New developments in instrumentation for ocean environmental engineering are allowing unprecedented levels of trace contaminant measurement in the deep ocean. With funding from the U.S. National Science Foundation (NSF), our engineering design team constructed a new mass spectrometer-based in situ analysis system for work in the deep ocean environment over prolonged deployment periods. Our design goals were a depth capability of up to 4,000 m water depth (400 bars hydrostatic pressure) and autonomous operation for periods of up to six months to a year, depending upon the type of external battery system used or other deployment circumstances, e.g., availability of a power cable or fuel cell power source. We chose a membrane introduction mass spectrometry (MIMS) sampling approach, which allows for dissolved gases and volatile organics introduction into the mass spectrometer vacuum system. The MIMS approach and the hydrophobic, silicon-coated membrane chosen both draw upon our previous experience with this technology in the deep ocean. The membrane has been tested to 400 bars in a series of long-term hydrostatic pressure tests, which extend the 200-bar working depth rating of this membrane by a factor of 2. Long-term deployment capability of the moderately powered, approximately 100 W system, was accomplished by power management of the embedded computer system and custom electronics with Windows-based and custom software now fully-developed and bench tested. The entire system fits within a 6.5-inch outside diameter pressure housing that is approximately five feet long. It consists of a 1 to 200 amu range quadrupole mass spectrometer equipped with Faraday and electron multiplier detectors, compact turbo-molecular and backing diaphragm vacuum pumps, internal rechargeable batteries, and internal waste vacuum chamber. Sample routing past the MIMS is accomplished by computer-controlled solenoid valves. We designed the pressure housings of both 6AL4V and type 2 titanium alloys that are rated to working depths of >4,000 m and are essentially corrosion proof over long-term deployments. We designed and integrated a fail-safe valving system for both rapid response to high-pressure MIMS failure and a pressure-switch circuit and high-pressure solenoid valve to detect and protect against slow leaks of the MIMS. To route sample waters to the MIMS-based instrument, we also designed and built a rugged plastic plenum that couples to the face of the sampler head, the latter of which consists of the MIMS inlet and a full-ocean rated thermister temperature probe with an operational range from −5 to 50°C. These instrumentation innovations will be described in the paper.
Segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer for measurements of a broad range of volatile organic compounds in seawater