09:40 - 10:20
10:20 - 10:50
10:50 - 11:30
11:30 - 12:00
12:00 - 13:30
13:30 - 14:10

14:10 - 14:50
14:50 - 15:20
15:20 - 18:00

Day 2 (Thu 14th) - Planets as Integrated Systems
Victoria Meadows (U Washington, USA)
Exoplanets: A New Era of Comparative Planetology (p. 14)
Yuk Yung (Caltech, USA)
Chemistry of the Atmospheres of Planets and Exoplanets (p. 15)
CoffeeCaroline Dorn (U Bern, Switzerland)Interiors of low-mass exoplanets: what can we learn from observations? (p. 16)
Q&A and discussion
Discussion leaders: Dave Stevenson
Lunch
David Catling (U Washington, USA)
Planetary atmospheres, biospheres, and chemical disequilibrium (p. 17)
Axel Kleidon (MPI Jena, Germany)
What can thermodynamics tell us about the functioning of the Earth system, its habitability,
and its evolution? (p. 18)
CoffeeRoger Buick (U Washington, USA)
Evolution of Earth's biogeochemical nitrogen cycle: an example of an integrated systeminfluencing planetary habitability (p. 19)
Q&A and discussion
Poster viewing

Day 3 (Fri 15th) - Starting Conditions and Requirements for Prebiotic Chemistry
Steve Vance (JPL, USA)
Atmosphere disequilibration in different planetary contexts (p. 20)
Yuichiro Ueno (ELSI, Japan)
Disequilibrium of prebiotic atmosphere: C-H-O systems and role of water (p. 21)
CoffeeEverett Shock (ASU, USA)
Geologic Sources of Chemical Disequilibria on Terrestrial Planets (p. 22)
Q&A and discussion
Discussion leaders: Jim Cleaves
Lunch
Wolfgang Nitschke (IMM/BIP, France)
From thermodynamic disequilibria in alkaline hydrothermal vents to dissipative structures
giving birth to life (p. 23)
Ken Takai (JAMSTEC, Japan)
Prebiotic chemistry for energy and central metabolisms in early ocean of Earth (and Mars)(p. 24)
CoffeeWrapup discussion "Why?"
Discussion leaders: Eric Smith & Steve Mojzsis

	
  
	
  
	
  
	
  
	
  
	
  

	
  

2	
  

Day 0 – Introductory day
Planet formation and volatile delivery to terrestrial planets
Shigeru Ida (ELSI/Titech)
Observations show rich diversity and surprisingly high occurrence rate of exoplanetary systems. It isalso expected that earth-size planets commonly exist in habitable zones of exoplanetary systems, inwhich liquid water can exist on planetary surface. However, protoplanetary disks where planets areformed have too low gas density for H2O ice grains to condense in the habitable zones; the icy grains
can condense in outer colder disk regions. Note that other important elements for life, C and N,
condense in further colder regions. Thus, for planets in habitable zones to indeed harbor life, H2O, C
and N must be delivered to the planets from outer disk regions by some mechanism. I will discuss
scattering of icy planetesimals (1-100 km size bodies) by giant planets, orbital migration of icy
planets due to planet-disk gravitational interactions, and orbital migration of pebbles (1-100 cm size
bodies) due to gas drag, as possible mechanisms to deliver H2O, C and N.

	
  

3	
  

The Nature of Planets
Dave Stevenson (Caltech)
Our own solar system has diverse planets but exoplanetary observations have taught us that therichness of planets is far greater than our local sample. This should not surprise us since the nature ofa planet depends on how it was built and the materials available, and there is surely no single,
universal story of planet formation even though there is universality of the general principles ofphysics and chemistry. Chance (the stochastic nature of the process) also matters. Planets haveinteracting components: We must not think of the atmosphere (or ocean) as being isolated from theinterior. Can we figure out the planet by looking at the atmosphere? It may be possible; to someextent this is what we do locally. It is a major challenge of exoplanetary studies. But at this early stage
in our understanding of exoplanets, we have at most four things to work with: Location (orbit of theplanet and nature of the central star together with its cosmochemical make-up, e.g. metallicity), planet
mass (often from Doppler, but greatly augmented by TTV), planet radius (from transit), and (in a few
cases) something about the nature of the atmosphere or clouds. Location is important and has often
been emphasized because of the concept of a “habitable zone” (though I will argue that this concept ispartly anthropocentric and possibly unimaginative). Certainly, overall composition matters, but also
the oxygen fugacity (crucial in understanding the speciation of carbon, for example). Mass and radius
have enabled us to recognize some compositional systematics, though in many cases it is ambiguous
because capture of a hydrogen atmosphere substantially contributes to the radius but not the mass.
This is testament to timing (in our solar system, the terrestrial planets approached their final masses
after the nebula had departed). Other kinds of information (e.g., magnetic fields, existence of
exomoons or rings, direct imaging, detailed spectroscopy) will eventually help.

