In Situ Detection of Species Relevant to the Carbon Cycle in Seawater with Submersible Potentiometric Probes

We report on the development of a submersible probe for the simultaneous potentiometric detection of carbonate, calcium, and pH in seawater. All-solid-state electrodes incorporating nanomaterials provide an adequate response time (<10 s), stability (drifts of <0.9 mV h(-1)), reproducibility (calibration parameter deviation of <0.7%), and accuracy (deviation of <8% compared to reference techniques) for real-time monitoring of seawater using a flow system. The functioning of the deployable prototype was checked in an outdoor mesocosm and via long-term monitoring in Genoa Harbor. The electrodes worked properly for 3 weeks, and the system demonstrated the capability to autonomously operate with routines for repetitive measurements, data storage, and management. In situ profiles observed in Genoa Harbor and Arcachon Bay were validated using on site and ex situ techniques. The validation of in situ-detected carbonate is a challenge because both re-equilibration of the sample with atmospheric CO2 and the use of apparent thermodynamic constants for speciation calculations lead to some differences (<20% deviation). The submersible probe is a promising tool for obtaining rapid and trustworthy information about chemical levels in marine systems. Moreover, the fluidic approach allows for the integration of other ion sensors that may require sample pretreatment.