In this Account, we highlight recent work in the developing field of mineralogy of Saturn’s moon Titan, focusing on binary co-crystals of small organic molecules. Titan has a massive inventory of organic molecules on its surface that are formed via photochemistry in the atmosphere and likely processing on the surface as well. Physical processes both in the atmosphere and on the surface can lead to molecules interacting at cryogenic temperatures. Recent laboratory work has demonstrated that co-crystals between two or more molecules can form under these conditions. In the organic-rich environment of Titan, such co-crystals are naturally occurring minerals and a critical area of research to understand the physical, chemical, and possibly even biological and prebiotic processes occurring in this alien world. With a future NASA mission, Dragonfly, slated to land on Titan in the next decade, much work is needed to understand organic mineralogy in order to properly interpret the data from this and past Titan missions, such as Cassini-Huygens. By cataloging Titan minerals and their properties, we can begin to connect these behaviors to large-scale surface features observed on Titan (labyrinth terrain, lake evaporites, karst, dunes, etc.), and possible processes leading to their formation (erosion, deposition, etc.). To date, seven co-crystals (aside from clathrates and hydrates) have been experimentally reported to form under Titan-relevant conditions, with an eighth predicted by theoretical modeling. This Account will summarize the formation and properties of these cryominerals and discuss the implications for surface processes on Titan. Enhanced thermal expansion and decreased crystal size, for example, may lead to fracturing and/or more rapid erosion of co-crystal-based deposits; density changes upon co-crystal formation may also play a role in organic diagenesis and metamorphism on Titan. Some cryominerals with stability only under certain conditions may preserve the evidence of Titan’s history, such as cryovolcanic activity, ethane fluvial/pluvial exposure, and outgassing of CO₂ from the interior of the moon. In this Account, we will also highlight areas of future work, such as the characterization of pure molecular solids and the search for ternary (and more complex) co-crystals. We note that on Titan, organic chemistry dominates, which gives a unique opportunity for chemists to play an even more significant role in planetary science discoveries and likewise in discoveries motivated by planetary science to inform fundamental organic and physical chemistry research.

The composition of Europa’s subsurface ocean is a critical determinant of its habitability. However, our current understanding of the ocean composition is limited to its expression on the surface. This work investigates experimentally the composition of mixed sodium–magnesium–sulfate–chloride solutions when frozen to 100 K, simulating conditions that likely occur as ocean fluids are emplaced onto Europa’s surface. Micro-Raman spectroscopy is used to characterize phase composition of the frozen brines at 100 K. Our results show that solutions containing Na⁺, Cl⁻, Mg²⁺, and preferentially crystallize into Na₂SO₄ and MgCl₂ hydrated minerals upon freezing, even at elevated [Mg²⁺]/[Na⁺] ratios. The detection of epsomite (MgSO₄•7H₂O) on Europa’s surface, if confirmed, may thus imply a relatively sodium-poor ocean composition or a radiolytic process that converts MgCl₂ to MgSO₄ as suggested by Brown & Hand. The formation of NaCl on the surface, while dependent upon a number of factors such as freezing rate, may indicate an ocean significantly more concentrated in sodium than in magnesium.

Liquid ethane is present in the lakes and seas observed on Titan's surface by the Cassini‐Huygens mission. While interaction between liquid hydrocarbons and water ice is expected to result in the formation of clathrate hydrates, such reaction (and its kinetics) has not yet been demonstrated for cryogenic liquids under relevant planetary conditions. In this paper, we report the first experimental evidence for rapid formation of clathrates upon direct contact of liquid ethane with water ice at 1 bar using micro‐Raman spectroscopy. Kinetics experiments conducted in the temperature range 150–173 K yield an activation energy of 14.8 ± 2.2 kJ/mol, which is suggestive of a diffusion‐controlled mechanism for clathrate formation. This implies that a clathrate reservoir can form within seasonal time scales on Titan if liquid ethane comes into contact with a pre‐existing icy bedrock, which may hold important implications for the structure and dynamics of Titan's crust and its global evolution.

Benzene is found on Titan and is a likely constituent of the putative evaporite deposits formed around the hydrocarbon lakes. We have recently demonstrated the formation of a benzene‐ethane co‐crystal under Titan‐like surface conditions. Here we investigate the kinetics of formation of this new structure as a function of temperature. We show that the formation process would reach completion under Titan surface conditions in ~18 h and that benzene precipitates from liquid ethane as the co‐crystal. This suggests that benzene‐rich evaporite basins around ethane/methane lakes and seas may not contain pure crystalline benzene, but instead benzene‐ethane co‐crystals. This co‐crystalline form of benzene with ethane represents a new class of materials for Titan's surface, analogous to hydrated minerals on Earth. This new structure may also influence evaporite characteristics such as particle size, dissolution rate, and infrared spectral properties.