	
  

4	
  

Disequilibria and the requirements for (successful) pre-biotic chemistryNorm Sleep (Stanford)
Life gathers energy and materials from its environment, reproduces with some fidelity, and thendisperses. There is expectation that tracks of early energy sources exist in extant life. Thresholdtheory provides a relevant testable framework. Nascent life competes with nonlife. An organism
became quite abundant once it passed a threshold in gathering, reproduction, and dispersal. There is
likely a clean origin of life and a clean bottleneck associated with major biological innovations. With
regard to geology, the presence of various rock types, circulating hydrous fluids, solar radiation,
asteroid impacts, and the hydrologic cycle make disequilibria inevitable on Mars, Ceres, and the early
Earth. In all cases, one must vet putative prebiotic environments, as life as greatly modified the crustand even the mantle of the Earth. One approach is to work backward from energy sources for extant
life. Carbon dioxide and dihydrogen and carbon monoxide are chemical sources. Extant life harvests
photoelectric currents. Other energy sources do not have uses by extant organisms. Osmotrophic life
might live from chemical (including pH) gradients. Life might benefit from turning olivine into
serpentine. Life likely evolved anoxygenic photosynthesis by 4.1 Ga before much geological record.
It is thus helpful to work forward from conditions after the moon-forming impact. Seeding terrestrial
life from Mars or Ceres is more testable than origin on the Earth because the geological record
persists.

	
  

5	
  

Day 1 - The Formation of Venus, Earth and Mars

Chemistry in terrestrial planet forming regions of protoplanetary disks	  Collete Salyk (Vassar College, USA)In this talk, I will present an astronomer’s perspective on our current understanding of disk chemistryin terrestrial planet-forming regions, focussing on the protoplanetary disk phase, which encompasses
the first few Myr of planet formation. I’ll begin by discussing the challenges associated with theseobservations, followed by a description of the cutting-edge techniques that allow us to overcome
some of these challenges. Then, I will focus on a few observational results (and works in progress)
most relevant for terrestrial planet diversity. In particular, I will discuss observations of bulk
molecular chemistry in terrestrial planet forming regions, evidence for the condensation sequence, andattempts to constrain rates of radial mixing.

	
  

6	
  

The Formation of Terrestrial Planets from the Direct Accretionof Pebbles
Hal Levison (SWRI-Boulder)
Building the terrestrial planets has been a challenge for planet formation models. In particular,classical theories have been unable to reproduce the small mass of Mars and instead predict that aplanet near 1.5 AU should roughly be the same mass as the Earth (Chambers 2001, Icarus 152,205).
Recently, a new model, known as 'viscously stirred pebble accretion' (VSPA), has beendeveloped that can explain the formation of the gas giants (Levison+ 2015, Nature, 524, 322). Thismodel envisions that the cores of the giant planets formed from 100 to 1000 km bodies that directly
accreted a population of pebbles (Lambrechts & Johansen 2012, A&A 544, A32) - centimeter- tometer-sized objects that slowly grew in the protoplanetary disk. Here, I review the development ofterrestrial planet models and describe a new set of calculations (Levison+ 2015, PNAS 112, 14180)
that apply VSPA to the terrestrial planet region. I will show that these VSPA can reproduce the basic
structure of the inner Solar System, including a small Mars and a low-mass asteroid belt. In particular,
for an initial population of planetesimals with sizes similar to those of the main belt asteroids, VSPA
becomes inefficient beyond ~1.5 AU. As a result, Mars's growth is stunted and nothing large in theasteroid belt can accumulate.

