Underground Hydrogen Storage (UHS) provides a large-scale and safe solution to balance the fluctuations in energy production from renewable sources and energy consumption but requires a proper and detailed characterization of the candidate reservoirs. The scope of this study was to estimate the hydrogen diffusion coefficient for real caprock samples from two natural gas storage reservoirs that are candidates for underground hydrogen storage. A significant number of adsorption/desorption tests were carried out using a Dynamic Gravimetric Vapor/Gas Sorption System. A total of 15 samples were tested at the reservoir temperature of 45 °C and using both hydrogen and methane. For each sample, two tests were performed with the same gas. Each test included four partial pressure steps of sorption alternated with desorption. After applying overshooting and buoyancy corrections, the data were then interpreted using the early time approximation of the solution to the diffusion equation. Each interpretable partial pressure step provided a value of the diffusion coefficient. In total, more than 90 estimations of the diffusion coefficient out of 120 partial pressure steps were available, allowing a thorough comparison between the diffusion of hydrogen and methane: hydrogen in the range of 1 × 10⁻¹⁰ m²/s to 6 × 10⁻⁸ m²/s and methane in the range of 9 × 10⁻¹⁰ m²/s to 2 × 10⁻⁸ m²/s. The diffusion coefficients measured on wet samples are 2 times lower compared to those measured on dry samples. Hysteresis in hydrogen adsorption/desorption was also observed.

Harmonic Pulse Testing (HPT) has been developed as a type of well testing applicable during ongoing field operations because a pulsed signal is superimposed on background pressure trend. Its purpose is to determine well and formation parameters such as wellbore storage, skin, permeability, and boundaries within the investigated volume. Compared to conventional well testing, HPT requires more time to investigate the same reservoir volume. The advantage is that it does not require the interruption of well and reservoir injection/production before and/or during the test because it allows the extraction of an interpretable periodic signal from measured pressure potentially affected by interference. This makes it an ideal monitoring tool. Interpretation is streamlined through diagnostic plots mimicking conventional well test interpretation methods. To this end, analytical solutions in the frequency domain are available. The methodology was applied to monitor stimulation operations performed at an Enhanced Geothermal System site in Pohang, Korea. The activities were divided into two steps: first, a preliminary sequence of tests, injection/fall‐off, and two HPTs, characterized by low injection rates and dedicated to estimate permeability prior to stimulation operations, and then stimulation sequence characterized by a higher injection rate. During the stimulation operations other HPT were performed to monitor formation properties behavior. The interpretation of HPT data through the derivative approach implemented in the frequency domain provided reliable results in agreement with the injection test. Moreover, it provided an estimation of hydraulic properties without cessation of stimulation operations, thus confirming the effectiveness of HPT application for monitoring purposes.