Nitrile gas chemistry in Titan’s atmosphere

This work presents the first study of the gaseous products resulting from the partial dissociation of methane and nitrogen in the PAMPRE experimental setup simulating Titan’s atmospheric chemistry.Using cryogenic trapping, the gaseous products generated from the chemical reactions occurring in the reactor have been trapped. Analyses of these products by gas chromatography coupled to mass spectrometry have allowed the detection and identification of more than 30 reaction products. Most of them are identified as nitrile species, accompanied by aliphatic hydrocarbons and a few aromatics compounds. The observed species are in agreement with the data from the recent Cassini-Huygens mission as well as from other laboratory setups capable of dissociating nitrogen and methane. This work emphasizes the probable importance of nitrogen-bearing compounds in the chemistry taking place in Titan’s atmosphere.Furthermore, a quantification of mono-nitriles with saturated alkyl chains has been performed relatively to hydrogen cyanide and shows a power law dependence in their concentration. This dependence is consistent with the Cassini-INMS data and Titan’s photochemical models.An empirical relationship has been extracted from our experimental data: [C_xH_2x−1N] = 100x⁻⁵, where x is the number of carbon atoms in the nitrile molecule. This relationship can be directly used in order to foretell the concentration of heavier nitriles induced by chemistry in Titan’s atmosphere.     

Ground-based measurements of the methane distribution on Titan

Using spectra taken with NIRSPEC (Near Infrared Spectrometer) and adaptive optics on the Keck II telescope, we resolved the latitudinal variation of the 3ν₂ band of CH₃D at 1.56 μm. As CH₃D is less abundant than CH₄ by a factor of 50±10×10^-5, these CH₃D lines do not saturate in Titan’s atmosphere, and are well characterized by laboratory measurements. Thus they do not suffer from the large uncertainties of the CH₄ lines that are weak enough to be unsaturated in Titan. Our measurements of the methane abundance are confined to the latitude range of 32°S-18°N and longitudes sampled by a 0.04″ slit centered at ∼195°W. The methane abundance below 10 km is constant to within 20% in the tropical atmosphere sampled by our observations, consistent with the low surface insolation and lack of surface methane [Griffith, C.A., McKay, C.P., Ferri, F., 2008. Astrophys. J. 687, L41-L44].     

Sounding of Titan’s atmosphere at submillimeter wavelengths from an orbiting spacecraft

An investigation of the capabilities and science goals of a submillimeter-wave heterodyne sounder onboard a Titan orbiter is presented. Based on a model of Titan’s submillimeter spectrum, and including realistic instrumental performances, we show that passive limb observations of Titan’s submillimeter radiation would bring novel and unique information on the dynamical and chemical state of Titan’s atmosphere, particularly in the so far poorly probed 500-900 km region. The 300-360, 540-660 and 1080-1280 GHz spectral ranges appear especially promising, and could be explored with an instrument equipped with a tunable local oscillator system. Vertical temperature profiles can be determined up to ∼1200 km using rotational lines of CH₄, CO, and HCN. Winds can be measured over the 200-1200 km altitude range with an accuracy of 3-5 m/s from Doppler shift measurements of any strong optically thin line. Numerous molecular species are accessible, including H₂O, NH₃, CH₃C₂H, CH₂NH, and several nitriles (HC₃N, HC₅N, CH₃CN, and C₂H₃CN). Many of them are expected to be detectable in a large fraction of the atmosphere and in some cases at all levels, providing an observational link between stratospheric and thermospheric chemistry. Isotopic variants of some of these species can also be measured, providing new measurements of H, C, N, and O isotopic ratios. Mapping of the thermal, wind, and composition fields, best achieved from a polar orbit and with an articulated antenna, would provide a new view of the couplings between chemistry and dynamics over an extended altitude range of Titan’s atmosphere. Additional science goals at Saturn and Enceladus are briefly discussed.     