	
  

7	
  

Volatility scale, gravitational escape, and abundance of water and volatiles
in the Moon and EarthFrancis Albarède (ENS-Lyon)
Because the balance of melting and vaporization during impact biases estimates of how much lateveneer was added to the Earth, currently estimated at 0.5 percent from PGE abundances in theterrestrial mantle, the amount of volatile-rich material added to the Earth by late accretion isunderestimated by up to a factor of eight. Increasing the proportion of late veneer to two percent toaccount for the overlooked segregation metallic fraction of impactors to the terrestrial core, could
bring the amount of water in the mantle well above 1000 ppm and make the age of the Giant Lunar
Impact calculated using the priciples outled by Jacobson et al. (Nature Geosciences 2014) as early as
30 My after the formation of the formation of the Solar System.
In a series of landmark papers, Hauri and Saal (Nature and Science, 2008-2013) presented data on
water concentrations measured in melt inclusions in olivine from the volcaniclastic ‘orange’ and‘green’ glasses that compare with contents in terrestrial MORB. A number of moderately volatileelements such as F, Cl, and S have been outgassed from lunar basalts, but this observation is not in
itself evidence that water was present in the first place. So far no conclusive evidence has been foundthat other types of lunar basalts had ever contained such high water contents. Whether high watercontents reflect the processes associated with volcaniclastic glass emission rather than being an
indication that the lunar mantle is wet is therefore a valid question. Comparing elemental abundancesin the Moon and the Earth requires one to address the relative importance of gravitational loss andintrinsic volatility, which is the topic of the present talk. Gravitational loss should strongly fractionate
elements with comparable chemical properties and different atomic masses, typically halogens andalkali elements, among themselves, which is not what current compositional models of the Moonshow. The proto-lunar disk lacked hydrogen, which makes significant hydrodynamic entrainment
unlikely. Given the very fast accretion of the Moon, Jean’s loss from the exobase, which Ward (ApJ
2012) places at several thousands of kilomers above the lunar disk equatorial plane must haveremained a minor phenomenon. The pattern based on Albarede et al.’s (MAPS, 2014) bond-energy
scale is smooth pattern for both the Moon and the Earth. What makes the latter scale useful is thepossibility of inter/extrapolating the abundance of a particular element from those of neighboring
elements. This plot predicts that the abundance of water in the Moon is in the sub-ppm to the ppm
range, which is confirmed by the actual H2O/Ce ratios measured in non pyroclastic glasses by Chen etal. (EPSL, 2015). The observed level of depletion of moderately volatile elements in the Moon withrespect to BSE such a F and Rb (1/10), Zn and I (1/100), makes the nearly terrestrial H abundance

	
  

8	
  

postulated for the Moon unlikely. The lingering puzzle is why Earth and Moon received such different
volatile endowments. Embedded in this question are the modes and extent of late veneer delivery andthe age of the lunar impact.

	
  

9	
  

Origins and timing of volatile elements on earth and Mars in view of theresults of the Rosetta mission
Bernard Marty (U. Lorraine/CNRS-Nancy)
Recent measurements of the volatile composition of the coma of Comet 67P/ChuryumovGerasimenko (hereafter 67P) allow constraints to be set on the origin of volatile elements (water,
carbon, nitrogen, noble gases) on Mars and Earth. Analyses by the ROSINA mass spectrometry
system onboard the Rosetta spacecraft indicate that 67P ice has a D/H ratio three times that of theocean value and contains significant amounts of N2, CO, CO2, and importantly, argon. From massbalance calculations, and provided that 67P is representative of the cometary ice reservoir, weconclude that the contribution of cometary volatiles to the Earth's inventory was minor for water (≤1%), carbon (≤ 1%), and nitrogen species (a few % at most). However, cometary contributions to theterrestrial atmosphere may have been significant for the noble gases. They could have taken place
towards the end of the main building stages of the Earth, after the Moon-forming impact and during
either a late veneer episode or, more probably, the Terrestrial Late Heavy Bombardment around 4.03.8 billion years (Ga) ago. Contributions from the outer solar system via cometary bodies could
account for the dichotomy of the noble gas isotope compositions, in particular xenon, between the
mantle and the atmosphere. A mass balance based on 36Ar and organics suggests that the amount ofprebiotic material delivered by comets could have been quite considerable – equivalent to the presentday mass of the biosphere. On Mars, several of the isotopic signatures of surface volatiles (notably thehigh D/H ratios) are clearly indicative of atmospheric escape processes. Nevertheless, we suggest thatcometary contributions after the major atmospheric escape events, e.g., during a Martian Late Heavy
Bombardment towards the end of the Noachian era, could account for the Martian elemental
C/N/36Ar ratios, solar-like krypton isotope composition and high 15N/14N ratios.

