Evolution of Titan’s atmosphere during the Late Heavy Bombardment Nadejda Marouninaa, Gabriel Tobiea, Sabrina Carpya, Julien Monteuxa,b, Benjamin Charnayc, Olivier Grasseta aLaboratoire de Plan´etologie et G´eodynamique, Universit´ede Nantes, CNRS, UMR-6112, 2, rue de la Houssini`ere, 44322 Nantes cedex France. bLaboratoire Magmas et Volcans, Universit´eBlaise Pascal – CNRS – IRD, OPGC, 5 rue Kessler, 63038 Clermont-Ferrand, France cVirtual Planetary Laboratory, University of Washington, Seattle, WA 98195, USA Abstract The mass and composition of Titan’s massive atmosphere, which is dominated by N2 and CH4 at present, have probably varied all along its history owing to a combination of exogenous and endogenous processes. In the present study, we investigate its fate during the Late Heavy Bombardment (LHB) by modeling the competitive loss and supply of volatiles by cometary im- pacts and their consequences on the atmospheric balance. For surface albedos ranging between 0.1 and 0.7, we examine the emergence of an atmosphere during the LHB as well as the evolution of a primitive atmosphere with various masses and compositions prior to this event, accounting for impact-induced crustal NH3-N2 conversion and subsequent outgassing as well as impact- induced atmospheric erosion. By considering an impactor population characteristic of the LHB, we show that the generation of a N2-rich atmosphere with a mass equivalent to the present-day one requires ammonia mass fraction of 2 to 5 %, depending on surface albedos, in an icy layer of at least 50 km below the surface, implying an undifferentiated interior at the time of LHB. Except for high surface albedos (AS ≥ 0:7) where most of the released N2 remain frozen at the surface, our calculations indicate that the high-velocity impacts led to a strong atmospheric erosion. For a differentiated Titan with a thin ammonia-enriched crust (≤ 5 km) and AS < 0:6 , any atmosphere preexisting before the LHB should be more than 5 times more massive than at present, in order to sustain an atmosphere equivalent to the present-day one. This implies that either a massive atmosphere was formed on Titan during its accretion or that the nitrogen-rich atmosphere was generated after the LHB. Keywords: Titan, atmosphere; impact processes; atmosphere, evolution 1. Introduction Saturn’s largest satellite Titan is the only satellite in the Solar System possessing a dense atmosphere. Presently, it is composed predominantly of N2(∼98%) and CH4(∼ 2%) (e.g. Griffith et al., 2013). However, this atmospheric composition has probably varied through time since the accretion of the satellite due to various external and internal processes. Owing to continuous photochemical destruction and atmospheric escape, the lifetime of atmospheric methane is cur- rently of the order of ∼20 Ma (e.g. Griffith et al., 2013). Moreover, the isotopic 13C/12C ratio in Preprint submitted to Icarus May 27, 2015 CH4, measured by the mass spectrometer of the Huygens probe (GCMS) (Niemann et al., 2010), indicates that the present-day methane is not fractionated relative to Solar System standards, im- plying that it has been recently injected in the atmosphere (less than 1 Gyr ago (Mandt et al., 2012)). The origin of N2 is probably more ancient. The main constraint on its origin is provided by 36 −7 the Ar/N2 ratio measured by the Huygens GCMS (∼2.7×10 , Niemann et al. (2010)), which 5 36 is ∼3×10 times smaller than the solar value (Owen, 1982). As N2 and Ar should be trapped in similar rates either by direct condensation or clathration in the solar nebula (Owen, 1982; Mousis et al., 2002), this low value indicates that the nitrogen was not originally captured as N2 but as easily condensible nitrogen compounds such as NH3 (Atreya et al., 2009). Moreover, Mandt 14 15 et al. (2014) showed that the N/ N ratio measured in Titan’s N2 (Niemann et al., 2010) is con- sistent with isotopic ratio recently inferred from NH2 radicals produced by the photodissociation of NH3 in comets (Rousselot et al., 2014; Shinnaka et al., 2014), providing additional evidence for ammonia as the main source of nitrogen on Titan. Several mechanisms have been proposed to explain the conversion of NH3 into N2 at Titan’s conditions: photochemical conversion (Atreya et al., 1978), impact-induced conversion in the atmosphere (McKay et al., 1988; Ishimaru et al., 2011) or in a NH3-enriched icy crust (Sekine et al., 2011), as well as endogenic processes (Glein et al., 2009; Tobie et al., 2012). Here we focus on the conversion proposed by Sekine et al. (2011). Delivery of volatiles by impact has likely occurred all along Titan’s history (Griffith and Zahnle, 1995), with more intense flux during the accretion period and the Late Heavy Bombard- ment (LHB). Following the Nice model (Gomes et al., 2005; Morbidelli et al., 2005; Tsiganis et al., 2005), this intense bombardment would have affected the entire Solar System, due to the destabilization of the planetesimal disk beyond