Development and assessment of an analytical system for the accurate and continual measurement of total dissolved inorganic carbon

An automated coulometric titration system based on that described by Johnson, Sieburth, Williams and Brandstrom (1987, Mar. Chem., 21: 117–133) has been evolved for the accurate and continual measurement of total dissolved inorganic carbon (TCO₂). The instrument achieves an analytical precision (1 SD) of ±0.5–1.0 μmol kg⁻¹ (0.025–0.05%). The accuracy of the system has been examined by a limited comparison with other coulometric-based titrators and with a manometric-based system; agreement was to 1 μmol kg⁻¹. The capability for automatic continual analysis allows surface mapping of TCO₂; a sample rate of 10 analyses h⁻¹ gives a mapping resolution of 1–2 km. Provision for frequent standardization with a liquid substandard has been included in the development. The ability to achieve high-density analyses while maintaining interlaboratory consistency and standardization constitutes a vital contribution to surveys of ocean carbon chemistry (e.g. Joint Global Ocean Flux Study, World Ocean Circulation Experiment).