Methane hydrate is thought to have been the dominant methane-containing phase in the nebula from which Saturn, Uranus, Neptune and their major moons formed. It accordingly plays an important role in formation models of Titan, Saturn's largest moon. Current understanding assumes that methane hydrate dissociates into ice and free methane in the pressure range 1-2 GPa (10-20 kbar), consistent with some theoretical and experimental studies. But such pressure-induced dissociation would have led to the early loss of methane from Titan's interior to its atmosphere, where it would rapidly have been destroyed by photochemical processes. This is difficult to reconcile with the observed presence of significant amounts of methane in Titan's present atmosphere. Here we report neutron and synchrotron X-ray diffraction studies that determine the thermodynamic behaviour of methane hydrate at pressures up to 10 GPa. We find structural transitions at about 1 and 2 GPa to new hydrate phases which remain stable to at least 10 GPa. This implies that the methane in the primordial core of Titan remained in stable hydrate phases throughout differentiation, eventually forming a layer of methane clathrate approximately 100 km thick within the ice mantle. This layer is a plausible source for the continuing replenishment of Titan's atmospheric methane.

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It has long been known that crystalline hydrates are formed by many simple gases that do not interact strongly with water, and in most cases the gas molecules or atoms occupy 'cages' formed by a framework of water molecules. The majority of these gas hydrates adopt one of two cubic cage structures and are called clathrate hydrates. Notable exceptions are hydrogen and helium which form 'exotic' hydrates with structures based on ice structures, rather than clathrate hydrates, even at low pressures. Clathrate hydrates have been extensively studied because they occur widely in nature, have important industrial applications, and provide insight into water-guest hydrophobic interactions. Until recently, the expectation-based on calculations-had been that all clathrate hydrates were dissociated into ice and gas by the application of pressures of 1 GPa or so. However, over the past five years, studies have shown that this view is incorrect. Instead, all the systems so far studied undergo structural rearrangement to other, new types of hydrate structure that remain stable to much higher pressures than had been thought possible. In this paper we review work on gas hydrates at pressures above 0.5 GPa, identify common trends in transformations and structures, and note areas of uncertainty where further work is needed.

The structure of a new methane hydrate has been solved at 3 GPa from neutron and x-ray powder diffraction data. It is a dihydrate in which a 3D H-bonded network of water molecules forms channels surrounding the methane molecules. The network is closely related to that of ice-Ih and the methane-water system appears to be the first in which a cage clathrate hydrate is transformed into an ice-related hydrate (a "filled ice").