	
  

10	
  

Giant impacts and early evolution of terrestrial planets
Hidenori Genda (ELSI-Titech)
There are wide varieties of physical and chemical states among terrestrial planets in our solar system,
such as their sizes, orbits, spin states (also the presence of a moon), the amount and composition of
atmosphere, the presence of ocean and life etc. How have these varieties been built? Here we focus on
the formation stage of the terrestrial planets. This is because very energetic events occur during theplanet formation, such as the collisions among planetesimals and protoplanets. Especially, several
tens of Mars-sized protoplanets collide with each other to form the terrestrial planets during the laststage of the terrestrial planet formation. This stage is called the giant impact stage. Such energetic
collisions should have a great influence on the various features of the terrestrial planets. For example,
giant impacts are responsible for the creation of the Moon and the Martian satellites, and planets withextremely large cores such as Mercury. Giant impacts also affect volatile budget in terrestrial planets,
and lead to magma oceans. Cooling of a magma ocean and escape of water vapor results in adifference in water content on Earth and Venus. Even in extrasolar planetary systems, giant impact
events are thought to be common.
Recently, tens of warm debris disks around extra-solar-type (FGK) young stars have been observed.
These warm debris disks are estimated to be located roughly 1 AU to several AU from the central
stars, which corresponds to the terrestrial planet region in the solar system. Based on their stellar ages
and locations of the debris disks, the relation between these warm debris disks and giant impact
events has recently been discussed.

	
  

11	
  

An atmospheric response against from impact bombardments on Earthand Venus: The role of impact ejecta
Kosuke Kurosawa (U. Chiba)
The fate of surface water on Venus is one of the most curious problems in comparative planetology.
The mechanism responsible for causing a water deficit on the Venusian surface must be explored tounderstand the origin of the significant difference in the surface environment between Earth andVenus. Here I would like to propose a new concept to explain water removal on a steam-covered
proto Venus, referred to as “impact-driven planetary desiccation”. Since water vapour isphotochemically unstable, a steam atmosphere dissociates into hydrogen and oxygen. Then, hydrogenescapes easily into space through hydrodynamic escape. The focus is on the intense impact
bombardment during the period of late accretion as generators of a significant amount of reducing
agent. The fine-grained ejecta remove the residual oxygen, the counter part of escaped hydrogen, via
the oxidation of iron-bearing rocks in a hot atmosphere. Thus, hypervelocity impacts cause net
desiccation of the planetary surface. I constructed a stochastic cratering model using a Monte Carloapproach to investigate the cumulative mass of nonoxidized, ejected rocks during the period. Next, an
upper limit on the total amount of removed water was calculated using the stoichiometric limit of theoxidation of basaltic rocks. It is shown that a thick steam atmosphere with a mass equivalent to that of
the terrestrial oceans would be removed. The cumulative mass of rocky ejecta released into theatmosphere reaches 1 wt% of the host planet, which is 10000 times of the current mass of the Earth’s
atmosphere. This process does not work efficiently on a ocean-covered proto Earth because theoxidation of impact ejecta would not proceed during its flight. These results suggest that the form of
surface water (i.e., ocean versus a steam atmosphere) is an important factor in determining the fate ofsurface water against to the impact bombardment.

	
  

12	
  

The Martian Crustal Dichotomy: an Ancient and Fundamental Feature
Patrick McGovern (LPI Houston)
The hemispheric dichotomy is a fundamental feature of Mars, expressed by a physiographic andgeologic divide between the heavily cratered southern highlands and the relatively smooth plains of
the northern lowlands. Joint analysis of gravity and topography data indicates that the dichotomy isrooted in crustal thickness variations, with the crust of the southern highlands thicker than that of thenorthern lowlands. The observed high density of impact craters and basins in the southern highlands
establishes that the crust there formed by the Early Noachian, the oldest characterized epoch ofMartian history. While images of the northern lowlands show few impacts, signifying a young
surface, laser altimetry reveals a population of buried impact structures spanning a large range ofsizes, in numbers that establish northern basement formation as also by the Early Noachian. Thus, thecrustal dichotomy is the most ancient preserved structural feature of Mars, and is superposed by still“ancient” but younger impact basins and volcanic provinces. Dichotomy formation mechanisms canbe grouped into endogenic (internal) and exogenic (external) categories. Endogenic mechanisms
invoke flow of the Martian mantle to deform an initially uniform-thickness crust: for example,
overturn of a crystallizing magma ocean or a degree-1 solid-state convection cell might thicken thecrust over a singular large downwelling in the south. Alternatively, abundant melting over a degree-1
upwelling could drive volcanic crustal thickening in the south. Exogenic mechanisms produce thedichotomy by removal of material in the north by one or more impacts. The most successful exogenic
hypothesis invokes formation of an elliptical Borealis basin via a single oblique impact, creating abasin outline consistent with the observed expression of the dichotomy boundary while avoiding
excessive heating and melting that would tend to diminish the crustal thickness variations.

