Abstract
At thermodynamic equilibrium, gas hydrates are arranged in the pore
space of host sediments to minimize free energy, including the energy of
interfaces. Through an analogy with frozen soil, we show that free
energy minimization in hydrate-bearing sediments requires the presence
of a water film of finite thickness separating hydrate from the sediment
grains. The thickness of this premelted layer may be predicted from a
balance of intermolecular forces acting across the film. Temperature and
porewater salinity are the strongest determiners of premelted layer
thickness. We show that, at temperatures and salinities typical of the
subsurface or commonly used in laboratory investigations of
hydrate-bearing porous media, the premelted layer varies in thickness
from microns to sub-nanometer, with thicker layers corresponding to
lower salinities and/or higher temperatures. Balance of intermolecular
forces predicts that hydrate will be completely nonwetting on
hydrophilic surfaces, including silica. We also show that flow through
premelted layers may be a significant component of the permeability of
hydrate-bearing sediments, particularly at moderate to high hydrate
saturation (>60%); and that the electrical conductivity of
the premelted layer at needs to be accounted for in assessments of
hydrate abundance from subsurface resistivity logs. This work highlights
the importance of considering premelted layers when predicting the
effects of hydrate on sediment properties.