The analysis of dissolved inorganic carbon in liquid using a microfluidic conductivity sensor with membrane separation of CO2

Abstract

Autonomous continuous analysis of oceanic dissolved inorganic carbon (DIC) concentration with depth is of great significance with regard to ocean acidification and climate change. However, miniaturisation of in situ analysis systems is hampered by the size, cost and power requirements of traditional optical instrumentation. Here, we report a low-cost microfluidic alternative based on CO2 separation and conductance measurements that could lead to integrated lab-on-chip systems for ocean float deployment, or for moored or autonomous surface vehicle applications. Conductimetric determination of concentration, in the seawater range of 1000–3000 µmol kg−1, has been achieved using a microfluidic thin-film electrode conductivity cell and a membrane-based gas exchange cell. Sample acidification released CO2 through the membrane, reacting in a NaOH carrier, later drawn through a sub-µL conductivity cell, for impedance versus time measurements. Precision values (relative standard deviations) were ~ 0.2% for peak height measurements at 2000 µmol kg−1. Comparable precision values of ~ 0.25% were obtained using a C4D electrophoresis headstage with similar measurement volume. The required total sample and reagent volumes were ~ 500 µL for the low volume planar membrane gas exchange cell. In contrast, previous conductivity-based DIC analysis systems required total volumes between 5000 and 10,000 µL. Long membrane tubes and macroscopic wire electrodes were avoided by incorporating a planar membrane (PDMS) in the gas exchange cell, and by sputter deposition of Ti/Au electrodes directly onto a thermoplastic (PMMA) manifold. Future performance improvements will address membrane chemical and mechanical stability, further volume reduction, and component integration into a single manifold.