	
  

13	
  

Day 2 - Planets as Integrated Systems

Exoplanets: A New Era of Comparative Planetology
Victoria Meadows (U. Washington)
We now know of over 2000 planets orbiting other stars, and several thousand additional planetary
candidates. These discoveries are revolutionizing our understanding of planet formation andevolution, while providing targets for the search for life beyond the Solar System. Exoplanets display
a larger diversity of planetary types than those seen in our Solar System – including terrestrials larger
than Earth, and low-density, low-mass objects. They are also found in planetary system architectures
very different from our own, even for stars similar to our Sun. Solar System and exoplanet studies canbe mutually beneficial: known Solar System planetary processes can inform our understanding of
exoplanets, while the diversity and broader perspective that exoplanets bring improves our overall
understanding of planetary science, with application to Solar System planets. Exoplanets challenge us
to consider the outcome of a planet’s evolution as an interplay between planet, star, and planetarysystem - for different planetary compositions, planetary system architectures and host star type. This
broader - yet integrated - view is especially relevant to studies of factors that affect planetary
habitability. In particular, while M dwarfs are the most likely habitable planet hosts in the Galaxy, thehabitability of planets orbiting them will be influenced not only by radiative, but also gravitational
effects. In advance of observations to characterize potentially habitable exoplanets, we will discuss
how Solar System planets inform the search for life elsewhere, and how we are using the rich heritageof planetary science models to explore the potential diversity of exoplanet environments and starplanet interactions. This research helps us identify the factors and processes that lead to, maintain or
preclude habitability - and further illuminates Earth’s unique position in our Solar System as the only
planet to support a surface biosphere.

	
  

14	
  

Chemistry of the Atmospheres of Planets and Exoplanets
Yuk Yung (Caltech)
We now understand the chemistry of planetary atmospheres in our Solar System ranging from theprimitive atmospheres of the giant planets to the highly evolved atmospheres of terrestrial planets andsmall bodies. Our understanding can be distilled into three important ideas: (1) The stability ofplanetary atmospheres against escape of their constituents to space, (2) the role of equilibrium
chemistry in determining the partitioning of chemical species, and (3) the role of disequilibrium
chemistry, which produces drastic departures from equilibrium chemistry. To these three ideas wemust also add a fourth: the role of biochemistry at Earth's surface, which makes its atmosphericchemistry unique in the cosmochemical environment. Only in the Earth's atmosphere do strong
reducing and oxidizing species coexist to such a degree. Life provides a means for using solar energy
to drive chemical reactions that would otherwise not occur; it represents a kind of photochemistry thatis special to Earth, at least within the Solar System. It remains to be seen how many worlds like Earththere are beyond the Solar System, especially as we are now exploring the exoplanets using Kepler,
TESS, HST, Spitzer, soon to be launched missions such as JWST and WFIRST, and ground-based
telescopes. The atmospheres of the Solar System provide a benchmark for studying exoplanets, which
in turn serve to test and extend our current understanding of planetary atmospheres. Ultimately, we
may be able to answer these profound questions: Are we alone in the universe? What makes a planet
habitable? How does life originate? And what is the destiny for life on our own planet?