Chemistry and evolution of Titan's atmosphere

The chemistry and evolution of Titan's atmosphere is reviewed in the light of the scientific findings from the Voyager mission. It is argued that the present N₂ atmosphere may be Titan's initial atmosphere rather than photochemically derived from an original NH₃ atmosphere. The escape rate of hydrogen from Titan is controlled by photochemical production from hydrocarbons. CH₄ is irreversibly converted to less hydrogen rich hydrocarbons, which over geologic time accumulate on the surface to a layer thickness of ～0.5 km. Magnetospheric electrons interacting with Titan's exosphere may dissociate enough N₂ into hot, escaping N atoms to remove ～0.2 of Titan's present atmosphere over geologic time. The energy dissipation of magnetospheric electrons exceeds solar e.u.v. energy deposition in Titan's atmosphere by an order of magnitude and is the principal driver of nitrogen photochemistry. The environmental conditions in Titan's upper atmosphere are favorable to building up complex molecules, particularly in the north polar cap region.     

Experimental and theoretical study of hydrocarbon photochemistry applied to Titan stratosphere

None of the Titan photochemical models currently available have been able to reproduce the full set of stratospheric molecular mixing ratios inferred from observations. In order to assess how well reaction sets describe hydrocarbon chemistry, theoretical modeling predictions were compared to the results of a laboratory experiment. A CH₄-C₂H₂ mixture was irradiated at 185 nm in an atmospheric simulation chamber and the evolution of the gas mixture was followed in situ and in real time by infrared spectroscopy. In parallel, a 0D theoretical model of the laboratory experiment was developed. A new reaction set describing Titan's chemistry was built and incorporated in the model. Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set was also used for comparison. The presence of small amounts of atmospheric O₂ in the experiment was properly accounted for and led us to suggest that oxygenated chemistry might be a source of C₂H₄ in Titan's atmosphere. With Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set, the model could not fit at all the experimental evolution of the compounds. This is explained by some of the choices made for crucial kinetic parameters such as the quantum yield of photolysis of C₂H₂. Also, the absence of some reactions led to the enhancement of pathways that would otherwise be negligible. For example, the lack of reactions between C₄H₄ and radicals induced an erroneously high photolysis rate for this species. With the reaction set built in this study, the model much better fits the experiment, especially when the “soot,” which includes C₄H₄, is recycled into C₂H₂. This shows that photochemistry of the larger species has a role in determining the lighter species concentrations and that considering that they are simply lost from the system is not a valid assumption. Including even an abridged set of C₄ + hydrocarbon reactions will be required in future photochemical models. Especially, photolysis rates and yields for C₂H₂, C₄H₂, and C₄H₄, are important parameters in need of a better determination.     

Analysis of Titan CH4 3.3 μm upper atmospheric emission as measured by Cassini/VIMS

After molecular nitrogen, methane is the most abundant species in Titan’s atmosphere and plays a major role in its energy budget and its chemistry. Methane has strong bands at 3.3 μm emitting mainly at daytime after absorption of solar radiation. This emission is strongly affected by non-local thermodynamic equilibrium (non-LTE) in Titan’s upper atmosphere and, hence, an accurate modeling of the non-LTE populations of the emitting vibrational levels is necessary for its analysis. We present a sophisticated and extensive non-LTE model which considers 22 CH₄ levels and takes into account all known excitation mechanisms in which they take part. Solar absorption is the major excitation process controlling the population of the v₃-quanta levels above 1000 km whereas the distribution of the vibrational energy within levels of similar energy through collisions with N₂ is also of importance below that altitude. CH₄-CH₄ vibrational exchange of v₄-quanta affects their population below 500 km. We found that the ν₃ → ground band dominates Titan’s 3.3 μm daytime limb radiance above 750 km whereas the ν₃ + ν₄ → ν₄ band does below that altitude and down to 300 km. The ν₃ + ν₂ → ν₂, the 2ν₃ → ν₃, and the ¹³CH₄ν₃ → ground bands each contribute from 5% to 8% at regions below 800 km. The ν₃ + 2ν₄ → 2ν₄and ν₂ + ν₃ + ν₄ → ν₂ + ν₄ bands each contribute from 2% to 5% below 650 km. Contributions from other CH₄ bands are negligible. We have used the non-LTE model to retrieve the CH₄ abundance from 500 to 1100 km in the southern hemisphere from Cassini-VIMS daytime measurements near 3.3 μm. Our retrievals show good agreement with previous measurements and model results, supporting a weak deviation from well mixed values from the lower atmosphere up to 1000 km.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

