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International audience; Spectral induced polarization (SIP) has the potential for monitoring reactive processes in the subsurface. While strong SIP responses have been measured in response to calcite precipitation, their origin and mechanism remain debated. Here we present a novel geo-electrical millifluidic setup designed to observe microscale reactive transport processes while performing SIP measurements. We induced calcite precipitation by injecting two reactive solutions into a porous medium, which led to highly localized precipitates at the mixing interface. Strikingly, the amplitude of the SIP response increased by 340% during the last 7% increase in precipitate volume. Furthermore, while the peak frequency in SIP response varied spatially over 1 order of magnitude, the crystal size range was similar along the front, contradicting assumptions in the classical grain polarization model. We argue that the SIP response of calcite precipitation in such mixing fronts is governed by Maxwell-Wagner polarization due to the establishment of a precipitate wall. Numerical simulations of the electric field suggested that spatial variation in peak frequency was related to the macroscopic shape of the front. These findings provide new insights into the SIP response of calcite precipitation and highlight the potential of geoelectrical millifluidics for understanding and modeling electrical signatures of reactive transport processes.

International audience; Spectral induced polarization (SIP) has shown potential to detect subsurface reactive transport processes. However, previous laboratory experiments could not associate the SIP response with the temporal development and spatial distribution of reactive transport processes in detail due to the opaque nature of porous media. We developed a novel experimental setup that consists of a millimeter scale 2D transparent porous medium and electrodes for SIP measurements to visually observe reactive transport processes down to the pore scale while performing SIP measurements (i.e. a 2D millifluidic setup). We used this setup to investigate the SIP response of calcite precipitation (CaCO₃). The image analysis and SIP measurements highlight that the SIP response does not necessarily represent the total mass of calcite precipitation in the measurement region. In addition, we numerically simulated the electric field distribution based on the observed calcite precipitation. The results suggested that the heterogeneous distribution of calcite precipitation within the investigated volume had an important influence on the SIP response. Given the heterogeneous and localized nature of many reactive processes, these findings clearly demonstrate the importance of investigating sub-resolution reactive processes for SIP measurements. The proposed novel experimental setup was shown to be suitable for this purpose.

SUMMARY Induced calcite precipitation is used in geotechnics to modify the mechanical and hydrological properties of the underground. Laboratory experiments have shown that spectral induced polarization (SIP) measurements can detect calcite precipitation. However, the results of previous studies investigating the SIP response of calcite precipitation were not fully consistent. This study aims to investigate how the SIP response of calcite depends on solute concentration to explain the differences in SIP response observed in previous studies. A four-phase experiment with SIP measurements on a column filled with sand was performed. In phase I, calcite precipitation was generated for a period of 12 d by co-injecting Na2CO3 and CaCl2 solutions through two different ports. This resulted in a well-defined calcite precipitation front, which was associated with an increase in the imaginary part of the conductivity ($\sigma ^{\prime\prime}$). In phase II, diluted solutions were injected into the column. This resulted in a clear decrease in $\sigma ^{\prime\prime}$. In phase III, the injection of the two solutions was stopped while calcite precipitation continued and solute concentrations in the mixing zone decreased. Again, this decreased $\sigma ^{\prime\prime}$. Finally, the injection rate of the Na2CO3 solution was reduced relative to that of the CaCl2 solution in phase IV. This resulted in a shift of the mixing zone away from the calcite precipitation front established in phase I and an associated decrease of $\sigma ^{\prime\prime}$. These results imply that the SIP response of calcite is highly sensitive to the solute concentration near the precipitates, which may explain previously reported conflicting results.

Landfill sites are significant sources of methane gas globally. Understanding the temporal variabilities of methane emissions from landfill sites is necessary for estimating such emissions. In this study, an automated monitoring system was used to monitor methane emission flux and concentration on daily and hourly time scales at a landfill site. Measured methane emission fluxes were almost negligible in the studied area. However, methane concentration at landfill surface at nighttime was significantly higher than those in the daytime, which demonstrates the importance of investigating methane emissions at an hourly time scale, including during nighttime. The daily and hourly variations in methane concentration were well correlated with either soil temperature or volumetric water content near the surface. The obtained relations indicate that the automated monitoring system measurements can facilitate a more comprehensive understanding of the methane emission mechanisms at different time scales.