	
  

15	
  

Interiors of low-mass exoplanets: what can we learn from observations?
Caroline Dorn (U. Bern)In recent years, the efforts in detecting small mass exoplanets below 10 Earth masses have yielded adiversity of candidates. One key question is whether these exoplanets are Earth-like in terms ofstructure and dynamics. If plate tectonics, as on Earth, is required to form life is a matter of debate.
But since the only planet where life has been identified is distinct from other terrestrial planets byplate tectonics, it is crucial to understand both the possible structures and dynamics of exoplanets inorder to determine their habitability. Of course, other types of planets may be able to harbor life.
In order to determine the range of probable interior structures for an exoplanet of generalcomposition, we perform a full probabilistic analysis that formally accounts for data and model
uncertainties. Our model assumes a possible four layer structure of iron core, silicate mantle, water ice
layer and an atmosphere of H, He, C, and O. Layer thicknesses and compositions of mantle andatmosphere are conditioned to planetary data.
We discuss the application of this method to five exoplanets for which not only mass and radius are
known as constraints but also additional abundance proxies. Theoretical studies and empiricalevidences from Solar System objects strengthen the possibility that the relative refractory element
composition of a planet is directly correlated to its host star composition, namely the ratios of Fe, Mg,
and Si. Constrained structural parameters are differently sensitive to our assumptions on these planet
bulk ratios. Our ability to constrain interior structure highly depends on data and data uncertainties.
The main focus of this talk is the characterization of exoplanets in terms of interior structure.
Dependencies of the tectonic regime (plate tectonics or stagnant lid) are reviewed. To determine thetectonic regime of an exoplanet will be extremely difficult due to severe limitations on constraining
key parameters that influence dynamics.

	
  

16	
  

Planetary atmospheres, biospheres, and chemical disequilibrium
David Catling (U. Washington)
The most interesting question about exoplanets is whether any of them are inhabited. Apart fromnoble gases, Earth’s atmosphere is biologically cycled, which has led to the idea of detecting life on
exoplanets from atmospheric absorption spectra. Earth’s atmosphere is anomalous because major (N2,O2) and minor gases (e.g., CO2, CH4, and N2O) are biogenic; the atmosphere also has muchchemical disequilibrium [1]. Of course, all planetary atmospheres are in disequilibrium to some extent
because of free energy from insolation, internal heat, or tidal heat. So, whether a biosphere can beinferred from disequilibrium is a question of degree. Certainly, when quantified as the Gibbs energyof an observed atmosphere minus that of all gases reacted to equilibrium, Earth’s atmosphere-oceansystem has ~20 to 2 million times larger disequilibrium than that of other Solar System atmospheres[2]. But the issue is subtle. First, planetary atmospheres evolve in composition and so must change
their disequilibrium with time. Second, the type of biosphere should affect whether there is significant
disequilibrium or not. Photosynthesis generates significant disequilibrium whereas simpler
chemosynthetic biospheres probably favor atmospheres close to thermodynamic chemical
equilibrium. Third, under certain circumstance, untapped chemical disequilibrium in an atmosphereindicates no biosphere rather than life, i.e., a “free lunch” that no one is eating. The presence ofrelatively abundant CO on Mars is an example. Fourth, several metrics could quantify disequilibrium
but they’re yet to be fully explored and their comparative merits need evaluation.

[1] Lovelock, J. E. (1975) Thermodynamics and the recognition of alien biospheres. Proc. R. Soc. Lon. B189,
167-181. [2] Krissansen-Totton, J., Bergsman, D. S., Catling, D. C. (2016) On detecting biospheres fromchemical thermodynamic disequilibrium in planetary atmospheres, Astrobiology, in press.

	
  

17	
  

What can thermodynamics tell us about the functioning of the Earthsystem, its habitability, and its evolution?
Axel Kleidon (MPI-Jena)
I present a thermodynamic view of the whole Earth system with the aim to describe the fundamental
constraints on its dynamics and magnitudes of processes, its evolution, and to evaluate the role of lifein the system. The starting point forms the Carnot limit, which follows directly from the first andsecond law of thermodynamics. It limits how much of the radiative heating can be converted intomechanical work that drives planetary motion. When this limit is combined with energy balances, ityields a maximum power limit, because a greater heat flux results in a lower temperature difference.
When this maximum power limit is applied to present-day conditions, it predicts the spatial andtemporal variation of the surface energy balance partitioning as well as its sensitivity to change very
well. We can then infer rates of mass cycling from this limit and thus infer magnitude of hydrologic
and geochemical cycling. Motion provides the means to exchange the moistened air from places
where water evaporates with drier air from where it condenses and it replaces products with reactants
where chemical reactions take place. It thus forms an essential process to maintain geochemical
cycling in a state of thermodynamic disequilibrium. This mass exchange provides essential resources
to and removes waste products of the metabolic reactions of life. We thus have a planetary description
from the radiative forcing to motion and mass cycling to biotic activity that places a particularemphasis on transport limitations of biogeochemical transformations that follow from thermodynamic
constraints, which can, however, be altered by changing the radiative properties of the planetarysystem. I discuss how this view of the thermodynamic Earth system can serve as a template tounderstand other planetary environments, link it to its habitability, and describe how it may help us tobetter understand planetary evolution.

