Solid State Sensor for Simultaneous Measurement of Total Alkalinity and pH of Seawater

A novel design is demonstrated for a solid state, reagent-less sensor capable of rapid and simultaneous measurement of pH and Total Alkalinity (A_T) using ion sensitive field effect transistor (ISFET) technology to provide a simplified means of characterization of the aqueous carbon dioxide system through measurement of two "master variables": pH and A_T. ISFET-based pH sensors that achieve 0.001 precision are widely used in various oceanographic applications. A modified ISFET is demonstrated to perform a nanoliter-scale acid-base titration of A_T in under 40 s. This method of measuring A_T, a Coulometric Diffusion Titration, involves electrolytic generation of titrant, H⁺, through the electrolysis of water on the surface of the chip via a microfabricated electrode eliminating the requirement of external reagents. Characterization has been performed in seawater as well as titrating individual components (i.e., OH^-, HCO₃^-, CO₃^2-, B(OH)₄^-, PO₄^3-) of seawater A_T. The seawater measurements are consistent with the design in reaching the benchmark goal of 0.5% precision in A_T over the range of seawater A_T of ∼2200-2500 μmol kg^-1 which demonstrates great potential for autonomous sensing.