High-Precision Performance of a Full-Ocean-Depth pH Sensor: Calibration and Assessment under Simulated Hadal Pressure...

Real-time in situ pH monitoring in the hadal zone is essential for resolving deep-sea carbon dynamics but is severely challenged by extreme hydrostatic pressures and complex biochemical environments. Current sensors often lack the necessary robustness and calibration protocols for full-ocean-depth applications. To address these challenges, we developed a solid-state electrochemical pH sensor system comprising a fouling-resistant sulfonated poly(ether ether ketone)/ionic liquid composite IrO_x (SP/IL-IrO_x) working electrode and a pressure-tolerant silica-stabilized ionic liquid (Si-StabIL) reference electrode. Using Tris-artificial seawater (Tris-AS) buffers, we established a standardized high-pressure calibration protocol and systematically evaluated sensor performance over the full-ocean-depth pressure range (0.1-120 MPa) under simulated hadal pressure conditions. The sensor exhibited near-Nernstian sensitivity with high reversibility and repeatability, with potential deviations of no more than 1.6 mV, corresponding to less than 0.03 pH units across the investigated pressure range. Long-term reliability was demonstrated by a minimal drift of only 0.01 pH units during continuous operation in the Tris-AS buffer at 120 MPa for 65 h. Crucially, the sensor captured the nonlinear, pressure-driven acidification of simulated hadal-zone seawater during a 7 day pressurization experiment while maintaining stable response in calibration buffers. These results demonstrate the robustness of the sensor system and provide an experimental basis for calibration and pH assessment under simulated full-ocean-depth pressure conditions.