	
  

18	
  

Evolution of Earth’s biogeochemical nitrogen cycle: an example of an
integrated system influencing planetary habitability
Roger Buick (U. Washington)
Nitrogen is a major nutrient for all terrestrial life, occurring in catalytic proteins, informational nucleic
acids and energetic ATP. Life’s distribution, abundance and evolution is thus dependent on the bioavailability of this essential element, but conversely life’s evolution has modified the distribution,
speciation and abundance of nitrogen. The biogeochemical cycling of nitrogen therefore shows a coevolutionary relationship with Earth’s biosphere and as a result, the nitrogen cycle has changed
markedly through time. In the Hadean and Eoarchean, abiotic fixation would have accounted for avery small flux of bio-available nitrogen from the atmosphere, severely limiting the size and diversityof the primordial biosphere. However, efficient biology fixation using Mo-nitrogenase wasestablished by 3.2 Ga in the Mesoarchean, leading to large biomass deposition in marine settings and(possibly) depletion of nitrogen from the atmosphere as a result of enhanced organic burial. During
the late Neoarchean in conjunction with the first whiffs of biogenic oxygen to the atmosphere, aerobic
nitrogen cycling was temporarily initiated, marked by positive fractionations of nitrogen isotopes
indicating active denitrification sending nitrogen gas back to the atmosphere. The Paleoproterozoic“Great Oxidation Event” and subsequent “oxygen overshoot” during the Lomagundi carbon isotopic
excursion marked widespread aerobic cycling with vigorous denitrification. Towards the end of the
Paleoproterozoic and through the Mesoproterozoic, expanded euxinic (sulfidic) conditions in theoceans during the “boring billion” years of environmental stasis caused spatial perturbations in thenitrogen cycle, with aerobic cycling near-shore but anaerobic fixation-dominated cycling offshore. As
sulfide strips dissolved copper from seawater, thus removing the key cofactor for the critical enzyme
in the last step of denitrification, a nitrous oxide greenhouse may have been operative at this time. It is
not clear when the nitrogen cycling attained its modern fully aerobic aspect, but it may have been aslate as the Devonian when the deep oceans may have finally become permanently oxidized. So, thetemporal changes in Earth’s nitrogen cycle illustrate the reciprocal co-evolution of the planetary
physical and biological environment, modulated in particular by the redox state of the oceans andatmosphere.

	
  

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Day 3 - Starting Conditions and Requirements for
Prebiotic Chemistry

Atmosphere disequilibration in different planetary contexts
Steve Vance (JPL-Caltech, EON)
I will discuss the planetary atmosphere as a chemical interface essential for life, and consider whether
the icy surface of Jupiter’s moon Europa may perform a similar role to that of Earth’s atmosphere.
Radiolysis of Europa’s surface ice produces oxidants at rates that may be compared with those of the
Earth system. The high flux of oxidants to Europa's ocean is only useful to life if the rocky interior
provides a reliable source of reductants and minerals to keep the engine of life running. I describemodels for hydrothermal activity on Europa that suggest that-rock alteration in Europa causes
hydrogen fluxes only slightly smaller than Earth's. Europa's ocean may have become reducing for abrief epoch, after a thermal-orbital resonance following accretion, creating an environment that may
have favored an independent origin of life. The range of estimated oxidant flux to Europa's ocean iscomparable to estimated hydrogen fluxes.

