Geology topics

Wyatt L. Du Frane

Publications and source records attributed to Wyatt L. Du Frane.

6 recordsLinked to original sources

USGS2021

Electrical properties of carbon dioxide hydrate: Implications for monitoring CO2 in the gas hydrate stability zone

CO 2 and CH 4 clathrate hydrates are of keen interest for energy and carbon cycle considerations. While both typically form on Earth as cubic structure I (sI), we find that pure CO 2 hydrate exhibits over an order of magnitude higher electrical conductivity ( σ ) than pure CH 4 hydrate at geologically relevant temperatures. The conductivity was obtained from frequency-dependent impedance ( Z ) measurements made on polycrystalline CO 2 hydrate (CO 2 ·6.0 ± 0.2H 2 O by methods here) with 25% gas-filled porosity, compared with CH 4 hydrate (CH 4 ·5.9H 2 O) formed and measured in the same apparatus and exhibiting closely matching grain characteristics. The conductivity of CO 2 hydrate is 6.5 × 10 −4 S/m at 273K with an activation energy ( E a ) of 46.5 kJ/mol at 260–281 K, compared with ∼5 × 10 −5 S/m and 34.8 kJ/m for CH 4 hydrate. Equivalent circuit modeling indicates that different pathways govern conduction in CO 2 versus CH 4 hydrate. Results show promise for use of electromagnetic methods in monitoring CO 2 hydrate formation in certain natural settings or in CO 2 /CH 4 exchange efforts.

Geophysical Research Letters↗

USGS2021

Electrical conductivity of pure CO2 hydrate and CH4 hydrate: Role of the guest molecule

To conclude a series of DOE-sponsored laboratory experiments in which our team measured electrical conductivity of methane hydrate-bearing samples, we investigated electrical conductivity of CO2 hydrate for direct comparison with methane hydrate. Their surprisingly distinct signatures could aid in the monitoring of CO2 in certain deep marine environments. To the best of our knowledge these are the first reported conductivity measurements on pure, polycrystalline CO2 hydrate.

Newsletter↗

USGS2020

Laboratory electrical conductivity of marine gas hydrate

Methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate, we infer by contaminant NaCl contributing to conduction in hydrate, to values in agreement with resistivities observed in well logs through hydrate The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater by an amount consistent with Archie's Law. All samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which show good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure‐induced dissociation supports previous conclusions that sediment increases dissociation rate.

Geophysical Research Letters↗

USGS2019

The effect of brine on the electrical properties of methane hydrate

Gas hydrates possess lower electrical conductivity (inverse of resistivity) than either seawater or ice, but higher than clastic silts and sands, such that electromagnetic methods can be employed to help identify their natural formation in marine and permafrost environments. Controlled laboratory studies offer a means to isolate and quantify the effects of changing individual components within gas‐hydrate‐bearing systems, in turn yielding insight into the behavior of natural systems. Here we investigate the electrical properties of polycrystalline methane hydrate with ≥25% gas‐filled porosity and in mixture with brine. Initially, pure methane hydrate was synthesized from H 2 O ice and CH 4 gas while undergoing electrical impedance measurement, then partially dissociated to assess the effects of pure pore water accumulation on electrical conductivity. Methane hydrate + brine mixtures were then formed by either adding NaCl (0.25–2.5 wt %) to high‐purity ice or by using frozen seawater as a reactant. Conductivity was obtained from impedance measurements made in situ throughout synthesis while temperature cycled between +15 °C and −25 °C. Several possible conduction mechanisms were subsequently determined using equivalent circuit modeling. Samples with low NaCl concentration show a doping/impurity effect and a log linear conductivity response as a function of temperature. For higher salt content samples, conductivity increases exponentially with temperature and the log linear relationship no longer holds; instead, we observe phase changes within the samples that follow NaCl–H 2 O–CH 4 phase equilibrium predictions. Final samples were quenched in liquid nitrogen and imaged by cryogenic scanning electron microscopy (cryo‐SEM) to assess grain‐scale characteristics.

Journal of Geophysical Research↗

USGS2015

Electrical properties of methane hydrate + sediment mixtures

Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. Toward this goal, we built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity ( σ ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EM field surveys. Here we report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. These results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.

Journal of Geophysical Research↗

USGS2011

Electrical properties of methane hydrate + sediment mixtures

As part of our DOE-funded proposal to characterize gas hydrate in the Gulf of Mexico using marine electromagnetic methods, a collaboration between SIO, LLNL, and USGS with the goal of measuring the electrical properties of lab-created methane (CH 4 ) hydrate and sediment mixtures was formed. We examined samples with known characteristics to better relate electrical properties measured in the field to specific gas hydrate concentration and distribution patterns. Here we discuss first-ever electrical conductivity (σ) measurements on unmixed CH 4 hydrate (Du Frane et al., 2011): 6 x 10-5 S/m at 5 °C, which is ~5 orders of magnitude lower than seawater. This difference allows electromagnetic (EM) techniques to distinguish highly resistive gas hydrate deposits from conductive water saturated sediments in EM field surveys. More recently, we performed measurements on CH 4 hydrate mixed with sediment and we also discuss those initial findings here. Our results on samples free of liquid water are important for predicting conductivity of sediments with pores highly saturated with gas hydrate, and are an essential starting point for comprehensive mixing models.

Fire in the Ice: NETL Methane Hydrate Newsletter↗