Temperature-dependent photoabsorption cross-sections of cyanoacetylene and diacetylene in the mid- and vacuum-UV: Application to Titan's atmosphere

Cyanoacetylene (HC₃N) and diacetylene (C₄H₂) play an important role in the photochemistry of Titan's atmosphere, in part because of their strong absorption between 110 and 180 nm. Accurate photoabsorption cross-sections at temperatures representative of Titan's atmosphere are required to interprete Cassini observations and to calculate photolysis rates used in photochemical models. Using synchrotron radiation as a tunable vacuum ultraviolet (VUV) light source, we have measured absolute photoabsorption cross-sections of C₄H₂ and HC₃N with a spectral resolution of 0.05 nm in the region between 80 and 225 nm and at different temperatures between 173 and 295 K. The measured cross-sections are used to model transmission spectra of Titan atmosphere in the VUV.     

Chemical reactions in the Titan’s troposphere during lightning

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.     

The composition of liquid methane-nitrogen aerosols in Titan’s lower atmosphere from Monte Carlo simulations

Molecular level Monte Carlo simulations have been performed with various model potentials for the CH₄-N₂ vapor-liquid equilibrium at conditions prevalent in the atmosphere of Saturn’s moon Titan. With a single potential parameter adjustment to reproduce the vapor-liquid equilibrium at a higher temperature, Monte Carlo simulations are in excellent agreement with available laboratory measurements. The results demonstrate the ability of simple pair potential models to describe phase equilibria with the requisite accuracy for atmospheric modeling, while keeping the number of adjustable parameters at a minimum. This allows for stable extrapolation beyond the range of available laboratory measurements into the supercooled region of the phase diagram, so that Monte Carlo simulations can serve as a reference to validate phenomenological models commonly used in atmospheric modeling. This is most important when the relevant region of the phase diagram lies outside the range of laboratory measurements as in the case of Titan. The present Monte Carlo simulations confirm the validity of phenomenological thermodynamic equations of state specifically designed for application to Titan. The validity extends well into the supercooled region of the phase diagram. The possible range of saturation levels of Titan’s troposphere above altitudes of 7 km is found to be completely determined by the remaining uncertainty of the most recent revision of the Cassini-Huygens data, yielding a saturation of 100 ± 6% with respect to CH₄-N₂ condensation up to an altitude of about 20 km.     

Evidence for layered methane clouds in Titan’s troposphere

Layered methane clouds in Titan’s troposphere with an upper methane ice cloud, a lower liquid methane-nitrogen cloud, and a gap in between were suggested from in situ measurements and ground-based observations. Here we report laboratory investigations under conditions that mimic Titan’s troposphere providing a detailed picture of the cloud layers. A solid methane cloud with a nitrogen content of less than 14% and a liquid methane-nitrogen cloud with a nitrogen content of ∼30% form above ∼19 km and below ∼16 km altitude, respectively. Contrary to previous assertions, long-lived supercooled liquid methane-nitrogen droplets can be sustained in the region in between. The results demonstrate that a cloud gap could only form in the presence of high amounts of other traces species (ethane nuclei, tholin particles, etc.).     

