International audienceAn electrochemical method for phosphate determination in seawater was based on the oxidation of molybdenum in order to form molybdates and protons and subsequently, to create the phosphomolybdic complex electrochemically detectable by means of amperometry at a rotating gold disk electrode [J. Jonca et al., Talanta 87 (2011) 161]. To avoid silicate interferences, the method required an appropriate ratio of protons over molybdates equal to 70. Since the ratio of protons over molybdates created during molybdenum oxidation is only 8, the previous method still needed addition of sulfuric acid and thus was not free from addition of liquid reagents. In the present work, this aspect is solved by modification of the electrochemical cell construction. The method is now totally free from addition of any liquid reagents and gives a possibility to determine phosphate by amperometry in the concentrations range found in the open ocean with a detection limit of 0.11 µM. Having in mind the energy savings for future in situ sensor development, amperometry at rotating gold disk electrode was replaced by differential pulse voltammetry at static one. Phosphate can then be determined with a detection limit of 0.19 µM. Both methods are characterized by good reproducibility with an average measurements precision of 5.7% (amperometry) and 3.8% (differential pulse voltammetry). Results also show a good accuracy with an average deviation from theoretical values of phosphate concentration of 3.1% for amperometry and 3.7% for differential pulse voltammetry
Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10(-6) mol L(-1). The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10(-6) cm(2) s(-1), consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10(-6) mol L(-1).
International audienceThis paper describes the electrochemical characterisation of gold and platinum microdevices mass fabricated using silicon technology. Specific attention was paid to allow in situ electrochemical detection of silicate in seawater. Thus, using a silicon nitride (Si 3 N 4) inorganic passivation layer patterned using Inductively Coupled Plasma Chemical Vapor Deposition (ICP-CVD), coupled with a non-aggressive lift-off based process, different electrodes were isolated electrically: one gold or platinum working electrode named " macroelectrode " (2 mm of diameter), four gold or platinum working ultramicroelectrodes (UME) (15 m of diameter), one platinum counter electrode and one silver electrode which can be used as a reference electrode after its chlorination. Their small size and mass fabrication make them very promising for oceanographic applications. As some components of microdevices release silicate and contaminate the solution, after being immersed in seawater, these microdevices were inserted in a specific cell that only puts the electrodes in contact with the seawater solution. Gold has been tested as a possible material for working electrodes but its lack of adherence to the passivation layer in seawater solutions led to non-accurate measurements. On the contrary, passivation layer on platinum electrodes resists to the seawater corrosive medium. The analytical performances of the platinum microdevices has been tested through different silicate calibrations and shows an outstanding accuracy and reproducibility when measurements are performed, especially with the macroelectrodes which showed only 2.8% signal variation after four months of use and a limit of quantification of 0.50 mol L −1 suitable for oceanographic applications
This study shows that electroanalysis may be used in vanillin biotechnological production. As a matter of fact, vanillin and some molecules implicated in the process like eugenol, ferulic acid, and vanillic acid may be oxidized on electrodes made of different materials (gold, platinum, glassy carbon). By a judicious choice of the electrochemical method and the experimental conditions the current intensity is directly proportional to the molecule concentrations in a range suitable for the biotechnological process. So, it is possible to imagine some analytical strategies to control some steps in the vanillin biotechnological production: by sampling in the batch reactor during the process, it is possible to determine out of line the concentration of vanillin, eugenol, ferulic acid, and vanillic acid with a gold rotating disk electrode, and low concentration of vanillin with addition of hydrazine at an amalgamated electrode. Two other possibilities consist in the introduction of electrodes directly in the batch during the process; the first one with a gold rotating disk electrode using linear sweep voltammetry and the second one requires three gold rotating disk electrodes held at different potentials for chronoamperometry. The last proposal is the use of ultramicroelectrodes in the case when stirring is not possible.
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