	
  

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Disequilibrium of prebiotic atmosphere: C-H-O systems and role of water
Yuichiro Ueno (ELSI/Titech)Redox disequilibrium of Hadean atmosphere is a key to enable the emergence of life on Earth. Simple
organic compounds can be synthesized by photochemistry that can initiate prebiotic synthesis ofcomplex organic molecules. In contrast to the other possible sources like Miller-Urey-type lightningand delivery of organics by extraterrestrial impact, UV-driven photochemistry could ceaselessly
supply organics everywhere on the surface of the Earth, thus has a potential to sustain further networkof reactions in the ocean. Also, photolysis of H2O likely produce redox gradient or disequilibrium atthe surface of the ocean or lake. In order to predict the photochemical production qualitatively andquantitatively, we have conducted a series of laboratory experiments of C-H-O system. The results
show that the speciation of synthesized compounds may be sensitive to the amount of water. Theirproduction rate depend largely on redox state of the system and actinic flux particularly shorter than
200 nm. These results suggest that not only atmospheric composition but also hydrosphere and its
redox state should be the key to control the fate of organic molecules supplied from early atmosphere
into hydrosphere.

	
  

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Geologic Sources of Chemical Disequilibria on Terrestrial Planets
Everett Shock (Arizona State U.)
Processes that combine chemical constituents that are far from equilibrium with each other generate
disequilibria. Planetary habitability reflects the supply of oxidation-reduction (redox) disequilibria
provided by planetary processes. Volcanism and active tectonics, as well as surface weathering andtransport are among the geologic processes on terrestrial planets that generate redox disequilibria. On
Earth, mantle convection, subduction, and an active hydrosphere augment the opportunities for the
emergence of redox disequilibria that can support microbial ecosystems. At high temperatures andpressures abiotic reactions rates can be fast enough for rapid re-equilibration. Redox reactions havesubstantial activation energies and are among the first reactions to depart from equilibrium uponcooling, which stifles the dissipation of chemical energy, and opens the door for catalysis. Lifeforms
emerge as adaptive catalytic systems challenged at first with beating abiotic catalysts, and ultimately
with partitioning the supply of redox disequilibria. Exploration has revealed microbial ecosystems
supported by the dissipation of geologically generated redox disequilibria in hydrothermal systems, indeeply buried sediments, and wherever rocks formed at high temperatures and pressures can bechemically weathered. That exploration is unlikely to be complete.

	
  

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From thermodynamic disequilibria in alkaline hydrothermal vents todissipative structures giving birth to life
Wolfgang Nitschke (IMM/BIP)
Life fundamentally is a thermodynamic far-from-equilibrium phenomenon. Combining the analysis of
the free-energy-converting mechanisms in extant life (“top-down approach”) and the survey of thetypes of strong thermodynamic disequilibria likely available on the early Earth (“bottom-up
approach”) points towards alkaline hydrothermal vents as promising hypothetical locales for life’s
origin. The two major types of thermodynamic disequilibria operating in extant life, that is, redox andpH gradients, are inherent features of these vents. The cascade of order-generating mechanisms fromthe cosmological level to the nanoscale eventually yielding the dissipative structures generating life in
the alkaline hydrothermal vent scenario will be briefly reviewed. The phenomena frustrating
thermodynamic equilibration of the redox and pH gradients in alkaline hydrothermal vents will be
detailed and likely archetypal free-energy-converting reactions (“engines”) inferred from theirdescendants in extant life. The inorganic metal catalysts playing crucial roles in such reactions inmodern life will be used as guides for deducing initial chemical/mineralogical conditions of thealkaline hydrothermal vent setting during life’s putative origin. Resulting ramifications for the
likelihood of life originating on Earth’s sister planets in the solar system will be discussed.

	
  

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Prebiotic chemistry for energy and central metabolisms in early ocean ofEarth (and Mars)Ken Takai (JAMSTEC)
It has been widely believed that the most ancient ancestral prokaryotes in the Earth would haveoriginated from deep-sea hydrothermal environments. Thus, it also seems the most likely thatpreceded prebiotic chemical evolution and birth of living forms would have taken place in same orsimilar hatchery places, deep-sea hydrothermal environments. The building blocks of prebiotic
chemistry would be derived from extraterrestrial sources (meteorites and cosmic particles) and/or
terrestrial sources (atmospheric generation and crustal hydrothermal circulations) and are mainly
CO2, C1-C3 organic acids and hydrocarbons, and NOx and ammonia in the deep-sea hydrothermal
environments. How was the living forms created from these very simple building blocks? The key
would be directional autocatalytic metabolisms and driven by abiotic energy sources and catalysts. I
would like to introduce our scenario that the directional autocatalytic metabolisms would haveintroduced monotheistic generation of living forms in the Earth and our experimental approaches tothis scenario. This scenario could be common in the early Earth, Mars and even Venus due to theirsimilar formation mechanisms.

	
  

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