Methane evolution from UV-irradiated spacecraft materials under simulated martian conditions: Implications for the Mars Science Laboratory (MSL) mission

Fifteen organic and three inorganic compounds were tested for methane (CH₄) evolution under simulated martian conditions of 6.9 mbar; UVC (200-280 nm) flux of 4 W m⁻²; 20 °C; simulated optical depth of 0.1; and a Mars gas composition of CO₂ (95.3%), N₂ (2.7%), Ar (1.7%), O₂ (0.13%), and water vapor (0.03%). All three inorganic compounds (i.e., NaCl, CaCO₃, graphite) failed to evolve methane at the minimum detection level 0.5 ppm, or above. In contrast, all organic compounds evolved methane when exposed to UV irradiation under simulated martian conditions. The polycyclic aromatic hydrocarbon, pyrene, released the most methane per unit of time at 0.175 nmol CH₄ g⁻¹ h⁻¹, and a spectral reflectance target material used for the MER rovers and Phoenix lander released the least methane at 0.00065 nmol CH₄ cm⁻² h⁻¹. Methane was also released from UV-killed bacterial endospores of Bacillus subtilis. Although all organic compounds evolved methane when irradiated with UV photons under martian conditions, the concentrations of residual organics, biogenic signature molecules, and dead microbial cells should be relatively low on the exterior surfaces of the MSL rover, and, thus, not significant sources of methane contamination. In contrast, kapton tape was found to evolve methane at the rate of 0.00165 nmol CH₄ cm⁻² h⁻¹ (16.5 nmol m⁻² h⁻¹) under the UV and martian conditions tested. Although the evolution of methane from kapton tape was found to decline over time, the large amount of kapton tape used on the MSL rover (lower bound estimated at 3 m²) is likely to create a significant source of terrestrial methane contamination during the early part of the mission.     

Remote sensing D/H ratios in methane ice: Temperature-dependent absorption coefficients of CH3D in methane ice and in nitrogen ice

The existence of strong absorption bands of singly deuterated methane (CH₃D) at wavelengths where normal methane (CH₄) absorbs comparatively weakly could enable remote measurement of D/H ratios in methane ice on outer Solar System bodies. We performed laboratory transmission spectroscopy experiments, recording spectra at wavelengths from 1 to 6 μm to study CH₃D bands at 2.47, 2.87, and 4.56 μm, wavelengths where ordinary methane absorption is weak. We report temperature-dependent absorption coefficients of these bands when the CH₃D is diluted in CH₄ ice and also when it is dissolved in N₂ ice, and describe how these absorption coefficients can be combined with data from the literature to simulate arbitrary D/H ratio absorption coefficients for CH₄ ice and for CH₄ in N₂ ice. We anticipate these results motivating new telescopic observations to measure D/H ratios in CH₄ ice on Triton, Pluto, Eris, and Makemake.     

Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

Meridional distribution of CH3C2H and C4H2 in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.     

Isotopic fractionation of methane in the martian atmosphere

The existence of methane in the martian atmosphere may be an indicator of subsurface life. Biological processes are known to fractionate the common isotopologues of methane, and hence measuring these isotopic ratios may yield constraints on the nature of the methane source. Any measurement of the isotopic ratios of atmospheric methane must consider the additional fractionation due to photochemistry in order to quantify the isotopic ratios of the source. Using a one-dimensional photochemical model, we find that photochemistry has a small (4.5‰) contribution to δ¹³C(CH₄) but has a large (114‰) contribution to δD(CH₄). Confirmation of these fractionation values will require additional laboratory data on key model inputs, particularly the ultraviolet absorption cross sections of ¹³CH₄ and kinetic rate coefficients for the reactions of ¹³CH₄ and CH₃D with OH and O(¹D) at pressures and temperatures relevant to the martian atmosphere.     

