Summary of the history and research of the U.S. Geological Survey gas hydrate properties laboratory in Menlo Park, California, active from 1993 to 2022

Abstract

The U.S. Geological Survey (USGS) Clathrate Hydrate Properties Project, active from 1993 to 2022 in Menlo Park, California, stemmed from an earlier project on the properties of planetary ices supported by the National Aeronautics and Space Administration’s (NASA’s) Planetary Geology and Geophysics Program. We took a material science approach in both projects, emphasizing chemical purity of samples, having controlled grain size and grain texture, and having verified crystal structures and phase relations. A foundational contribution from our USGS Gas Hydrate Properties Laboratory (GHPL) was in demonstrating the ability to reproducibly create such pure clathrate hydrate samples for study. Clathrate sample synthesis was achieved by heating sieved and weighed pure granular water ice in the presence of cold clathrate-forming gas or liquid. During heating, the ice melts at the grain scale and reacts with the gas to form clathrate. The resulting material has the desired uniformity and purity, with known intergranular porosity; our subsequent measurements showed that these clathrates exhibited the established clathrate structures and phase relations. This novel synthesis method was successful in creating clathrates of pure methane, ethane, propane, carbon dioxide, and multi-component gases. By mixing sand or silt with granular ice, we were also able to make clathrate-sediment aggregates with controlled grain textures. This simple method, adopted by many others in the community, permitted us to measure the physical and chemical properties of well-characterized and well-crystallized clathrates and clathrate/sediment aggregates. At about the same time, we adapted conventional scanning electron microscopy to cryogenic conditions for analysis of grain-scale characteristics of clathrates made in the GHPL as well as those collected from nature by drill core. The uniformity and reproducibility of our samples also allowed us to investigate how clathrates respond to environmental changes in chemistry, temperature, and pressure: we measured chemical exchange rates with dissolved gas species—such as noble gases and chlorofluorocarbons—as well as rates of clathrate dissolution and decomposition. These advances include the first accurate mapping of the conditions that promote the remarkable process of “anomalous preservation” at room pressure, a metastability that offers potential application for low-cost and safe transportation of natural gas from gas fields far from pipelines. Another advancement stemming from the GHPL was the compaction of as-synthesized porous clathrates to nearly full density by applying external pressure using three different techniques. Compaction allows for high-accuracy measurements of many fundamental physical and chemical properties of these materials, such as elastic wavespeeds and moduli, complete thermal properties, decomposition rates, thermal expansion, and clathrate equations of state. These properties and others, in turn, have helped USGS scientists to interpret geophysical well logs and active geophysical surveys, as well as model the rates of gas production from hydrate deposits in nature. Studying this class of icy minerals that occur in abundance on Earth and in the outer solar system has been a fascinating laboratory journey. Here, we summarize the history and major findings of the USGS GHPL in Menlo Park, including both in-house research as well as findings from the synergistic collaborations with other agencies and institutes that were key to the success of our laboratory. The Menlo Park GHPL was more formally incorporated within the USGS Gas Hydrates Project, a collaboration among multiple USGS Science Centers, in the early 2000s under the leadership of Deborah Hutchinson, and now under the leadership of Carolyn Ruppel and Timothy Collett.