Multi-Parametric Devices with Innovative Solid Electrodes for Long-Term Monitoring of pH and Redox-Potential of the actual pore water of COx formation in a future Nuclear Waste Repository

Abstract : We present innovative electrochemical probes for the monitoring of pH and redox potential in pore water in near-field rocks of a future deep geological radioactive waste repository at 500 m depth within the clayey Callovian-Oxfordian (COx) formation. The conceived experimental setup assembles two multi-parameter probes (MPPs), used together throughout two series of several months duration measurements in situ into the underground research laboratory of Andra at Bure, France. The two MPPs, connected in series, were up-flow fed with actual pore water of COx formation during several with a very low flowrate. Each MPP is composed of different individual probes containing the following: two monocrystalline antimony electrodes for pH sensing; eight AgCl/Ag-based reference or Cl − selective electrodes; four Ag 2 S/Ag-based reference or S 2− selective electrodes; eight platinum electrodes; two gold electrodes; two glassy-carbon electrodes; two ruthenium and two inox 316 electrodes, for redox potential measurements. The Open Circuit Potential (OCP) measurements of the developed sensors under different conditions and in quasi-actual conditions were compared to conventional reference electrode and pH electrodes in terms of performance, reliability and robustness and allowed to create calibration curves. Conductivity measurements, carried out along MPPs, will not be presented here. Overall, the conceived bundle of electrodes as designed works reliably during a timescale that is promising for monitoring the COx formation during its envisaged use for hosting a nuclear waste repository.