Neptune’s orbit. Because of the gravitational focusing of Saturn (Zahnle et al., 2003), the cumulative mass delivered on Titan during the LHB is estimated to 3×1020 kg (Barr et al., 2010). This intense bombardment, characterized by high impact velocities ( vesc, the escape velocity of the planet or the satellite), may have supplied a huge amount of volatiles (e.g. CH4 and NH3) either by direct contribution from impactor volatil- isation or by impact-induced degassing of Titan’s crust, as suggested by Sekine et al. (2011). High-velocity impactors are also expected to erode the atmosphere during the impact. Studies of impact-induced atmospheric erosion based either on analytic approaches or numerical simu- lations have been mostly focused on Mars and the Earth (Melosh and Vickery, 1989; Svetsov, 2000; Genda and Abe, 2005; Svetsov, 2007; Shuvalov, 2009). Parameterizations of impact- induced erosion were used by Pham et al. (2011) and de Niem et al. (2012) to investigate the atmospheric balance between erosion and volatile supply during the LHB on Mars, Earth and Venus. Here we follow a similar approach for Titan, combining a pressure-induced ammonia conversion from Sekine et al. (2011) and a parameterization of atmospheric erosion by impact from Shuvalov (2010). To investigate the predominant mechanism that governs the fate of Titan’s atmosphere during the LHB, we combine a stochastic approach for the impactor sampling and we monitor the atmo- spheric mass balance between the supply of N2 and CH4 by both impactor and crustal degassing and atmospheric erosion induced by impact. At pressures and temperatures expected on Titan, part of the supplied volatiles may condense at the surface. To estimate the partitioning between the volatiles in the atmosphere and those condensed at the surface, we implemented the atmo- spheric model developed by Lorenz et al. (1999) including radiative and gas-liquid equilibrium. 2 In the particular case of a pure N2 atmosphere, we use the atmospheric equilibrium constrained from 3D GCM simulations. A detailed description of the model is provided in the following section. Simulations of the evolution of Titan’s atmosphere during the LHB, considering a wide range of initial conditions, are presented in section 3. Implications for the origin and evolution of Titan’s atmosphere are discussed in section 4 and our conclusions are summarized in section 5. 2. Model description 2.1. Model of the atmospheric equilibrium The composition of Titan’s atmosphere may have varied throughout Titan’s history. As the mass and composition of Titan’s atmosphere before the LHB is uncertain, we consider various initial conditions prior to the LHB. The presence of methane in Titan’s atmosphere might only be recent and/or episodic (Tobie et al., 2006; Mandt et al., 2012). It is therefore possible that the atmosphere was composed solely of nitrogen at the time of the LHB. Then we consider either pure N2 or N2-CH4 atmospheres up to 10 times Titan’s present-day atmospheric mass. To model the radiative balance as well as the thermodynamic equilibrium between atmospheric and surface volatile reservoirs, we adopt two different modeling approaches for pure N2 and mixed N2-CH4 atmosphere model as detailed hereafter. 2.1.1. Pure N2 atmosphere In the case of a pure N2 atmosphere, the greenhouse effect is limited to collision-induced absorptions of N2 -N2, as N2 has no absorption band in the infrared and visible (Lorenz et al., 1997; Charnay et al., 2014). Equilibrium temperatures and pressures have been evaluated for surface albebos varying between 0.2 and 0.7 (see Table 1), from full 3D GCM simulations, us- ing the Generic LMDZ code employed and described in Charnay et al. (2014), accounting for Rayleigh scattering by N2 and N2 condensation and precipitation at the surface. These simula- tions showed that the greenhouse effect is counterbalanced by the increase of atmospheric albedo due to Rayleigh diffusion, so that the surface temperature is mostly determined by the surface albedo. Moreover, although the condensation of N2 and the atmospheric pressure are mostly controlled by the pole temperature, the GCM simulations showed that the average surface tem- perature remains a good parameter to predict the average atmospheric pressure and hence the average amount of condensed N2 at the surface. For a surface albedo As lower than 0.68, the sur- face temperature is above the freezing point and atmospheric N2 is in equilibrium with liquid N2 at the surface. For As > 0.68, the atmospheric N2 is in equilibrium with solid N2. Atmospheric pressures displayed in Table 1 correspond to saturation pressures of N2. Any excess of N2 is condensed at the surface. Although latitudinal variations of nitrogen condensation are expected based on GCM simulations (Charnay et al., 2014), we assume a uniform distribution of solids or liquids at the surface, and we consider the average temperature and pressure as representative of the surface conditions.