The aim of this work is to highlight the potential of using a modified gold electrode with controlled quantity of silver nanoparticles as a working electrode to detect low concentrations of nitrate in chloride solutions. Optimal charge for silver deposition has been determined to obtain the highest signal for the nitrate reduction as the electrocatalytic properties of the bimetallic electrode were directly influenced by its composition. According to the Volcano plot obtained the charge chosen was −52 μC for a 3 mm diameter electrode, corresponding to 4.6×1015 Ag atoms cm−2. It has been shown that dioxygen did not participate to the nitrate reduction mechanism. In order to decrease the limit of quantification, square wave voltammetry was preferred to less sensitive cyclic voltammetry. Nitrate was quantified in chloride solutions in the concentration range found in the open ocean, i. e. 0.39–50 μmol L−1 with a good linear regression (R2=0.9969). The stability of the bimetallic Au−Ag systems has been evaluated and showed almost no difference on the signal recorded over a 26 days period which is suitable to consider an in situ sensor development for marine applications.

An electrochemical sensor is proposed to measure silicate concentration, in situ, in the ocean without any addition of liquid reagent. From the analytical principle to the laboratory prototype toward the first in situ, immersible sensor, the evolution of the mechanical design is presented and discussed. The developed in situ electronics were compared to the commercial potentiostat and gave promising results to detect low silicate signals with a limit of quantification of 1 µmol L −1 .The flow rate of the pump appeared to be a crucial parameter in order to transfer the silicomolybdic complex formed from the "complexation cell" to the "detection cell" without dilution as well as to fill and rinse the whole circuit. The study of temperature effect revealed no influence on the electrochemical signal between ∼7 • and ∼21 • C. Finally the sensor was successfully deployed for the very first time on a mooring off Coquimbo, Chile and also integrated onto a PROVOR profiling float in the Mediterranean Sea off Villefranche-sur-Mer, France. The data collected and/or sent through satellite were in good agreement with the 2 reference samples and previously published values illustrating the great potential of this electrochemical sensor. A 7 days silicate time series from the mooring deployment off Chile is also presented.