New laboratory measurements of CH4 in Titan's conditions and a reanalysis of the DISR near-surface spectra at the Huygens landing site

Laboratory spectra of methane-nitrogen mixtures have been recorded in the near-infrared range (1.0-1.65 μm) in conditions similar to Titan's near surface, to facilitate the interpretation of the DISR/DLIS (DISR—Descent Imager/Spectral Radiometer) spectra taken during the last phase of the descent of the Huygens Probe, when the surface was illuminated by a surface-science lamp. We used a 0.03 cm⁻¹ spectral resolution, adequate to resolve the lines at high pressure (p_N2∼1.5 bar). By comparing the laboratory spectra with synthetic calculations in the well-studied ν₂+2ν₃ band (7515-7620 cm⁻¹), we determine a methane absorption column density of 178±20 cm atm and a temperature of 118±10 K in our experiment. From this, we derive the methane absorption coefficients over 1.0-1.65 μm with a 0.03 cm⁻¹ sampling, allowing for the extrapolation of the results to any other methane column density under the relevant pressure and temperature conditions. We then revisit the calibration and analysis of the Titan “lamp-on” DLIS spectra. We infer a 5.1±0.8% methane-mixing ratio in the first 25 m of Titan's atmosphere. The CH₄ mixing ratio measured 90 s after landing from a distance of 45 cm is found to be 0.92±0.25 times this value, thus showing no post-landing outgassing of methane in excess of ∼20%. Finally, we determine the surface reflectivity as seen between 25 m and 45 cm and find that the 1500 nm absorption band is deeper in the post-landing spectrum as compared to pre-landing.     

Atmospheric chemistry on Venus, Earth, and Mars: Main features and comparison

This paper deals with two common problems and then considers major aspects of chemistry in the atmospheres of Mars and Venus. (1) The atmospheres of the terrestrial planets have similar origins but different evolutionary pathways because of the different masses and distances to the Sun. Venus lost its water by hydrodynamic escape, Earth lost CO₂ that formed carbonates and is strongly affected by life, Mars lost water in the reaction with iron and then most of the atmosphere by the intense meteorite impacts. (2) In spite of the higher solar radiation on Venus, its thermospheric temperatures are similar to those on Mars because of the greater gravity acceleration and the higher production of O by photolysis of CO₂. O stimulates cooling by the emission at 15 μm in the collisions with CO₂. (3) There is a great progress in the observations of photochemical tracers and minor constituents on Mars in the current decade. This progress is supported by progress in photochemical modeling, especially by photochemical GCMs. Main results in these areas are briefly discussed. The problem of methane presents the controversial aspects of its variations and origin. The reported variations of methane cannot be explained by the existing data on gas-phase and heterogeneous chemistry. The lack of current volcanism, SO₂, and warm spots on Mars favor the biological origin of methane. (4) Venus’ chemistry is rich and covers a wide range of temperatures and pressures and many species. Photochemical models for the middle atmosphere (58-112 km), for the nighttime atmosphere and night airglow at 80-130 km, and the kinetic model for the lower atmosphere are briefly discussed.     

Titan’s atmosphere: An optimal gas mixture for aerosol production?

Here we present the first quantitative study of the gas to solid particle conversion in a Radio Frequency dusty plasma experiment simulating the complex atmospheric reactivity on Titan.Analogs of Titan’s aerosols have been produced in different N₂-CH₄ gas mixtures. Using in situ mass spectrometry, it has been found that, by varying the initial methane concentration, aerosols could be produced in methane steady state concentrations similar to Titan’s atmospheric conditions. In our experiment, an initial ∼5% methane concentration is necessary to ensure a ∼1.5% methane steady state concentration in the plasma.The tholin mass production rate has been quantified as a function of the initial methane concentration. A maximum was found for a steady state CH₄ concentration in agreement with Titan’s atmospheric CH₄ concentrations. At this maximum, the tholin C/N ratio is about 1.45 and the carbon gas to solid conversion yield is about 35%.We have modeled the mass production rate by a parabolic function, highlighting two competitive chemical regimes controlling the tholin production efficiency: an efficient growth process which is proportional to the methane consumption, and an inhibiting process which opposes the growth process and dominates it for initial methane concentrations higher than ∼5%. To explain these two opposite effects, we propose two mechanisms: one involving HCN patterns in the tholins for the growth process, and one involving the increasing amount of atomic hydrogen in the plasma as well as the increase in aliphatic contributions in the tholins for the inhibiting process. This study highlights new routes for understanding the chemical growth of the organic aerosols in Titan’s atmosphere.