Development of a reliable microelectrode dissolved oxygen sensor

This article reports the results of a careful experimental and analytical investigation which led to the development of an accurate and reproducible microelectrode dissolved oxygen sensor. Primarily designed for oceanographic applications but also applicable to environmental and water process monitoring, the sensor measures the diffusion controlled current to a bare Pt microdisc electrode for the reduction of oxygen. A successful reconditioning potential waveform is reported which yields a very stable amperometric response over continuous operation, with a maximum deviation of the limiting current under 1.5% over 24 h. An automated calibration method developed to accurately characterise the electrodes is described. Excellent linearity is obtained for all electrodes tested and in each case, the number of apparent electrons for the reduction of oxygen is reported. As an alternative to calibration, an analytical treatment which accounts for temperature and salinity effects is given to calculate the dissolved oxygen concentration directly from the limiting current. While the analytical approach yields a concentration relative error circa 11% for a 50 μm diameter Pt disc, the calibration, has lower errors and yields a detection limit down to 0.9 μM with the same disc. Although this investigation builds on established principles, this article describes, for the first time, the conditions required to obtain accurate and reproducible measurements and provides an estimate of their precision. Preliminary field trials to measure oxygen depth profiles in the ocean have proved very encouraging [R. Prien, R. Pascal, M. Mowlem, G. Denuault, M. Sosna, Development and first results of a new fast response microelectrode DO-sensor, in Oceans 2005—Europe, Vols. 1 and 2, 2005, pp. 744–747].