Manual collection and processing of seawater samples for dissolved gas analyses are technically challenging, time consuming and costly. Accordingly, in situ analysis techniques present attractive alternatives to conventional gas measurement procedures. To meet the demands of sustained, high-resolution chemical observations of the oceans, the University of South Florida and SRI International developed underwater mass spectrometer systems for quantitative measurements of dissolved gases and volatile organic compounds. This work describes the influence of variable in situ conditions on the performance of a membrane introduction mass spectrometer used for measurements in both the water column and sediment porewater.

Laboratory experiments to simulate the effects of field conditions on the membrane were performed by varying sample flow rate, salinity, hydrostatic pressure, and chemistry. Data indicate that membrane permeability has a strong dependence on hydrostatic pressure, and a weak dependence on salinity. Under slow flow conditions bicarbonates in solution contributed to carbon dioxide instrument response as a result of carbon system equilibration processes in the boundary layer at the membrane interface. In addition, method development was undertaken to enable underwater sediment porewater analyses and quantitative (calibrated) measurements of total dissolved inorganic carbon (DIC). This work establishes the capability of membrane introduction mass spectrometry to measure two compatible variables (DIC and dissolved CO₂) for comprehensive CO₂-system characterizations.

In addition to laboratory studies three types of field observation were obtained in this work. High-resolution vertical profiles of dissolved gases in the Gulf of Mexico were obtained through system calibration and characterization of the influence of hydrostatic pressure on the behavior of polydimethylsiloxane membranes. In the South Atlantic Bight, sediment porewater profiles of dissolved gases were repeatedly obtained over a 54 hr period. Data trends were in agreement with high remineralization rates facilitated by porewater advection. Finally, time-series underwater DIC measurements that were undertaken proved to be in good accord with results obtained using conventional techniques. These measurements constitute the first quantitative observations of dissolved gas ocean profiles, sediment porewater profiles, and DIC measurements by underwater mass spectrometry.